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WO1999009023A1 - Benzothiophene derivates as herbicides - Google Patents

Benzothiophene derivates as herbicides Download PDF

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Publication number
WO1999009023A1
WO1999009023A1 PCT/EP1998/005247 EP9805247W WO9909023A1 WO 1999009023 A1 WO1999009023 A1 WO 1999009023A1 EP 9805247 W EP9805247 W EP 9805247W WO 9909023 A1 WO9909023 A1 WO 9909023A1
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WIPO (PCT)
Prior art keywords
alkyl
haloalkyl
substituted
formula
alkenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1998/005247
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French (fr)
Inventor
Hermann Rempfler
Andrew Edmunds
Alain De Mesmaeker
Karl Seckinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Pharma GmbH Austria
Novartis AG
Original Assignee
Novartis Erfindungen Verwaltungs GmbH
Novartis AG
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Filing date
Publication date
Application filed by Novartis Erfindungen Verwaltungs GmbH, Novartis AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Priority to BR9811314-3A priority Critical patent/BR9811314A/en
Priority to CA002291101A priority patent/CA2291101A1/en
Priority to AU93441/98A priority patent/AU732154B2/en
Priority to EP98946374A priority patent/EP1005467A1/en
Publication of WO1999009023A1 publication Critical patent/WO1999009023A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to novel herbicidally active substituted bicyclic benzoyi derivatives, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth.
  • Isoxazolyl- and pyrazolyl-benzoyi and bicyclic benzoyi derivatives having herbicidal activity are known and are described, for example, in WO 96/26192, WO 96/26206 and WO 97/08164.
  • the present invention therefore relates to compounds of formula I
  • R 2 o and R 2 ⁇ are each independently of the other C C 4 alkyl; or R 20 and R 21 together are -(CH 2 ) n1 -;
  • R 2 is hydrogen or C ⁇ -C 4 alkyl
  • R 3 and R are each independently of the other hydrogen, C C 4 alkyl or halogen; n is 0, 1 or 2; R 5 is C C 4 alkyl, CrC 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C C 4 alkoxy, C 1 -C haloalkoxy, C ⁇ -C 4 alkyl-S(O) n2 , (CrC alkyl)2NS(O) 2 , C C 4 alkyl-S(O) 2 O, halogen, nitro or cyano; n 2 is O, 1 or 2;
  • Q is OH, halogen or a group (Q 2 ),
  • R 6 and R 7 are each independently of the other hydrogen, OH, CrOjalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 4 alkoxycarbonyl, CrC 4 alkyl-S(O) n2 , CrC 4 alkyl-NHS(O) 2 , phenyl or phenyl substituted by C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, CrC alkoxy, C ⁇ -C 4 haloalkoxy, CrC alkylcarbonyl, CrC 4 alkoxycarbonyl, amino, d-C alkylamino, di-C ⁇ -C 4 alkylamino, CrC 4 alkyl-S(O) n2 , C C 4 alkyl-S(O) 2 O, C ⁇ -C 4 haloalkyI-S(O) n2 , C C 4 haloalkyl-S(O) 2 O, CrC
  • W is oxygen, sulfur, -C(R 18 ) 2 - or -N(R 22 )- ; n 6 is 0 or 1 , or when W is -C(R 18 ) 2 - , n 6 may additionally be 2 or 3; each R 18 independently of the other is hydrogen, C C 4 alkyl, C C 4 haloalkyl or C C 4 alkoxy- carbonyl; or R 18 together with one of the adjacent substituents R 7 forms a single bond when n 6 is 1 , and the remaining geminal R 6 and R 7 are other than hydrogen;
  • R 2 is hydrogen, C ⁇ -C 4 alkyl or C ⁇ -C 4 alkoxycarbonyl
  • R 8 is OH, CrC 4 alkoxy, CrC alkylcarbonyloxy, C C alkoxycarbonyloxy, R 23 R 24 N-C(O)O, phenylthio, C C 4 alkylthio, C C 4 alkyl-S(O) 2 O, (C C 4 alkoxy) 2 P(O)O, C 1 -C 4 alkyl(C 1 -C 4 - alkoxy)P(O)O, H(d-C 4 alkoxy)P(O)O or benzoyloxy;
  • R 23 and R 24 are each independently of the other hydrogen or d-C 4 alkyl
  • Y is oxygen, sulfur or -(CH 2 ) n5 -; n 5 is O, 1 , 2, 3 or 4;
  • R 9 is hydrogen, C ⁇ -C 6 alkyl, d-C 4 alkylcarbonyl, d-C 4 alkoxycarbonyl, (C C alkyl)NHCO or (C 1 -C 4 alkyl) 2 NCO;
  • R 10 , R 11 and R 12 are each independently of the others hydrogen, d-C 4 alkyl, C C 4 alkoxy- carbonyl, phenyl or phenyl substituted by C ⁇ -C 4 alkyl, C C 4 haloalkyl, C ⁇ -C 4 alkoxy, C C 4 - haloalkoxy, C ⁇ -C 4 alkylcarbonyl, C C 4 alkoxycarbonyl, amino, d-C alkylamino, di-d-daikyl- amino, C ⁇ -C 4 alkyl-S(O) n2 , C C 4 alkyl-S(O)2 ⁇ , C ⁇ -C 4 haloalkyl-S(O)n , C ⁇ -C 4 haloalkyl-S(O) 2 O, CrC 4 alkyl-S(O) 2 NH, C C 4 alkyl-S(O) 2 N(C ⁇ -C 4 alkyl), halogen, nitro, COOH or
  • R 13 is hydrogen; halogen; C C 4 alkyl; C C alkyl substituted by unsubstituted or R 17 - substituted phenyl; C ⁇ -C 4 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl; C 2 -C 6 alkynyl; C 2 -C 6 alkynyl substituted by unsubstituted or R 17 - substituted phenyl; C 3 -C 6 haloalkenyl; C 3 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 3 -C 6 cycloalkyl substituted by halogen, R 15 or COOR ⁇ 6 ; COOR 16 ; COR 15 ; cyano; nitro; CONH 2 ; (d-C 4 - alkyl)NHCO; (CrC 4
  • R 15 is d-C 4 alkyl, C C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C -C 6 alkynyl, C 3 -C 6 halo- alkynyl, phenyl or R ⁇ 7 -substituted phenyl;
  • R 16 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl
  • R 17 is halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, d-C 4 alkoxy-C ⁇ -C 4 alkyl, C ⁇ -C alkoxy-C 3 -C 6 alkenyl, d-C alkoxy-C 3 -C 6 - alkynyl, cyano, nitro, COOH, C C 4 alkoxycarbonyl, CrC 4 haloalkoxycarbonyl, C C 4 alkyl- S(O) n2 , C 1 -C 4 haloalkyl-S(O) n2 , phenyl-S(O) n 2; phenyl-S(O) n2 substituted on the phenyl ring by halogen, d-C
  • R 14 is d-C 4 alkyl, C ⁇ -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 halo- alkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by halogen, C C 4 alkyl, C C 4 halo- alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl or phenyl substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COOH, d-C al
  • halogen is to be understood as meaning iodine or, preferably, fluorine, chlorine or bromine.
  • alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, cyanoalkyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylaminocarbonyl, dialkyl- aminocarbonyl, (alkyl) 2 NS(O) 2 , alkyl(alkoxy)P(O)O, alkyl substituted by unsubstituted or R 17 - substituted phenyl, alkenyl substituted by unsubstituted or R 17 -substituted phenyl, alkoxy- carbonylalkenyl, alkylS(O) 2 N(alkyl), (alkyl) 2 NCO, (alkyl) 2 NCS ,alkenyl-S(O) n2 substituted by unsub
  • Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
  • alkenyl radicals examples include vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
  • alkynyl radicals examples include ethynyl, propargyl, 1-methyl- propargyl, 3-butynyl, but-2-yn-1 -yl, 2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4- yn-1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
  • Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
  • Suitable haloalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1 -yl and 4,4,4-trichlorobut-2-en-1-yl.
  • alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
  • Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trifluoro-but-2-yn-1 -yl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
  • Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl, but-2-en-1-ylsulfonyl, pentenylsulfonyl or 2-hexenylsulfonyl.
  • Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
  • Alkylamino is, for example, methylamino, ethylamino or an isomer of propyl- or butyl-amino.
  • Dialkylamino is, for example, dimethylamino, diethyiamino or an isomer of dipropyl- or dibutyl-amino.
  • Alkylcarbonyl is especially acetyl or propionyl.
  • Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or tert-butoxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
  • Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy or pentafluoroethoxy.
  • cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or per- halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromo- cyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl, 2- fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2- dich
  • Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
  • Phenyl per se, or as part of a substituent may be unsubstituted or substituted, in which case the substituents may be in the ortho-, meta- or para-position.
  • substituents are, for example, d-C 4 - alkyl, C ⁇ -C alkoxy, halogen or C ⁇ -C haloalkyl.
  • cyanoalkyl alkylcarbonyl, alkoxycarbonylalkenyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy and haloalkoxycarbonyl
  • the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
  • the compounds of formula I wherein Q is a group Q 5 may also be in the form of mixtures of the following isomeric forms l 6 , l and le:
  • the invention includes all those isomeric forms to l 4> Ic, l 6 , l 7 and le and their mixtures to l 4 and Ic, and l 6 , l 7 and le.
  • the invention likewise includes the salts that the compounds of formula I having azide
  • sulfonamide groups are able to form with bases.
  • bases e.g. alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium.
  • Suitable salt formers are described, for example, in WO 97/41112.
  • alkali metal and alkaline earth metal hydrides attention is drawn, for example, to sodium hydride and calcium hydride, and among the carbonates attention is drawn to the carbonates of sodium, potassium, caesium, calcium, barium, magnesium and lithium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-C ⁇ 8 alkylamines, C ⁇ -C hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptyiamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyioctadecylamine
  • the salts of compounds of formula I having basic groups, especially having basic amino groups, for example alkylamino and dialkylamino groups, in the definition of R 6 , R 7 or R 17 are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid
  • sulfuric acid phosphoric acid
  • the compounds of formula I may also be in the form of rotational isomers (atropisomers).
  • Ri is d-C 4 alkyl, d-C 4 haloalkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkyl, d-C 4 alkoxycarbonyl, cyano, cyano-C C 4 alkyl, CHO, C ⁇ -C 4 alkyl-
  • ON CH, C 2 -C 6 alkenyl, d-C 4 alkoxycarbonyl-C 2 -C 6 alkenyl or a group — CH(OR 20 )OR 21 ;
  • W is oxygen, sulfur, -C(R 18 ) 2 - or -N(R 22 )-; each R 18 independently of the other is hydrogen, C ⁇ -C alkyl or C ⁇ -C 4 alkoxycarbonyl; and R 22 is hydrogen, d-C 4 alkyl or C C 4 alkoxycarbonyl.
  • R 8 is OH, C C alkoxy, C ⁇ -C 4 alkylcarbonyloxy, phenylthio or C ⁇ -C 4 alkylthio;
  • R 10 , Rn and R 12 are each independently of the others hydrogen, d-C 4 alkyl or C C alkoxycarbonyl;
  • R 13 is halogen, d-C 4 alkyl, C 3 -C 6 - cycloalkyl, COOR ⁇ 6 , COR 15 or cyano;
  • R is C C 4 alkyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 halo- alkyl
  • R 6 and R 7 are each independently of the other d-C 4 alkyl or
  • R ⁇ to R 5 and n are as defined and X is a leaving group, e.g. halogen, in an inert organic solvent in the presence of a base with a compound of formula IV
  • Zi is NR 10
  • Z 2 is oxygen
  • R 6 , R , R9, R 1 0, W, n 6 and n 5 are as defined for formula I, to form a compound of formula Ic
  • Ri to R 5 and n are as defined for formula I; Q is a group (Q 5 ); and
  • Rn and R 2 are as defined for formula I is carried out analogously to known procedures and comprises either:
  • Ri to R 5 and n are as defined and X is a leaving group, e.g. halogen, with a compound of formula IVa
  • Rn and R ⁇ 2 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula le
  • Ri to R 5 and n are as defined for formula I;
  • Q is a group (Q 6 );
  • R ⁇ 3 i IS hydrogen, d-C 4 alkyl, C ⁇ -C alkyl substituted by unsubstituted or R 17 -substituted phenyl, d-C haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, C 2 -C 6 alkynyl, C 2 -C 6 alkynyl substituted by unsubstituted or R 17 -substituted phenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl substituted by halogen, R 15 or COOR ⁇ 6 ;
  • Ri to R 5 , R i4 and n are as defined, in the presence of a base, carbon disulfide and an alkylating reagent of formula VI wherein R 25 is d-C 4 alkyl, d-C 4 alkyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, d-C 4 alkoxy-C 2 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R 17 - substituted phenyl, C -C 6 alkynyl or C 2 -C 6 alkynyl substituted by unsubstituted or R 17 - substituted phenyl; R ⁇ 7 is as defined for formula I, and Xi is a leaving group, e.g. halogen or sulfonate, into a compound of formula VII
  • Ri to R 5 , R M , R 25 and n are as defined, then cyclising that compound with hydroxyl- amine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If wherein R to R 5 , R 14 and n are as defined, R 13 is R 25 S and R 25 is CrC 4 alkyl, C ⁇ -C 4 alkyl substituted by unsubstituted or R ⁇ -substituted phenyl, d-C 4 alkoxy-C 2 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl, C 2 -C 6 alkynyl or C 2 -C 6 - alkynyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, and then oxidising that compound, for example with meta-chlor
  • Ri, R 3 to R 5 and n are as defined for formula I and R 2 is CH 3 is carried out analogously to known procedures and comprises either:
  • R 5 is as defined for formula I and R 28 is d-C 4 alkyl, with a compound of formula XXV
  • Hal is chlorine, bromine or iodine, to yield a compound of formula XXIII
  • R 1 R 3 to R 5 and n are as defined for formula I and R 2 is CH 3 is carried out analogously to known procedures and comprises reacting a compound of formula XXa
  • R 5 is as defined and R 28 is d-C 4 alkyl, with a compound of formula XXVa
  • Ri to R 5 and n are as defined for formula I and Q is halogen is carried out analogously to known procedures and comprises treating a compound of formula Id
  • Ri to R 5 and n are as defined, with a halogenating agent.
  • the starting materials used are carboxylic acid derivatives of formula III wherein X is a leaving group, e.g. halogen, for example iodine, bromine or especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino or part of
  • an activated ester e.g. (formed from dicyclohexylcarbodiimide
  • N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide and the corresponding carboxylic acid).
  • Those starting materials are reacted in an inert organic solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, and in the presence of a base, for example an alkylamine, e.g. triethylamine, an aromatic amine, e.g. pyridine or 4-dimethylaminopyridine (DMAP), with a dione derivative of formula IV to form isomeric enol ethers of formula Ic.
  • the esterification takes place at temperatures of from 0°C to 110°C.
  • a base for example an alkylamine, e.g. triethylamine, or a carbonate, e.g. potassium carbonate, and a catalytic amount of a cyanide source, for example acetone cyanohydrin or potassium cyanide.
  • an inert solvent for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene
  • a base for example an alkyl
  • the compounds of formula I wherein Q is a group Q 5 can be obtained in a manner analogous to that described, for example, in Reaction Scheme 1 or Tetrahedron 36, 2409 (1976), either
  • the reaction is advantageously carried out in a solvent, for example an amide, e.g. N,N-dimethylformamide (DMF), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), or a nitrile, e.g. acetonitrile.
  • a solvent for example an alcohol, e.g.
  • the carboxylic acids of formula Id can be prepared analogously to known procedures, e.g. in accordance with the methods given in Reaction Schemes 4 and 5 below.
  • DMSO dimethyl sulfoxide
  • ketone e.g. acetone
  • nitrile e.g. acetonitrile
  • a base for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride.
  • the reaction temperatures are generally in the range of from 0°C to 110°C.
  • the subsequent Claisen rearrangement of the allyl ether of formula XXI in Reaction Scheme 4 can be carried out, for example, thermally at temperatures of from 100°C to 300°C, optionally in an inert solvent, for example an aromatic hydrocarbon, e.g. xylene.
  • an inert solvent for example an aromatic hydrocarbon, e.g. xylene.
  • the thermal Claisen rearrangement can be carried out, for example, also without a solvent in a microwave oven.
  • Such Claisen rearrangements are described, for example, in C. Ferri, "Retician der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff..
  • the resulting phenol derivative of formula XXII is then acylated, for example with a thiocarbamoyl halide of formula XXVI, e.g. N,N-dimethyl- thioformyl chloride, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g.
  • a thiocarbamoyl halide of formula XXVI e.g. N,N-dimethyl- thioformyl chloride
  • an aprotic solvent for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sul
  • acylation is advantageously carried out at temperatures of from 0°C to 110°C.
  • a metal hydroxide e.g. sodium hydroxide
  • a mineral acid e.g. hydrochloric acid or sulfuric acid
  • Suitable solvents are, for example, water, ethers, e.g. tetrahydrofuran, halogenated hydrocarbons, e.g. dichloromethane, and aromatic hydrocarbons, e.g. toluene.
  • the resulting benzothiophene derivative of formula Id wherein R 2 is methyl and n is 0 can then be oxidised in accordance with various standard methods.
  • the oxidation is carried out, for example, with hydrogen peroxide in an acidic solvent, for example an organic acid, e.g.
  • acetic acid or with an organic peracid, for example meta- chloroperbenzoic acid (m-CPBA), in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene.
  • m-CPBA meta- chloroperbenzoic acid
  • an inert solvent for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene.
  • the reaction temperatures for the oxidation are generally in the range of from 0°C to 110°C.
  • the electrophilic bromination according to Route b) in Reaction Scheme 4 is carried out, for example, analogously to Chem. Communic. 1972, 214.
  • the bromination of the salicylic acid derivative of formula XX can be effected, for example, in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, and in the presence of a Lewis acid, for example titanium halide, e.g. titanium tetrachloride, at temperatures of from 0°C to 100°C.
  • the coupling product of formula XXII obtained by Route b) can then, for example in a manner analogous to that described under Route a), be acylated, rearranged, hydrolysed and cyclised, and optionally oxidised to form a compound of formula Id.
  • DMSO dimethyl sulfoxide
  • ketone e.g. acetone
  • nitrile e.g. acetonitrile
  • a base for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride, at temperatures of from 0°C to 200°C.
  • the activated carboxylic acid derivatives of formulae III and I in Reaction Schemes 1 and 2 (Route a)) wherein X is a leaving group, for example halogen, e.g. bromine, iodine or especially chlorine, can be prepared according to known standard procedures as described, for example, by C. Ferri in "Restrokeen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff., such as, for example, in accordance with Reaction Scheme 6 below.
  • a halogenating agent for example a thionyl halide, e.g. thionyl chloride or bromide; a phosphorus halide or phosphorus oxyhalide, e.g. phosphorus pentachloride or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl bromide; or an oxalyl halide, e.g.
  • oxalyl chloride or by the use of a reagent for forming activated esters, for example N,N'- dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X.
  • a reagent for forming activated esters for example N,N'- dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X.
  • the compound of formula X is a halogenating agent
  • the group X is, for example, a leaving group, for example halogen, e.g. fluorine, bromine or iodine or especially chlorine
  • Wi is, for example, PCI 2 , SOCI, SOBr or CICOCO.
  • the operation is optionally carried out in an inert organic solvent, for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1 ,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the reaction mixture, preferably at from 40 to 150°C, and in the presence of a catalytic amount of N,N-dimethylformamide.
  • an inert organic solvent for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1 ,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the
  • Ri to R 5 and n are as defined for formula I and R 28 is d-C 4 alkyl, for example via Claisen condensation, or from the compounds of formula III by reaction with a ketocarboxylic acid salt of formula XXVIII
  • R ⁇ 4 is as defined for formula I and M + is an alkali metal ion (see, for example, WO 96/26192, EP-A-0 496 631 ).
  • the salicylic acid derivatives of formula XX (Reaction Scheme 4) are either known (some of them being commercially available, for example when R 5 is amino (4-aminosalicylic acid)) or can readily be prepared by standard procedures, for example starting from 4-aminosalicylic acid via diazotisation, Sandmeyer reaction and aromatic, nucleophilic substitution (see e.g. J. March, "Advanced Organic Chemistry", 4th Edition, John Wiley & Sons, New York, 1992, pages 641 -676) or Heck reaction of the resulting halide.
  • the benzoic acid derivatives of formula XXa (Reaction Scheme 5) are either known or can readily be obtained by bromination of the corresponding benzoic acid derivatives (see Reaction Scheme 4, Route b)).
  • reagents of formulae VI, VIII, X, XXV, XXVa, XXVb and XXVI used in Reaction Schemes 3 to 6 are either known or can be prepared analogously to disclosed procedures.
  • a large number of known standard procedures are available, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. EP-A-0 796 856).
  • the end products of formula I can in conventional manner be isolated by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluant.
  • solvents in which they are not readily soluble such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons
  • the sequence in which it is advantageous to carry out certain reactions in order to avoid possible secondary reactions will also be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers.
  • the isomers can be separated according to methods known per se.
  • the compounds of formula I may be used in 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.
  • adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • surfactants conventionally employed in formulation technology, which are described in, inter alia, "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 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, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I can be used successfully either in the form of a mixture of the isomeric forms li to l and Ic (Q is a group Qi to Q 4 and R 8 is OH) or l 6 , 17 and le (Q is a group Q 5 ) or in the form of pure isomeric forms to l or Ic, or l 6 , I7 or le, generally on plants or the locus thereof, at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • the concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques.
  • the weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus
  • Echinochloa, Scirpus Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottbo
  • reaction mixture is poured into an ice-water mixture and extracted by shaking with ethyl acetate.
  • the ethyl acetate phase is washed with water, then with brine, dried over sodium sulfate and concentrated by evaporation.
  • the residue is chromatographed on silica gel (eluant: ethyl acetate/hexane 1/3), yielding 114.5 g (85 % of theory) of the desired product in the form of an oil.
  • Example P6 4-Chloro-2-methyl-1 ,1 -dioxo-2.3-dihvdro-benzofblthiophene-7-carboxylic acid
  • Example P7 4-Chloro-2-methyl-1.1 -dioxo-2.3-dihvdro-benzorblthiophene-7-carboxylic acid chloride
  • _ ⁇ ⁇ _ C o ⁇ ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox
  • CD S o 3 O Q X - ⁇ Z 2

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Abstract

Compounds of formula (I) wherein R1 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxycarbonyl, cyano, cyano-C1-C4alkyl, hydroxy-C1-C4alkyl, amino-C1-C4alkyl, CHO, C1-C4alkyl-ON=CH, C2-C6alkenyl, C1-C4alkoxycarbonyl-C2-C6alkenyl or a group -CH(OR20)OR21; R20 and R21 are each independently of the other C1-C4alkyl; or R20 and R21 together are -(CH2)n1-; n1 is 2, 3 or 4; R2 is hydrogen or C1-C4alkyl; R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or halogen; n is 0, 1 or 2; R5 is C1-C4alkyl, C1-C4haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4alkoxy, C1-C4haloalkoxy,C1-C4alkyl-S(O)n2, (C1-C4alkyl)2NS(O)2, C1-C4alkyl-S(O)2O, halogen, nitro or cyano; n2 is 0, 1 or 2; Q is OH, halogen or a group (Q1), (Q2), (Q3), (Q4), (Q5), or (Q6); and R6 to R14, W, Y and n6 are as defined in claim 1, and agrochemically acceptable salts and stereoisomers of those compounds of formula (I) have good pre- and post-emergence selective herbicidal properties. The preparation of the compounds and their use as herbicidal active ingredients are described.

Description

BENZOTHIOPHENE DERIVATES AS HERBICIDES
The present invention relates to novel herbicidally active substituted bicyclic benzoyi derivatives, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth.
Isoxazolyl- and pyrazolyl-benzoyi and bicyclic benzoyi derivatives having herbicidal activity are known and are described, for example, in WO 96/26192, WO 96/26206 and WO 97/08164.
New substituted bicyclic benzoyi derivatives having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I
Figure imgf000003_0001
wherein
Ri is d-C4alkyl, Cι-C4haloalkyl, CrC alkoxy-Cι-C alkyl, Cι-C4alkoxycarbonyl, cyano, cyano- C C4alkyl, hydroxy-Cι-C4alkyl, amino-C C4alkyl, CHO, C C4alkyl-ON=CH, C2-C6alkenyl,
Cι-C4alkoxycarbonyl-C2-C6alkenyl or a group — CH(OR20)OR21 ;
R2o and R2ι are each independently of the other C C4alkyl; or R20 and R21 together are -(CH2)n1-;
Figure imgf000003_0002
R2 is hydrogen or Cι-C4alkyl;
R3 and R are each independently of the other hydrogen, C C4alkyl or halogen; n is 0, 1 or 2; R5 is C C4alkyl, CrC4haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C C4alkoxy, C1-C haloalkoxy, Cι-C4alkyl-S(O)n2, (CrC alkyl)2NS(O)2, C C4alkyl-S(O)2O, halogen, nitro or cyano; n2 is O, 1 or 2;
Q is OH, halogen or a group (Q2),
Figure imgf000004_0001
Figure imgf000004_0002
R6 and R7 are each independently of the other hydrogen, OH, CrOjalkyl, C2-C6alkenyl, C2-C6alkynyl, d-C4alkoxycarbonyl, CrC4alkyl-S(O)n2, CrC4alkyl-NHS(O)2, phenyl or phenyl substituted by Cι-C4alkyl, Cι-C4haloalkyl, CrC alkoxy, Cι-C4haloalkoxy, CrC alkylcarbonyl, CrC4alkoxycarbonyl, amino, d-C alkylamino, di-Cι-C4alkylamino, CrC4alkyl-S(O)n2, C C4alkyl-S(O)2O, Cι-C4haloalkyI-S(O)n2, C C4haloalkyl-S(O)2O, CrC4alkyl-S(O)2NH, C C4alkyl-S(O)2N(C1-C4alkyl)I halogen, nitro, COOH or cyano; or R6 and R7 are each independently of the other C C4haloalkyl, -NH-CrC4alkyl, -N(CrC4alkyl)2, Cι-C6alkoxy, cyano, nitro or halogen; or adjacent R6 and R7 together are -(CH2)n3-; n3 is 2, 3, 4, 5 or 6;
W is oxygen, sulfur, -C(R18)2- or -N(R22)- ; n6 is 0 or 1 , or when W is -C(R18)2- , n6 may additionally be 2 or 3; each R18 independently of the other is hydrogen, C C4alkyl, C C4haloalkyl or C C4alkoxy- carbonyl; or R18 together with one of the adjacent substituents R7 forms a single bond when n6 is 1 , and the remaining geminal R6 and R7 are other than hydrogen;
R2 is hydrogen, Cι-C4alkyl or Cι-C4alkoxycarbonyl;
R8 is OH, CrC4alkoxy, CrC alkylcarbonyloxy, C C alkoxycarbonyloxy, R23R24N-C(O)O, phenylthio, C C4alkylthio, C C4alkyl-S(O)2O, (C C4alkoxy)2P(O)O, C1-C4alkyl(C1-C4- alkoxy)P(O)O, H(d-C4alkoxy)P(O)O or benzoyloxy;
R23 and R24 are each independently of the other hydrogen or d-C4alkyl;
Y is oxygen, sulfur or -(CH2)n5-; n5 is O, 1 , 2, 3 or 4;
R9 is hydrogen, Cι-C6alkyl, d-C4alkylcarbonyl, d-C4alkoxycarbonyl, (C C alkyl)NHCO or (C1-C4alkyl)2NCO;
R10, R11 and R12 are each independently of the others hydrogen, d-C4alkyl, C C4alkoxy- carbonyl, phenyl or phenyl substituted by Cι-C4alkyl, C C4haloalkyl, Cι-C4alkoxy, C C4- haloalkoxy, Cι-C4alkylcarbonyl, C C4alkoxycarbonyl, amino, d-C alkylamino, di-d-daikyl- amino, Cι-C4alkyl-S(O)n2, C C4alkyl-S(O)2θ, Cι-C4haloalkyl-S(O)n , Cι-C4haloalkyl-S(O)2O, CrC4alkyl-S(O)2NH, C C4alkyl-S(O)2N(Cι-C4alkyl), halogen, nitro, COOH or cyano;
R13 is hydrogen; halogen; C C4alkyl; C C alkyl substituted by unsubstituted or R17- substituted phenyl; Cι-C4haloalkyl; C2-C6alkenyl; C2-C6alkenyl substituted by unsubstituted or R17-substituted phenyl; C2-C6alkynyl; C2-C6alkynyl substituted by unsubstituted or R17- substituted phenyl; C3-C6haloalkenyl; C3-C6haloalkynyl; C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, R15 or COORι6; COOR16; COR15; cyano; nitro; CONH2; (d-C4- alkyl)NHCO; (CrC4alkyl)2NCO; (d-C4haloalkyl)NHCO; (C C4haloalkyl)2NCO; C C4alkyl- S(O)n2; Cι-C alkyl-S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl; C1-C4- alkoxy-C2-C6alkyl-S(O)n2; C2-C6alkenyl-S(O)n2; C2-C6alkenyl-S(O)n2 substituted by unsubstituted or R17-substituted phenyl; C2-C6alkynyl-S(O)n2; or C2-C6alkynyl-S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl;
R15 is d-C4alkyl, C C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C -C6alkynyl, C3-C6halo- alkynyl, phenyl or Rι7-substituted phenyl;
R16 is hydrogen, Cι-C4alkyl or d-C4haloalkyl;
R17 is halogen, d-C4alkyl, d-C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, d-C4alkoxy-Cι-C4alkyl, Cι-C alkoxy-C3-C6alkenyl, d-C alkoxy-C3-C6- alkynyl, cyano, nitro, COOH, C C4alkoxycarbonyl, CrC4haloalkoxycarbonyl, C C4alkyl- S(O)n2, C1-C4haloalkyl-S(O)n2, phenyl-S(O)n2; phenyl-S(O)n2 substituted on the phenyl ring by halogen, d-C4alkyl, d-C4haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, d-C4- alkoxycarbonyl, Cι-C4alkyl-S(O)n2, Cι-C4haloalkyl-S(O)n2, Cι-C alkylcarbonyl, di-d-C4alkyl- amino, C C4alkoxy, d-C4haloalkoxy, d-C4alkyl-S(O)2O or C C4haloalkyl-S(O)2O; C C4- alkylcarbonyl, di-d-C4alkylamino, C C alkyl-S(O)2NH, d-C4alkyl-S(O)2N(Cι-C4alkyl), Cι-C4haloalkyl-S(O)2NH, d-C4haloalkyl-S(O)2N(d-C4alkyl), NH2S(O)2) (C C4alkyl)NHS(O)2, (d-C4alkyl)2NS(O)2, CONH2, (C C4alkyl)NHCO, (C C4alkyl)2NCO, NH2CS, (d-C4alkyl)NHCS, (Cι-C4alkyl)2NCS, CrC4alkoxy, d-d aloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC4alkyl-S(O)2O, CrC4haloalkyl-S(O)2O, phenyl-S(O)2O or phenyl- S(O)2O substituted on the phenyl ring by halogen, d-C alkyl, Cι-C4haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, C C4alkoxycarbonyl, d-C alkyl-S(O)n2, C C4haloalkyl- S(O)n2, Cι-C4alkylcarbonyl, di-Cι-C alkylamino, Cι-C4alkoxy, d-C4haloalkoxy, C C4alkyl- S(O)2O or C C4haloalkyl-S(O)2O; and
R14 is d-C4alkyl, Cι-C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6halo- alkynyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by halogen, C C4alkyl, C C4halo- alkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, phenyl or phenyl substituted by halogen, d-C4alkyl, d-C4haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, d-C alkoxycarbonyl, CrC4alkyl-S(O)n2, CrC4haloalkyl-S(O)n2, C C alkylcarbonyl, di-C C4alkylamino, d-C alkoxy, d-C4haloalkoxy, C C4alkyl-S(O)2O or d-C4haloalkyl- S(O)2O, and the agrochemically acceptable salts and stereoisomers of those compounds of formula I.
In the above definitions, halogen is to be understood as meaning iodine or, preferably, fluorine, chlorine or bromine.
The alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, cyanoalkyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylaminocarbonyl, dialkyl- aminocarbonyl, (alkyl)2NS(O)2, alkyl(alkoxy)P(O)O, alkyl substituted by unsubstituted or R17- substituted phenyl, alkenyl substituted by unsubstituted or R17-substituted phenyl, alkoxy- carbonylalkenyl, alkylS(O)2N(alkyl), (alkyl)2NCO, (alkyl)2NCS ,alkenyl-S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl, alkoxyalkenyl, alkenyloxy and alkynyloxy.
Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
Examples of alkenyl radicals that may be mentioned are vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
Examples of alkynyl radicals that may be mentioned are ethynyl, propargyl, 1-methyl- propargyl, 3-butynyl, but-2-yn-1 -yl, 2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4- yn-1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
Suitable haloalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1 -yl and 4,4,4-trichlorobut-2-en-1-yl. Of the alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trifluoro-but-2-yn-1 -yl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl, but-2-en-1-ylsulfonyl, pentenylsulfonyl or 2-hexenylsulfonyl.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
Alkylamino is, for example, methylamino, ethylamino or an isomer of propyl- or butyl-amino.
Dialkylamino is, for example, dimethylamino, diethyiamino or an isomer of dipropyl- or dibutyl-amino.
Alkylcarbonyl is especially acetyl or propionyl.
Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or tert-butoxy.
Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy or pentafluoroethoxy.
The cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or per- halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromo- cyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl, 2- fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2- dichloro-3,3-difluorocyclobutyl, fluorocyclopentyl, difluorocyclopentyl, chlorocyclopentyl, perfluorocyclopentyl, chlorocyclohexyl and pentachlorocyclohexyl.
Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
Phenyl per se, or as part of a substituent, such as, for example, phenylthio or benzoyloxy, may be unsubstituted or substituted, in which case the substituents may be in the ortho-, meta- or para-position. Unless specifically indicated, substituents are, for example, d-C4- alkyl, Cι-C alkoxy, halogen or Cι-C haloalkyl.
Corresponding meanings may also be given to the substituents in combined definitions, such as, for example, alkyl-S(O)-, alkyl-ON=CH-, (alkyl)2NCO-, alkenyl-SO-, alkynyl-S(O)n2-, alkylcarbonyloxy-, haloalkoxycarbonyl-, haloalkyl-S(O)2O-, haloalkyl-SO-, (alkyl)2NS(O)2-, alkyl-S(O)2O-, alkyl substituted by unsubstituted or R17-substituted phenyl, alkenyl substituted by unsubstituted or R17-substituted phenyl, alkyl-S(O)2NH-, haloalkyl-S(O)2NH-, alkylNHS(O)2-, alkylNHCO-, haloalkylNHCO-, (alkyl)2NCS-, H(alkoxy)P(O)O-, alkyl(alkoxy)P(O)O-, (alkoxy)2P(O)O-, alkoxycarbonyl-alkenyl, alkyl-S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl, alkoxy-alkyl-S(O)n2- and alkynyl-S(O)n2-.
In the definitions of cyanoalkyl, alkylcarbonyl, alkoxycarbonylalkenyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy and haloalkoxycarbonyl, the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
The compounds of formula I wherein Q is a group Qi to Q4 and R8 is OH can be in the form of mixtures of the following isomeric forms to l4 and Ic:
Figure imgf000010_0001
In the above isomeric compounds of formulae to l and Ic: when Zi = C(R6)R7, Z2 = (W)n6, Z3 = C(R6)R7 and n4 = 0, the right-hand portion of the isomeric compounds represents the group Q^ when Zi = CH, Z2 = O, S or -(CH2)n5-, Z3 = CH and n = 2, the right-hand portion of the isomeric compounds represents the group Q2; when ZT = CH2, Z2 = CHNHRg, Z3 = CH2 and n4 = 0, the right-hand portion of the isomeric compounds represents the group Q3; or when Zi = NR10, Z2 = O, Z3 = C(R6)R7 and n = 0, the right-hand portion of the isomeric compounds represents the group Q4.
The compounds of formula I wherein Q is a group Q5 may also be in the form of mixtures of the following isomeric forms l6, l and le:
Figure imgf000011_0001
^ /;
Figure imgf000011_0002
le
The invention includes all those isomeric forms to l4> Ic, l6, l7 and le and their mixtures to l4 and Ic, and l6, l7 and le.
The invention likewise includes the salts that the compounds of formula I having azide
hydrogen, for example the compounds of formulae l3 and l6 (l3)
Figure imgf000011_0003
and (I6), and the derivatives having carboxylic acid and
Figure imgf000011_0004
sulfonamide groups (e.g. carboxy-substituted phenyl, alkyl-S(O)2NH and haloalkyl-S(O)2NH groups) are able to form with bases. Those salts are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium. Suitable salt formers are described, for example, in WO 97/41112.
Among the alkali metal and alkaline earth metal hydrides attention is drawn, for example, to sodium hydride and calcium hydride, and among the carbonates attention is drawn to the carbonates of sodium, potassium, caesium, calcium, barium, magnesium and lithium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-Cι8alkylamines, Cι-C hydroxyalkylamines and C2-C4- alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptyiamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyioctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanol- amine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The salts of compounds of formula I having basic groups, especially having basic amino groups, for example alkylamino and dialkylamino groups, in the definition of R6, R7 or R17 are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
The possibility of the presence of at least one asymmetrical carbon atom in the compounds of formula I, for example in the substituent R^ where Ri is a branched alkyl, alkenyl, halo- alkyl or alkoxyalkyl group, or where Ri and R2 and/or R3 and R4) and R6 and R7 are different from one another, means that the compounds may occur in the form of optically active single isomers or in the form of racemic mixtures.
Because rotation between the benzoyi and the Qi to Q6 ring systems is hindered, the compounds of formula I may also be in the form of rotational isomers (atropisomers).
In the present invention, "compounds of formula I" is to be understood as including both the pure optical antipodes and the racemates or diastereoisomers and atropisomers.
When an aliphatic C=C or C=N-O double bond (syn/anti) is present, geometric isomerism may occur. The present invention relates to those isomers also.
Preference is given to compounds of formula I wherein Ri is d-C4alkyl, d-C4haloalkyl, Cι-C4alkoxy-Cι-C4alkyl, d-C4alkoxycarbonyl, cyano, cyano-C C4alkyl, CHO, Cι-C4alkyl-
ON=CH, C2-C6alkenyl, d-C4alkoxycarbonyl-C2-C6alkenyl or a group — CH(OR20)OR21 ;
W is oxygen, sulfur, -C(R18)2- or -N(R22)-; each R18 independently of the other is hydrogen, Cι-C alkyl or Cι-C4alkoxycarbonyl; and R22 is hydrogen, d-C4alkyl or C C4alkoxycarbonyl.
Also preferred are compounds of formula I wherein Q is a group
Figure imgf000013_0001
(Q6); Re and R7are each
Figure imgf000013_0002
independently of the other C C4alkyl or d-C4alkyl-S(O)n2; n2 is 0; R8 is OH, C C alkoxy, Cι-C4alkylcarbonyloxy, phenylthio or Cι-C4alkylthio; R10, Rn and R12 are each independently of the others hydrogen, d-C4alkyl or C C alkoxycarbonyl; R13 is halogen, d-C4alkyl, C3-C6- cycloalkyl, COORι6, COR15 or cyano; R is C C4alkyl, C3-C6alkynyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by halogen, d-C4alkyl, d-C4haloalkyl, C3-C6alkenyl, C3-C6halo- alkenyl, C3-C6alkynyl, C3-C6haloalkynyl or phenyl; R15 is d-C4alkyl, d-C4haloalkyl, C3-C6- alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl or phenyl; and R16 and Y are as defined for formula I.
Also preferred are compounds of formula I wherein Q is a group (Qi) or
Figure imgf000014_0001
(Q3); R6 and R7 are each independently of the other d-C4alkyl or
Figure imgf000014_0002
Cι-C alkyl-S(O)n2; n2 is 0; R8 is OH, C C4alkoxy, d-C4alkylcarbonyloxy, phenylthio or d-C4alkylthio; w is oxygen or -C(Rι8)2-; Rιs is hydrogen; n6 is 1 ; and R9 is (d-C4alkyl)- NHCO or (d-C4alkyl)2NCO.
Preference is given also to compounds of formula I wherein n is 1 or 2.
The process according to the invention for the preparation of compounds of formula I
Figure imgf000014_0003
wherein Ri to R5 and n are as defined for formula I; Q is a group (QΛ
Figure imgf000014_0004
(Q4); R8 is OH; and R6,
Figure imgf000015_0001
7, R9, R10, W, n6 and Y are as defined for formula I is carried out analogously to known procedures and comprises either
a) reacting a compound of formula III
Figure imgf000015_0002
wherein R^ to R5 and n are as defined and X is a leaving group, e.g. halogen, in an inert organic solvent in the presence of a base with a compound of formula IV
Figure imgf000015_0003
wherein
Zi is C(R6)R7, Z2 is (W)n6) Z3 is C(R6)R and n4 is 0 (= group Q,);
Zj is CH, Z2 is oxygen, sulfur or -(CH2)n5- (=Y), Z3 is CH and n4 is 2 (= group Q2);
Zi is CH2, Z2 is CHNHRg, Z3 is CH2 and n4 is 0 (= group Q3); or
Zi is NR10, Z2 is oxygen, Z3 is C(R6)R7 and n is 0 (= group Q4), and R6, R , R9, R10, W, n6 and n5 are as defined for formula I, to form a compound of formula Ic
Figure imgf000015_0004
and then isomerising that compound, for example in the presence of a base and a catalytic amount of a cyanide source; or
b) reacting a compound of formula Id
Figure imgf000016_0001
wherein Ri to R5 and n are as defined, with a compound of formula IV
Figure imgf000016_0002
wherein Z1 ( Z , Z3 and n4 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula Ic
Figure imgf000016_0003
and then isomerising that compound, for example as described under Route a).
The process according to the invention for the preparation of compounds of formula I
Figure imgf000016_0004
wherein Ri to R5 and n are as defined for formula I; Q is a group (Q5); and
Figure imgf000017_0001
Rn and R 2 are as defined for formula I is carried out analogously to known procedures and comprises either:
a) reacting a compound of formula III
Figure imgf000017_0002
wherein Ri to R5 and n are as defined and X is a leaving group, e.g. halogen, with a compound of formula IVa
Figure imgf000017_0003
wherein Rn and Rι2 are as defined, in an inert organic solvent in the presence of a base to form a compound of formula le
Figure imgf000017_0004
and then isomerising that compound, for example in the presence of a base and a catalytic amount of a cyanide source; or
b) reacting a compound of formula Id
Figure imgf000018_0001
wherein Ri to R5 and n are as defined, with a compound of formula IVa
Figure imgf000018_0002
wherein Rn and Rι2 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula le
Figure imgf000018_0003
and then isomerising that compound as described under Route a).
The process according to the invention for the preparation of compounds of formula
Figure imgf000018_0004
wherein Ri to R5 and n are as defined for formula I; Q is a group (Q6); Rι3 i IS
Figure imgf000018_0005
hydrogen, d-C4alkyl, Cι-C alkyl substituted by unsubstituted or R17-substituted phenyl, d-C haloalkyl, C2-C6alkenyl, C2-C6alkenyl substituted by unsubstituted or Rι7-substituted phenyl, C2-C6alkynyl, C2-C6alkynyl substituted by unsubstituted or R17-substituted phenyl, C3-C6haloalkenyl, C3-C6haloalkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl substituted by halogen, R15 or COORι6; C C alkyl-S(O)n2, Cι-C4alkyl-S(O)n2 substituted by unsubstituted or R17- substituted phenyl, Cι-C4alkoxy-C2-C6alkyl-S(O)n2, C2-C6alkenyl-S(O)n2, C2-C6alkenyl-S(O)n2 substituted by unsubstituted or Ri7-substituted phenyl, C2-C6alkynyl-S(O)n2 or C2-C6alkynyl- S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl; and R14 to Rι7 and n2 are as defined for formula I, is carried out analogously to known procedures and comprises either:
a) converting a compound of formula V
Figure imgf000019_0001
wherein Ri to R5, Ri4 and n are as defined, in the presence of a base, carbon disulfide and an alkylating reagent of formula VI
Figure imgf000019_0002
wherein R25 is d-C4alkyl, d-C4alkyl substituted by unsubstituted or Rι7-substituted phenyl, d-C4alkoxy-C2-C6alkyl, C2-C6alkenyl, C2-C6alkenyl substituted by unsubstituted or R17- substituted phenyl, C -C6alkynyl or C2-C6alkynyl substituted by unsubstituted or R17- substituted phenyl; Rι7 is as defined for formula I, and Xi is a leaving group, e.g. halogen or sulfonate, into a compound of formula VII
Figure imgf000019_0003
wherein Ri to R5, RM, R25 and n are as defined, then cyclising that compound with hydroxyl- amine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If
Figure imgf000020_0001
wherein R to R5, R14 and n are as defined, R13 is R25S and R25 is CrC4alkyl, Cι-C4alkyl substituted by unsubstituted or R^-substituted phenyl, d-C4alkoxy-C2-C6alkyl, C2-C6alkenyl, C2-C6alkenyl substituted by unsubstituted or R17-substituted phenyl, C2-C6alkynyl or C2-C6- alkynyl substituted by unsubstituted or Rι7-substituted phenyl, and then oxidising that compound, for example with meta-chloroperbenzoic acid (m-CPBA); or
b) converting a compound of formula V
Figure imgf000020_0002
wherein Ri to R5, R 4 and n are as defined, with an orthoacid amide of formula VIII
R26°;c-N(R2 277) >2 (VIII), R260 R13 wherein Rι3 is hydrogen, d-C4alkyl, d-C4alkyl substituted by unsubstituted or R17- substituted phenyl, d-C4haloalkyl, C2-C6alkenyl, C2-C6alkenyl substituted by unsubstituted or Ri7-substituted phenyl, C2-C6alkynyl, C2-C6alkynyl substituted by unsubstituted or Rι7- substituted phenyl, C3-C6haloalkenyl, C3-C6haloalkynyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by halogen, Rι5 or COORι6; R15 to R17 are as defined for formula I; and R26 and R27 are each independently of the other Cι-C4alkyl, into a compound of formula IX
Figure imgf000020_0003
wherein Ri to R5, R13, Rι4, n and R 7 are as defined, and then cyclising that compound in the presence of hydroxylamine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If
Figure imgf000021_0001
The process according to the invention for the preparation of compounds of formula Id
Figure imgf000021_0002
wherein Ri, R3 to R5 and n are as defined for formula I and R2 is CH3 is carried out analogously to known procedures and comprises either:
a) etherifying a compound of formula XX
Figure imgf000021_0003
wherein R5 is as defined for formula I and R28 is d-C4alkyl, with a compound of formula XXV
R, R, I 1
C=C— CH,— Hal (XXV),
wherein Ri, R3 and R are as defined for formula I and Hal is halogen, to form a compound of formula XXI
Figure imgf000022_0001
wherein R , R3 to R5 and R28 are as defined, subjecting that compound to a Claisen rearrangement and then acylating the resulting compound of formula XXII
Figure imgf000022_0002
with a compound of formula XXVI
S
II (XXVI),
Hal-C-N(C C4alkyl)2
wherein Hal is chlorine, bromine or iodine, to yield a compound of formula XXIII
(XXIII),
Figure imgf000022_0003
which is subjected to a rearrangement and yields a compound of formula XXIV
Figure imgf000022_0004
then hydrolysing and cyclising that compound to form a compound of formula Id
Figure imgf000023_0001
wherein Ri and R3 to R5 are as defined, R2 is CH3 and n is 0, and then oxidising that compound (n is 1 or 2); or
b) first brominating a compound of formula XX
Figure imgf000023_0002
wherein R5 and R28 are as defined, to yield a compound of formula XXb
Figure imgf000023_0003
subjecting that compound to a coupling reaction in the presence of a catalyst and an organometal reagent of formula XXVb
1 3
CH2=C-C-Sn(R29)3 (XXVb), R„
wherein R1 f R3 and R are as defined and R29 is d-C4alkyl, to yield a compound of formula XXII
Figure imgf000023_0004
wherein Ri, R3 to R5 and R28 are as defined, and reacting that compound further analogously to the method described under Route a) to form a compound of formula Id. The process according to the invention for the preparation of compounds of formula Id
Figure imgf000024_0001
wherein R1 ( R3 to R5 and n are as defined for formula I and R2 is CH3 is carried out analogously to known procedures and comprises reacting a compound of formula XXa
Figure imgf000024_0002
wherein R5 is as defined and R28 is d-C4alkyl, with a compound of formula XXVa
R, R.. I 1
C=C— CH,— SH (XXVa),
wherein R1 ( R3 and R4 are as defined, to yield a compound of formula XXIa
Figure imgf000024_0003
subjecting that compound to a Claisen rearrangment to yield a compound of formula XXIIa
(XXIIa),
Figure imgf000024_0004
which is then hydrolysed and cyclised to form a compound of formula Id
Figure imgf000025_0001
wherein Ri and R3 to R5 are as defined, R2 is CH3 and n is 0, and then oxidising that compound (n is 1 or 2).
The process according to the invention for the preparation of compounds of formula I
Figure imgf000025_0002
wherein Ri to R5 and n are as defined for formula I and Q is halogen is carried out analogously to known procedures and comprises treating a compound of formula Id
Figure imgf000025_0003
wherein Ri to R5 and n are as defined, with a halogenating agent.
The preparation of the compounds of formula I is illustrated in more detail in the following Reaction Schemes 1 to 6. Reaction Scheme 1 Route a):
Figure imgf000026_0001
Route b):
base e.g. (C2H5)3N, coupling reagent e.g.
Figure imgf000026_0002
Figure imgf000026_0003
solvent e.g. CH3CN, 0-110°C
Figure imgf000026_0004
In Reaction Scheme 1 when Z, = C(R6)R7, Z2 = (W)n6, Z3 = C(R6)R7 and n4 = 0, the right-hand portion of the compounds of formula I represents the group Qi; when Zi = CH, Z2 = O, S or -(CH2)n5-, Z3 = CH and n4 = 2, the right-hand portion of the compounds of formula I represents the group Q2; when Zi = CH2, Z2 = CHNHRg, Z3 = CH2 and n4 = 0, the right-hand portion of the compounds of formula I represents the group Q3; or when Zi = NRι0, Z2 = O, Z3 = C(R6)R7 and n4 = 0, the right-hand portion of the compounds of formula I represents the group Q .
Reaction Scheme 2 Route a):
Figure imgf000027_0001
Figure imgf000027_0002
le I (Q=Q5)
base e.g. (C,H5)3N, coupling reagent e.g.
Figure imgf000028_0001
Figure imgf000028_0002
solvent, e.g. CH3CN, 0-1 10°C
Figure imgf000028_0003
Reaction Scheme 3
Route a)
Figure imgf000029_0001
NH.OH • HCl, base e.g. [O] e.g. m-CPBA
NaOAc/C2H5OH
Figure imgf000029_0002
lf (R13=R25S-)
Figure imgf000029_0003
lf (R13=R25SO- or R25S02-)
Route b):
Figure imgf000029_0004
V
IX
Figure imgf000029_0005
For the preparation of compounds of formula I wherein Q is a group Qi to Q and R8 is OH, according to Reaction Scheme 1 , Route a), the starting materials used are carboxylic acid derivatives of formula III wherein X is a leaving group, e.g. halogen, for example iodine, bromine or especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino or part of
an activated ester, e.g. (formed from dicyclohexylcarbodiimide
Figure imgf000030_0001
(DCC) and the corresponding carboxylic acid) or 2 s ~~ i '3 3'2 (formed from
N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid). Those starting materials are reacted in an inert organic solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, and in the presence of a base, for example an alkylamine, e.g. triethylamine, an aromatic amine, e.g. pyridine or 4-dimethylaminopyridine (DMAP), with a dione derivative of formula IV to form isomeric enol ethers of formula Ic. The esterification takes place at temperatures of from 0°C to 110°C.
The isomerisation of the ester derivatives of formula Ic to form the dione derivatives of formula I (R8 = OH) can be carried out, for example, analogously to EP-A-0 369 803 in the presence of a base, for example an alkylamine, e.g. triethylamine, or a carbonate, e.g. potassium carbonate, and a catalytic amount of a cyanide source, for example acetone cyanohydrin or potassium cyanide.
According to Reaction Scheme 1 , Route b), the desired diones of formula I (R8 = OH) can be obtained, for example, analogously to Chem. Lett. 1975, 1045 by esterification of the carboxylic acids of formula Id with the dione derivatives of formula IV in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, in the presence of a base, for example an alkylamine, e.g. triethylamine, and a coupling agent, for example 2-chloro-1 -methyl-pyridinium iodide. The esterification is carried out, depending upon the solvent used, at temperatures of from 0°C to 1 10°C and yields first, as described under Route a), the isomeric ester of formula Ic, which can be isomerised as described under Route a), for example in the presence of a base and a catalytic amount of a cyanide source, to form the desired dione derivative of formula I (R8 = OH). According to Reaction Scheme 2, the compounds of formula I wherein Q is a group Q5 can be obtained in a manner analogous to that described, for example, in Reaction Scheme 1 or Tetrahedron 36, 2409 (1976), either
a) by esterification of a carboxylic acid derivative of formula III with the hydroxypyrazole derivative of formula IVa in an inert organic solvent and in the presence of a base, or b) by esterification of the carboxylic acid of formula Id with the hydroxypyrazole derivative of formula IVa in an inert solvent in the presence of a base and a coupling agent, and subsequent isomerisation of the intermediately formed ester of formula le, for example with the aid of a base and a catalytic amount of cyanide source.
The preparation of the compounds of formula I wherein Q is the group Q6 can be carried out in accordance with Reaction Scheme 3 advantageously either
via Route a) by reacting the β-diketone derivative of formula V, e.g. analogously to Synthesis 1991 , 301 ; ibid. 1988, 793; or Tetrahedron 32, 3055 (1976), with carbon disulfide in the presence of a base, for example a carbonate, e.g. potassium carbonate, a metal hydride, e.g. sodium hydride, or potassium fluoride on aluminium, and an alkylating reagent of formula VI wherein XT is a leaving group, e.g. halogen, for example iodine, bromine or
especially chlorine, R25OSO2O-, CH3SO2O- or ■ The reaction is
Figure imgf000031_0001
advantageously carried out in a solvent, for example an amide, e.g. N,N-dimethylformamide (DMF), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), or a nitrile, e.g. acetonitrile. The resulting ketene thioacetal of formula VII is cyclised with the aid of hydroxylamine hydrochloride in the presence of a base, for example sodium acetate, in a solvent, for example an alcohol, e.g. ethanol, or an ether, for example tetrahydrofuran, to form a compound of formula If wherein R13 is R25S-. The cyciisation reaction is advantageously carried out at temperatures of from 0°C to 100°C. If desired, the compound of formula If can be oxidised analogously to known standard procedures, e.g. with peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to form the corresponding sulfone or sulfoxide of formula If (Rι3 = R25SO- or R25SO2-); or can be carried out
via Route b), by converting the β-diketone derivative of formula V analogously to J. Het. Chem. 20, 645 (1983) with an orthoacid amide of formula VIII, for example dimethylformamide dimethyl acetal, into the enamine derivative of formula IX and then cyclising that derivative with the aid of hydroxylamine hydrochloride, in the presence of a base, e.g. sodium acetate, in a solvent, for example an alcohol, e.g. ethanol, to form a compound of formula If.
The preparation of the 4-benzoylisoxazole derivatives of formula I (Q=Q6) wherein R13 is COORie, COR15, cyano, nitro or CONH2 can also be carried out, for example, analogously to WO 96/21357 and references cited therein.
The carboxylic acids of formula Id can be prepared analogously to known procedures, e.g. in accordance with the methods given in Reaction Schemes 4 and 5 below.
Reaction Scheme 4 Route a)
Figure imgf000033_0001
Claisen rearrangement
rearrangement T, solvent
Figure imgf000033_0002
Id (R2=CH3; n= 0)
Figure imgf000033_0003
Id (R2=CH3; n= 1 or 2 )
Route b):
OR.S
Figure imgf000034_0001
Figure imgf000034_0002
base, 0-200°C
Claisen rearrangement
1 ) hydrolysis
2) cyclisation
Figure imgf000034_0004
Figure imgf000034_0003
XXIIa ld(R2=CH3;n=0)
Figure imgf000034_0005
ld(R2=CH3;n=1 or 2) The alkenylation of the salicylic acid derivative of formula XX wherein R28 is d-C4alkyl in accordance with Route a) in Reaction Scheme 4 is carried out, for example, analogously to standard etherification methods by means of reaction with an allyl halide of formula XXV wherein Hal is halogen, especially chlorine, bromine or iodine, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1 -methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g. acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride. The reaction temperatures are generally in the range of from 0°C to 110°C.
The subsequent Claisen rearrangement of the allyl ether of formula XXI in Reaction Scheme 4 can be carried out, for example, thermally at temperatures of from 100°C to 300°C, optionally in an inert solvent, for example an aromatic hydrocarbon, e.g. xylene. Alternatively the thermal Claisen rearrangement can be carried out, for example, also without a solvent in a microwave oven. Such Claisen rearrangements are described, for example, in C. Ferri, "Reaktionen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff..
In accordance with Reaction Scheme 4, the resulting phenol derivative of formula XXII is then acylated, for example with a thiocarbamoyl halide of formula XXVI, e.g. N,N-dimethyl- thioformyl chloride, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g, acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride. The acylation is advantageously carried out at temperatures of from 0°C to 110°C.
The rearrangement of the thiocarbamate of formula XXIII in Reaction Scheme 4 is effected, for example, thermally in an inert solvent, for example an ether, e.g. diphenyl ether, at temperatures of from 100°C to 300°C and yields the thiolcarbamate of formula XXIV. That compound is then hydrolysed and cyclised using base or acid catalysis to form a compound of formula Id wherein R2 = CH3 and n = 0. This is effected advantageously either with a metal hydroxide, e.g. sodium hydroxide, or with a mineral acid, e.g. hydrochloric acid or sulfuric acid, at temperatures of from 0°C to 110°C. Suitable solvents are, for example, water, ethers, e.g. tetrahydrofuran, halogenated hydrocarbons, e.g. dichloromethane, and aromatic hydrocarbons, e.g. toluene. The resulting benzothiophene derivative of formula Id wherein R2 is methyl and n is 0 can then be oxidised in accordance with various standard methods. Advantageously the oxidation is carried out, for example, with hydrogen peroxide in an acidic solvent, for example an organic acid, e.g. acetic acid, or with an organic peracid, for example meta- chloroperbenzoic acid (m-CPBA), in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene. The reaction temperatures for the oxidation are generally in the range of from 0°C to 110°C. The degree of oxidation at the sulfur atom (n = 1 or 2) can be controlled by the amount of oxidising agent.
The above reaction sequence via acylation of the phenol derivative of formula XXII to form a thiocarbamate of formula XXIII, rearrangement of the latter compound to form a thiol- carbamate of formula XXIV and hydrolysis and cyclisation to form a compound of formula Id (n = 0) is carried out, for example, analogously to Org. Synth. 51 , 139 (1971 ), and the oxidation to form a compound of formula Id (n = 1 or 2) is carried out, for example, as described in H. O. House, "Modern Synthetic Reactions" W. A. Benjamin, Inc., Menlo Park, California, 1972, pages 334-335 and 353-354.
The electrophilic bromination according to Route b) in Reaction Scheme 4 is carried out, for example, analogously to Chem. Communic. 1972, 214. The bromination of the salicylic acid derivative of formula XX can be effected, for example, in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, and in the presence of a Lewis acid, for example titanium halide, e.g. titanium tetrachloride, at temperatures of from 0°C to 100°C. The subsequent coupling of the resulting bromosalicylic acid derivative of formula XXb to a trialkyltin-olefin of formula XXVb wherein R29 is d-C alkyl is carried out analogously to Angew. Chem. 98, 504 (1986) in an organic solvent, for example an ether, e.g. tetrahydrofuran, an aromatic hydrocarbon, e.g. toluene, and in the presence a palladium catalyst, for example tetrakis(triphenylphosphine)palladium. The reaction temperature is advantageously from 0°C to 200°C. The coupling product of formula XXII obtained by Route b) can then, for example in a manner analogous to that described under Route a), be acylated, rearranged, hydrolysed and cyclised, and optionally oxidised to form a compound of formula Id.
The aromatic nucleophilic substitution of the ortho-bromobenzoic acid ester of formula XXa wherein R28 is d-C4alkyl in Reaction Scheme 5 can be carried out analogously to known procedures, as described, for example, in J. March, "Advanced Organic Chemistry", 4th Edition, John Wiley & Sons, New York, 1992, pages 641-676. Accordingly, the benzoic acid ester of formula XXa is reacted with an alkenyl sulfide of formula XXVa in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2- pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g. acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride, at temperatures of from 0°C to 200°C.
The subsequent Claisen rearrangement of the resulting thioallyl ether of formula XXIa in Reaction Scheme 5 can advantageously be carried out in a manner analogous to that described in J. Org. Chem. USSR 13, 2437 (1977) and under Reaction Scheme 4 for the allyl ether of formula XXI, at temperatures of from 100°C to 300°C. The subsequent hydrolysis and cyclisation of the thiophenol of formula XXIIa and the optional oxidation of the resulting dihydrobenzo[b]thiophene derivative of formula Id (n=0) are advantageously likewise carried out as already described under Reaction Scheme 4.
The activated carboxylic acid derivatives of formulae III and I in Reaction Schemes 1 and 2 (Route a)) wherein X is a leaving group, for example halogen, e.g. bromine, iodine or especially chlorine, can be prepared according to known standard procedures as described, for example, by C. Ferri in "Reaktionen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff., such as, for example, in accordance with Reaction Scheme 6 below.
Reaction Scheme 6
Figure imgf000037_0001
III or I
In accordance with Reaction Scheme 6, the preparation of the compounds of formula III (X = leaving group) and I (X = halogen) is carried out, for example, advantageously by the use of a halogenating agent, for example a thionyl halide, e.g. thionyl chloride or bromide; a phosphorus halide or phosphorus oxyhalide, e.g. phosphorus pentachloride or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl bromide; or an oxalyl halide, e.g. oxalyl chloride, or by the use of a reagent for forming activated esters, for example N,N'- dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X. Where the compound of formula X is a halogenating agent, the group X is, for example, a leaving group, for example halogen, e.g. fluorine, bromine or iodine or especially chlorine, and Wi is, for example, PCI2, SOCI, SOBr or CICOCO.
The operation is optionally carried out in an inert organic solvent, for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1 ,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the reaction mixture, preferably at from 40 to 150°C, and in the presence of a catalytic amount of N,N-dimethylformamide. Such reactions are known and various variations thereof in respect of the leaving group X are described in the literature.
The compounds of formulae V, VII and IX (Reaction Scheme 3) are novel. They are important intermediates for the synthesis of the compounds of formula If. The invention therefore relates also to those compounds.
The compounds of formula IV (Reaction Scheme 1 ) wherein Zi = C(R6)R7, Z2 = (W)n6, Z3 = C(R6)R7 and n = 0 are known and can be prepared in a manner analogous to that described, for example, in US-A-5 006 150, WO 97/08164, DE-OS-3 818 958 and DE-OS-3 902 818.
The compounds of formula IV (Reaction Scheme 1 ) wherein Zi = CH, Z2 = O, S or -(CH2)n5-, Z3 = CH and n4 = 2 are known and can be prepared in a manner analogous to that described, for example, in EP-A-0 338 992.
The compounds of formula IV (Reaction Scheme 1 ) wherein Zi = CH2, Z2 = CHNHRg, Z3 = CH2 and n4 = 0 are known and can be prepared in a manner analogous to that described, for example, in EP-A-0 278 907.
The compounds of formula IV (Reaction Scheme 1 ) wherein ZΛ = NR10, Z2 = O, Z3 = C(R6)R7 and n = 0 are known and can be prepared in a manner analogous to that described, for example, in WO 96/26192 and US-A-5 336 662. The compounds of formula IVa (Reaction Scheme 2) wherein Rn and Ri2 are as defined for formula I are known and can be prepared in a manner analogous to that described, for example, in WO 96/26206 and WO 97/08164.
The compounds of formula V in Reaction Scheme 3 can be obtained in accordance with standard procedures, for example from the corresponding esters of formula XXVII
(XXVII),
Figure imgf000039_0001
wherein Ri to R5 and n are as defined for formula I and R28 is d-C4alkyl, for example via Claisen condensation, or from the compounds of formula III by reaction with a ketocarboxylic acid salt of formula XXVIII
COO" M+ CH2 (XXVIII), scoa.
wherein Rι4 is as defined for formula I and M+ is an alkali metal ion (see, for example, WO 96/26192, EP-A-0 496 631 ).
The salicylic acid derivatives of formula XX (Reaction Scheme 4) are either known (some of them being commercially available, for example when R5 is amino (4-aminosalicylic acid)) or can readily be prepared by standard procedures, for example starting from 4-aminosalicylic acid via diazotisation, Sandmeyer reaction and aromatic, nucleophilic substitution (see e.g. J. March, "Advanced Organic Chemistry", 4th Edition, John Wiley & Sons, New York, 1992, pages 641 -676) or Heck reaction of the resulting halide.
The benzoic acid derivatives of formula XXa (Reaction Scheme 5) are either known or can readily be obtained by bromination of the corresponding benzoic acid derivatives (see Reaction Scheme 4, Route b)).
The reagents of formulae VI, VIII, X, XXV, XXVa, XXVb and XXVI used in Reaction Schemes 3 to 6 are either known or can be prepared analogously to disclosed procedures. For the preparation of all other compounds of formula I functionalised in accordance with the definitions of Ri and R2 (2-position of the dihydrobenzo[b]thiophene ring), a large number of known standard procedures are available, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. EP-A-0 796 856).
For the preparation of all other compounds of formula I functionalised in accordance with the definition of R8 wherein Q is a group Qi to Q4, a large number of known standard procedures are available, for example alkylation, acylation and treatment with a sulfur reagent (e.g. P2S5 or Lawesson), the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. WO 97/08164 and DE-OS-3 902 818).
All other compounds within the scope of formula I can readily be prepared, taking into account the chemical properties of the dihydrobenzo[b]thiophene or Q moiety in relation to the structure of the dihydrobenzo[b]thiophene or Q rings, in a manner analogous to that described in Preparation Examples P1 to P1 1 or, for example, to that described in the patent specifications indicated.
The end products of formula I can in conventional manner be isolated by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluant. The sequence in which it is advantageous to carry out certain reactions in order to avoid possible secondary reactions will also be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers. The isomers can be separated according to methods known per se.
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 minerai 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 in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
In addition, the surfactants conventionally employed in formulation technology, which are described in, inter alia, "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 compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I can be used successfully either in the form of a mixture of the isomeric forms li to l and Ic (Q is a group Qi to Q4 and R8 is OH) or l6, 17 and le (Q is a group Q5) or in the form of pure isomeric forms to l or Ic, or l6, I7 or le, generally on plants or the locus thereof, at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, 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 : 2-Allyloχv-4-chlorobenzoic acid methyl ester
Figure imgf000043_0001
50 g (0.36 mol) of potassium carbonate are added, with stirring, to 56 g (0.3 mol) of 4- chlorosalicylic acid methyl ester in 200 ml of dimethyl sulfoxide. When the slightly exothermic reaction has subsided, 40 g (0.33 mol) of allyl bromide are added dropwise at 25°C. The reaction mixture is stirred at 22°C for 16 hours, poured into water and extracted by shaking with diethyl ether. The combined ether phases are washed with water, dried with sodium sulfate and concentrated by evaporation. The residue is recrystallised from a small amount of hexane. 62 g (91.2 % of theory) of the desired product having a melting point of 61-62°C are obtained.
Example P2: 2-Hvdroxy-3-(3-propenvO-4-chlorobenzoic acid methyl ester
Figure imgf000043_0002
97.9 g (0.432 mol) of 2-allyloxy-4-chlorobenzoic acid methyl ester (Example P1 ) are melted in a round-bottomed flask and irradiated in a microwave oven at 500 watts for 5 minutes. An exothermic reaction takes place. The reaction mixture is allowed to cool and yields 97.1 g (99.1 % of theory) of the desired product having a melting point of 32-35d. Example P3: 2-Oxy-(N,N-dimethyl-thiocarbamoyl)-3-(3-propenyl)-4-chtorobenzoic acid methyl ester
Figure imgf000044_0001
97 g (0.428 mol) of 2-hydroxy-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P2) and 69 g (0.5 mol) of potassium carbonate are stirred in 400 ml of dimethylformamide for 1/2 hour. A solution of 55.6 g (0.45 mol) of N,N-dimethyl-thiocarbamoyl chloride in 200 ml of dimethylformamide is then added dropwise thereto. The reaction mixture is stirred at 22°C for 22 hours. To complete the reaction, 1 1 g (0.09 mol) of N,N- dimethyl-thiocarbamoyl chloride and 15 g (0.11 mol) of potassium carbonate are added. After a further 24 hours at 22°C, the reaction mixture is poured into an ice-water mixture and extracted by shaking with ethyl acetate. The ethyl acetate phase is washed with water, then with brine, dried over sodium sulfate and concentrated by evaporation. The residue is chromatographed on silica gel (eluant: ethyl acetate/hexane 1/3), yielding 114.5 g (85 % of theory) of the desired product in the form of an oil.
Example P4: 2-Mercapto-(N,N-dimethyl-carbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester
Figure imgf000044_0002
1 14.5 g (0.365 mol) of 2-oxy-(N,N-dimethyl-thiocarbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P3) dissolved in 150 ml of diphenyl ether are added dropwise, in the course of 5 hours, to 100 ml of diphenyl ether at 205-210'C. The temperature is maintained at 205°C for a further 1 1/2 hours. After cooling, the diphenyl ether is distilled off at a pressure of 0.04 mbar. The residue is chromatographed on silica gel (eluant: ethyl acetate/hexane 1/1 ), yielding 90.2 g (78.8 % of theory) of the desired product in the form of an oil.
Example P5: 4-Chloro-2-methyl-2.3-dihvdro-benzorblthiophene-7-carboxylic acid
Figure imgf000045_0001
90.2 g (0.287 mol) of 2-mercapto-(N,N-dimethylcarbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P4) is heated under reflux for 20 hours in 150 ml of acetic acid and 200 ml of concentrated hydrochloric acid. The reaction mixture is concentrated in a rotary evaporator and the residue is stirred with water and cooled. The solid substance is filtered off and drying is carried out in vacuo at 60d, yielding 66 g (100 % of theory) of the expected product having a melting point of 215-218 C.
Example P6: 4-Chloro-2-methyl-1 ,1 -dioxo-2.3-dihvdro-benzofblthiophene-7-carboxylic acid
Figure imgf000045_0002
20 g (0.0875 mol) of 4-chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P5) are suspended in 150 ml of acetic acid and heated to 70°C. 24 ml of approx. 35 % hydrogen peroxide are then added dropwise thereto. The reaction is exothermic. At 80°C, the heating bath is removed and the dropwise addition is continued in such a manner that the temperature remains at 80°C. The reaction mixture is then maintained at 70-75°C for 1 hour. The reaction mixture is then concentrated using a rotary evaporator until crystals are deposited. Water is then added; the mixture is cooled and the precipitated crystals are filtered off. After drying in vacuo at 60d, 17 g (74 % of theory) of the desired product having a melting point of 223-225d are obtained. Example P7: 4-Chloro-2-methyl-1.1 -dioxo-2.3-dihvdro-benzorblthiophene-7-carboxylic acid chloride
Figure imgf000046_0001
16.7 g (0.06 mol) of 4-chloro-2-methyl-1 ,1 -dioxo-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P6) are heated to 90°C in 100 ml of toluene. 3 drops of dimethylformamide are added and then 9.5 g (0.08 mol) of thionyl chloride are added dropwise thereto in the course of 20 minutes, a clear solution being obtained. The reaction mixture is heated at 100°C for 3 hours and then concentrated by evaporation using a rotary evaporator, yielding 17 g of the desired product in the form of a solid substance.
Example P8: (2.3-Dihydro-4-chloro-2-methylbenzorb1thiophen-7-yl)(2-hvdroxy-6-oxo-1 - cvclohexen-1 -vDmethanone S.S-dioxide
Figure imgf000046_0002
9.5 g (0.094 mol) of triethylamine are added at 5°C to 3.6 g (0.0314 mol) of 1 ,3- cyclohexanedione in 80 ml of methylene chloride. At 5 C, 8.8 g (0.0314 mol) of 4-chloro-2- methyl-1 ,1-dioxo-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid chloride (Example P7) in 20 ml of methylene chloride are added dropwise. After 1 hour at 22°C, 0.5 ml of acetone cyanohydrin are added. After 5 1/2 hours, the reaction mixture is extracted by shaking with 2N hydrochloric acid. The methylene chloride phase is separated off, dried with sodium sulfate and concentrated by evaporation, and the residue is dissolved in a small amount of warm acetone. On being left to stand the product crystallises out. After filtration, 5.5 g (50 % of theory) of the expected product having a melting point of 170-172°C are obtained. Example P9: 4-Chloro-2-methyl-2.3-dihvdro-benzofb hiophene-7-carboxylic acid chloride
Figure imgf000047_0001
45.7 g (0.2 mol) of 4-chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P5), 23.8 g (0.22 mol) of thionyl chloride and a few drops of dimethylformamide are heated in 300 ml of toluene at 100°C for 18 hours. Concentration by evaporation yields the desired product, which can be used further without purification.
Example P10: (2.3-Dihvdro-4-chloro-2-methylbenzorblthiophen-7-vM1 ,3-dimethyl-5- hydroxy-1 H-pyrazol-4-yl)methanone
Figure imgf000047_0002
2.3 g (0.02 mol) of 1 ,3-dimethylpyrazolone-5 and 2.2 g (0.022 mol) of triethylamine are suspended in 80 ml of ethyl acetate and cooled to 5°C, and then 5.0 g (0.02 mol) of 4- chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid chloride (Example P9) in 20 ml of ethyl acetate are added. The reaction mixture is stirred at 22°C for 18 hours, the salts are filtered off and concentration by evaporation is carried out using a rotary evaporator. The residue is dissolved in 70 ml of dimethylformamide, and 2.2 g (0.022 mol) of triethylamine and 0.2 g of potassium cyanide are added. The reaction mixture is left to stand at 22°C for 18 hours and the dimethylformamide is evaporated off. Ethyl acetate and 5 ml of glacial acetic acid are added to the residue and the resulting solution is extracted by shaking with water. The organic phase is separated off, dried with sodium sulfate and concentrated by evaporation. Trituration with diethyl ether yields the desired product having a melting point of 191 -193°C. Example P11 : (2.3-Dihvdro-4-chloro-2-methylbenzorb1thiophen-7-yl)(1.3-dimethyl-5- hydroxy-1 H-pyrazol-4-yl methanone S.S-dioxide
Figure imgf000048_0001
2.0 g (0.0115 mol) of 3-chloroperbenzoic acid dissolved in 30 ml of methylene chloride are added to 1.7 g (0.0052 mol) of (2,3-dihydro-4-chloro-2-methylbenzo[b]thiophen-7-yl)(1 ,3- dimethyl-5-hydroxy-1 H-pyrazol-4-yl)methanone (Example P10) in 40 ml of methylene chloride. The reaction mixture is left to stand at 22°C for 2 days and is extracted by shaking with saturated, aqueous sodium hydrogen carbonate solution. The hydrogen carbonate phase is acidified with concentrated hydrochloric acid and the resulting precipitate is filtered off. The solid substance so obtained is triturated with diethyl ether and isolated by filtration, yielding 1.6 g of the desired product having a melting point of 230-233d.
In analogous manner, and in accordance with methods such as those described in the general Reaction Schemes 1 to 5 and the references indicated therein, it is also possible to prepare the preferred compounds listed in the following Tables.
Table 1 : A preferred group of compounds of formula I corresponds to general formula Id
(Id), wherein the meanings of the corresponding substituents
Figure imgf000048_0002
Ri to R5 and n are given in Table A, so that 819 specific compounds of formula Id are disclosed. Table 2: A further preferred group of compounds of formula I corresponds to general
formula Ig (lg), wherein the meanings of the corresponding
Figure imgf000049_0001
substituents Ri to R5 and n are given in Table A, so that 819 specific compounds of formula Ig are disclosed.
Table 3: A further preferred group of compounds of formula I corresponds to general
formula lh (lh), wherein the meanings of the corresponding
Figure imgf000049_0002
substituents Ri to R5 and n are given in Table A, so that 819 specific compounds of formula lh are disclosed.
Table 4: A further preferred group of compounds of formula I corresponds to general
formula li (li), wherein the meanings of the corresponding
Figure imgf000049_0003
substituents Ri to R5 and n are given in Table A, so that 819 specific compounds of formula li are disclosed.
Table 5: A further preferred group of compounds of formula I corresponds to general
formula Ij (Ij), wherein the meanings of the
Figure imgf000049_0004
corresponding substituents Ri to R5 and n are given in Table A, so that 819 specific compounds of formula ij are disclosed. Table 6: A further preferred group of compounds of formula I corresponds to general
formula Ik (Ik), wherein the meanings of the
Figure imgf000050_0001
corresponding substituents Ri to R5 and n are given in Table A, so that 819 specific compounds of formula Ik are disclosed.
Table A
Compd. R2 Ri R3 R4 Rs n No.
.001 H CH3 H H Cl 0
.002 H CH3 H H F 0
.003 H CH3 H H Br 0
.004 H CH3 H H SO2Me 0
.005 H CH3 H H SMe 0
.006 H CH3 H H SO2NMe2 0
.007 H CH3 H H CF3 0
.008 H CH3 H H CH3 0
.009 H CH3 H H CH(CH3)2 0
.010 H CH3 H H NO2 0
.011 H CH3 H H OCH3 0
.012 H CH3 H H OCF2CF3 0
.013 H CH3 H H CN 0
.014 H CH3 H H Cl
.015 H CH3 H H F
.016 H CH3 H H Br
.017 H CH3 H H SO2Me
.018 H CH3 H H SMe
.019 H CH3 H H SO2NMe2
.020 H CH3 H H CF3 ompd. R2 Ri R3 R4 Rs n No.
.021 H CH3 H H CH3
.022 H CH3 H H CH(CH3)2
.023 H CH3 H H NO2
.024 H CH3 H H OCH3
.025 H CH3 H H OCF2CF3
.026 H CH3 H H CN
.027 H CH3 H H Cl 2
.028 H CH3 H H F 2
.029 H CH3 H H Br 2
.030 H CH3 H H SO2Me 2
.031 H CH3 H H SMe 2
.032 H CH3 H H SO2NMe2 2
.033 H CH3 H H CF3 2
.034 H CH3 H H CH3 2
.035 H CH3 H H CH(CH3)2 2
.036 H CH3 H H NO2 2
.037 H CH3 H H OCH3 2
.038 H CH3 H H OCF2CF3 2
.039 H CH3 H H CN 2
Figure imgf000051_0001
.043 H CH3CH2 H H SO2Me 0
.044 H CH3CH2 H H SMe 0
.045 H CH3CH2 H H SO2NMe2 0
.046 H CH3CH2 H H CF3 0
.047 H CH3CH2 H H CH3 0
.048 H CH3CH2 H H CH(CH3)2 0
.049 H CH3CH2 H H NO2 0
.050 H CH3CH2 H H OCH3 0
.051 H CH3CH2 H H OCF2CF3 0 Compd. R2 Ri R3 R4 Rs n No.
.052 H CH3CH2 H H CN 0
.053 H CH3CH2 H H Cl
.054 H CH3CH2 H H F
.055 H CH3CH2 H H Br
.056 H CH3CH2 H H SO2Me
.057 H CH3CH2 H H SMe
.058 H CH3CH2 H H SO2NMe2
.059 H CH3CH2 H H CF3
.060 H CH3CH2 H H CH3
.061 H CH3CH2 H H CH(CH3)2
.062 H CH3CH2 H H NO2
.063 H CH3CH2 H H OCH3
.064 H CH3CH2 H H OCF2CF3
.065 H CH3CH2 H H CN
.066 H CH3CH2 H H Cl 2
.067 H CH3CH2 H H F 2
.068 H CH3CH2 H H Br 2
.069 H CH3CH2 H H SO2Me 2
.070 H CH3CH2 H H SMe 2
.071 H CH3CH2 H H SO2NMe2 2
Figure imgf000052_0001
.073 H CH3CH2 H H CH3 2
.074 H CH3CH2 H H CH(CH3)2 2
Figure imgf000052_0002
.077 H CH3CH2 H H OCF2CF3 2
Figure imgf000052_0003
.081 CH3 CH3CH2 H H Br 0
.082 CH3 CH3CH2 H H SO2Me 0 i— O O to •— O vo OO
Figure imgf000053_0001
ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox 33
o X oX o o X o o X o oX o o o o o o o o o o o o o o o o o o o o o o ox o ω X ω X X X X X X X X ωX X ω X ωX x x x x x x x x x x ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox o X o X oX oX oX Xo Xo oX
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x ID
x x x x x x x x x x x x x x x x x x x x x x x x x X X X X X X 13
Figure imgf000053_0002
M M M IO M J N M M o o
Compd. R2 Ri R3 R4 R5 n No.
.114 CH3 CH3CH2 H H NO2 2
.115 CH3 CH3CH2 H H OCH3 2
.116 CH3 CH3CH2 H H OCF2CF3 2
.117 CH3 CH3CH2 H H CN 2
.118 H CH3 H CH3 Cl 0
.119 H CH3 H CH3 F 0
.120 H CH3 H CH3 Br 0
.121 H CH3 H CH3 SO2Me 0
.122 H CH3 H CH3 SMe 0
.123 H CH3 H CH3 SO2NMe2 0
.124 H CH3 H CH3 CF3 0
.125 H CH3 H CH3 CH3 0
.126 H CH3 H CH3 CH(CH3)2 0
.127 H CH3 H CH3 NO2 0
.128 H CH3 H CH3 OCH3 0
.129 H CH3 H CH3 OCF2CF3 0
.130 H CH3 H CH3 CN 0
.131 H CH3 H CH3 Cl
.132 H CH3 H CH3 F
.133 H CH3 H CH3 Br
.134 H CH3 H CH3 SO2Me
.135 H CH3 H CH3 SMe
.136 H CH3 H CH3 SO2NMe2
.137 H CH3 H CH3 CF3
.138 H CH3 H CH3 CH3
.139 H CH3 H CH3 CH(CH3)2
.140 H CH3 H CH3 NO2
.141 H CH3 H CH3 OCH3
.142 H CH3 H CH3 OCF2CF3
.143 H CH3 H CH3 CN
.144 H CH3 H CH3 Cl 2 Compd. R2 Ri R3 R4 Rs n No.
.145 H CH3 H CH3 F 2
.146 H CH3 H CH3 Br 2
.147 H CH3 H CH3 SO2Me 2
.148 H CH3 H CH3 SMe 2
.149 H CH3 H CH3 SO2NMe2 2
.150 H CH3 H CH3 CF3 2
.151 H CH3 H CH3 CH3 2
.152 H CH3 H CH3 CH(CH3)2 2
.153 H CH3 H CH3 NO2 2
Figure imgf000055_0001
.155 H CH3 H CH3 OCF2CF3 2
.156 H CH3CH2 H CH3 CN 2
.157 H CH3CH2 H CH3 Cl 0
.158 H CH3CH2 H CH3 F 0
.159 H CH3CH2 H CH3 Br 0
.160 H CH3CH2 H CH3 SO2Me 0
Figure imgf000055_0002
.162 H CH3CH2 H CH3 SO2NMe2 0
.163 H CH3CH2 H CH3 CF3 0
.164 H CH3CH2 H CH3 CH3 0
.165 H CH3CH2 H CH3 CH(CH3)2 0
.166 H CH3CH2 H CH3 NO2 0
Figure imgf000055_0003
.168 H CH3CH2 H CH3 OCF2CF3 0
.169 H CH3CH2 H CH3 CN 0
.170 H CH3CH2 H CH3 Cl
.171 H CH3CH2 H CH3 F
.172 H CH3CH2 H CH3 Br
.173 H CH3CH2 H CH3 SO2Me
Figure imgf000055_0004
.175 H CH3CH2 H CH3 SO2NMe2 Compd. R2 Ri R3 R4 Rs n No.
.176 H CHsCH2 H CH3 CF3
.177 H CH3CH2 H CH3 CH3
.178 H CH3CH2 H CH3 CH(CH3)2
.179 H CH3CH2 H CH3 NO2
Figure imgf000056_0001
.181 H CHsCH2 H CH3 OCF2CF3
.182 H CHsCH2 H CH3 CN
.183 H CHsCH2 H CH3 Cl 2
.184 H CH3CH2 H CH3 F 2
.185 H CH3CH2 H CH3 Br 2
.186 H CH3CH2 H CH3 SO2Me 2
.187 H CH3CH2 H CH3 SMe 2
.188 H CH3CH2 H CH3 SO2NMe2 2
.189 H CH3CH2 H CH3 CF3 2
.190 H CHsCH2 H CH3 CH3 2
.191 H CH3CH2 H CH3 CH(CH3)2 2
.192 H CH3CH2 H CH3 NO2 2
.193 H CH3CH2 H CH3 OCH3 2
.194 H CH3CH2 H CH3 OCF2CF3 2
.195 H CHsCH2 H CH3 CN 2
.196 CH3 CH3CH2 H CH3 Cl 0
.197 CH3 CH3CH2 H CH3 F 0
.198 CH3 CH3CH2 H CH3 Br 0
.199 CH3 CH3CH2 H CH3 SO2Me 0
.200 CH3 CH3CH2 H CH3 SMe 0
.201 CH3 CH3CH2 H CH3 SO2NMe2 0
.202 CH3 CH3CH2 H CH3 CF3 0
.203 CH3 CH3CH2 H CH3 CH3 0
.204 CH3 CHsCH2 H CH3 CH(CH3)2 0
.205 CH3 CH3CH2 H CH3 NO2 0
.206 CH3 CH3CH2 H CH3 OCH3 0
Figure imgf000057_0001
Ox Ox Ox Ox xO Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox xO Ox xO
Figure imgf000057_0002
o X oX oX x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33 ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox Ϊ-Pπ o CO O Q CO r Q O-. o τι δ * o-' zz 5 o o eg> 8 o ° o z 5 o o o c 8 o
^ o 3: ιo o Q o o -ζ C xO C τOι z g» s φ ~ ^ φ O ,-?- « X ω ω τι Tl Φ s <» I «*> o Tl ro ro ro i ro ro ro ro r ro ro ro ro o o
to to o t
Ov σv σv σv
00 -o σv Ul
ox ox ox ox
Figure imgf000058_0001
Figure imgf000058_0002
ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox JJ
Figure imgf000058_0003
ro ro ro ro ro ro ro ro o o o o o o o o o o
Figure imgf000058_0004
ompd. R2 Ri R3 R4 R5 n
No.
.269 CH3 CH3CH2 CH3 CH3 CH(CH3)2 2
.270 CH3 CHsCH2 CH3 CH3 NO2 2
.271 CH3 CH3CH2 CH3 CH3 OCH3 2
.272 CH3 CH3CH2 CH3 CH3 OCF2CF3 2
.273 CH3 CH3CH2 CH3 CH3 CN 2
.274 H CH3 H Cl Cl 0
.275 H CH3 H Cl F 0
.276 H CH3 H Cl Br 0
.277 H CH3 H Cl SO2Me 0
.278 H CH3 H Cl SMe 0
.279 H CH3 H Cl SO2NMe2 0
.280 H CH3 H Cl CF3 0
.281 H CH3 H Cl CH3 0
.282 H CH3 H Cl CH(CH3)2 0
.283 H CH3 H Cl NO2 0
.284 H CH3 H Cl OCH3 0
.285 H CH3 H Cl OCF2CF3 0
.286 H CH3 H Cl CN 0
.287 H CH3 H Cl Cl
.288 H CH3 H Cl F
.289 H CH3 H Cl Br
.290 H CH3 H Cl SO2Me
.291 H CH3 H Cl SMe
.292 H CH3 H Cl SO2NMe2
.293 H CH3 H Cl CF3
.294 H CH3 H Cl CH3
.295 H CH3 H Cl CH(CH3)2
.296 H CH3 H Cl NO2
.297 H CH3 H Cl OCH3
.298 H CH3 H Cl OCF2CF3
.299 H CH3 H Cl CN Compd. R2 Ri R3 R4 R5 n No.
.300 H CH3 H Cl Cl 2
.301 H CH3 H Cl F 2
.302 H CH3 H Cl Br 2
.303 H CH3 H Cl SO2Me 2
Figure imgf000060_0001
.305 H CH3 H Cl SO2NMe2 2
.306 H CH3 H Cl CF3 2
.307 H CH3 H Cl CH3 2
.308 H CH3 H Cl CH(CH3)2 2
.309 H CH3 H Cl NO2 2
.310 H CH3 H Cl OCH3 2
.311 H CH3 H Cl OCF2CF3 2
.312 H CH3 H Cl CN 2
.313 H CH3CH2! H Cl Cl 0
.314 H CHsCH2 H Cl F 0
.315 H CH3CH2 H Cl Br 0
.316 H CH3CH2 H Cl SO2Me 0
Figure imgf000060_0002
.318 H CH3CH2 H Cl SO2NMe2 0
.319 H CH3CH2 H Cl CF3 0
.320 H CH3CH2 H Cl CH3 0
.321 H CH3CH2 H Cl CH(CH3)2 0
.322 H CH3CH2 H Cl NO2 0
Figure imgf000060_0003
.324 H CH3CH2 H Cl OCF2CF3 0
.325 H CHsCH2 H Cl CN 0
.326 H CH3CH2 H Cl Cl
.327 H CHsCH2 H Cl F
.328 H CH3CH2 H Cl Br
.329 H CH3CH2 H Cl SO2Me
.330 H CHsCH2 H Cl SMe
Figure imgf000061_0001
o x ox ox ox ox ox ox ox o X o X o x ox ox ox ox ox ox ox o X ox ox ox ox ox ox ox ox o X ox ox ox ox ox ox ox ox ox ox
Figure imgf000061_0002
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
Figure imgf000061_0003
o o ro ro ro ro ro ro ro ro ro ro ro ro r
o J J UJ UJ UJ UJ UJ J J UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ J UJ UJ UJ u> J J UJ UJ UJ
VO vo VO 00 00 00 00 00 00 00 00 00 00 ~J ^J -J -o -J J -J -J l -o ~J - σv σ
-fc J to t—* o vo 00 -o σv Ul -fc J t *~* o vo OOv σv σv σv to -j σv Ul 2 σJv σv
O VO oo ~J σv U to 9 a.
_^^ _=C oχ ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox
oπi ox ox ox ox ox ox ox ox ox ox ox ox ox ox xo ox ox ox ox ox o o c ω c xo x x ox ox ox ox oo co o ωo coo coo coo coo ωo ωo coo coo coo ωo coo coo oo coo coo coo coo co co co co co co co
Figure imgf000062_0001
x x x x x x x x x x x x x x x x x x x x x ox ox ox ox ox ox ox
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
Figure imgf000062_0002
ro ro ro ro ro ro ro ro ro ro ro r ro
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ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x ω o ° o
_ s_i CO o T o CO o O co
O " O o o o ro -π O τι O ~ o o 9 <Q O o o X o co z ^ o o «: w o ro φ ≤ z ιo X X o T ~ υ l ro O O τι o z -^ o o _, "
CD S o 3: O Q X -π Z 2
X ω _ φ ≤ φ φ Tl CD" φ Φ « ro ro ro ro ro ro ro o o o o o o o o o o o
Figure imgf000063_0001
o
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UJ UJ ) UJ UJ J UJ UJ UJ UJ to to to to to to
4^ UJ to <— * O v £o £ 00 ~-J σcv ui U fcJ fc to fc fc *>> ■fc. -f
— o VO 00 -J σv Ui 4^ J to o O 00 -o σv Ui z§
*> • O -σ 3
Q. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000064_0001
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
Figure imgf000064_0002
o o o o o o o o o o o o o ro ro ro ro ro ro
4^ 4>. -fc 4^ ^ 4^ -fc -fc -fc> -fc -fc -fc 4^ * ^ 4^ 4^ 4^ 4^ 4^ 4^ 4^ -fc 4^ 4^ 4^ 4^ , o o
00 00 00 oo 00 00 -J -4 -J -J -J -4 -J -o σv σv σv σv σv σv σv σv σv σv Ui Ul Ui Ui Uι O •3 Ui 4^ UJ to o O 00 σv Ui 4^ J to ►- o vo oo σv Ui 4^ UJ to ►-> o VO 0 ■ σ Ui 3 Q. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
O O O O O O oO O O O O O O O O O O o O r oo io o ro o r oo r oo r oo ro r oo r oo w o t o to o r oo r oo r oo r oo io o ro X o X
Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox o r
X o X
Figure imgf000065_0001
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
O co O O co
CO o ro τι ΩsS " R z -g o o g co S ra ~\ O S 8 Z 5sΩsO £SS 33 φ τι ωl si ϋ, ssS φ s€f sp -n Ω gg -π ωδ δi ϋ, ro ϊε® s -πas
-i -i. -i. -j- o o o o o o o o o o o o o ro ro ro ro ro ro ro ro ro r ro ro ro -*'
Compd. R2 Ri R3 R4 Rs n No.
.486 H CO2CH3 H H SMe
.487 H CO2CH3 H H SO2NMe2
.488 H CO2CH3 H H CF3
.489 H CO2CH3 H H CH3
.490 H CO2CH3 H H CH(CH3)2
.491 H CO2CH3 H H NO2
.492 H CO2CH3 H H OCH3
.493 H CO2CH3 H H OCF2CF3
.494 H CO2CH3 H H CN
.495 H CO2CH3 H H Cl 2
.496 H CO2CH3 H H F 2
.497 H CO2CH3 H H Br 2
.498 H CO2CH3 H H SO2Me 2
.499 H CO2CH3 H H SMe 2
.500 H CO2CH3 H H SO2NMe2 2
.501 H CO2CH3 H H CF3 2
.502 H CO2CH3 H H CH3 2
.503 H CO2CH3 H H CH(CH3)2 2
.504 H CO2CH3 H H NO2 2
Figure imgf000066_0001
.506 H CO2CH3 H H OCF2CF3 2
.507 H CO2CH3 H H CN 2
.508 H CH=O H H Cl 0
.509 H CH=O H H F 0
.510 H CH=O H H Br 0
.511 H CH=O H H SO2Me 0
.512 H CH=O H H SMe 0
.513 H CH=O H H SO2NMe2 0
.514 H CH=O H H CF3 0
.515 H CH=O H H CH3 0
.516 H CH=O H H CH(CH3)2 0 o
Ul Ui Ui Ui Ul Ul Ui Ui Ul Ul Ui Ul Ul Ul Ul Ui Ul Ul Ul Ul Ui Ui Ui Ul Ui Ul Ul Ui Ui Ul Ui
-fc. *. -fc. ■fc. 4^- a. -fc- 4^ UJ UJ J UJ UJ UJ UJ UJ U) J to t to to to to to to N> t *- — i—
-J σv Ul 4>> J t O VO 00 ~J σv Ul -fc UJ to o vo 00 -o σv Ul -fc J to 0 *0 00 -0 zo • .T3iJ
Q. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
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33 O II II II II II II II II II H II M II II II II M M II II II II II II II II II II II II Q O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
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Figure imgf000067_0001
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-J -J -J -J ~J -J --J -o -O σv σv σv v σv σv σv σv σv σv ui ui Ui Ui Ui Ul Ul Ul Ui Ui
00 -fc σv ui 4^
00 -J σv Ul 4^ UJ to o vo 4^ UJ to .— O vo oo -j σv ui 4^- UJ NJ >— O VO 00 9% a. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X
II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II z z z z z z z z z z z z z z z z z z z z z z z z z z z z o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X x x X X X X X X x x x x x x x x x X X X ω X c Xo X X X X
X X x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
X X x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000068_0001
ro ro ro ro ro ro o o o o o o o
O σv σv σv σv σv σv σv σ σv σv Ul Ui Ui Ul > o o o o <r> o o o o o o 00 00 oo -o ■ 3 σv *>• t ι— ' o σv 4^ •— ' o vo σv -fc t *- O O α.
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
o o o o o o X o o o o o o o o o o o o o o o o o o o o o o o X X X X X X
X X X X X X X T X X T T T. X X T T T X T T T T. T II II II II II II II
7 7 7 7 7 > z z z z z z z z z z z z z z z z z z z z z z
X X X o o o O n o n
X X X X X lo X X X X X X X X X X X X X X X X o
X o X o X o o
X X X o
X o
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000069_0001
o o o o o o o o o o o o o ro ro ro ro ro ro ro
σv σv σv σ σv σv σv σ σv σv σv σv σv σv σv σv σv σv σv σv σv σv σ σv σ σ
UJ UJ J UJ J UJ UJ to Nl t to to to to to N> to σv σ σ σv >- UJ UJ UJ o vo oo -j σv Ul -fc u> to >— ' o VO 00 -J σv Ui 4 J NJ >— • o O 00 σv ui W W M z o •
Figure imgf000070_0001
Figure imgf000070_0002
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
o o o o o o o o o o o o o o o o o o x x x x x x x x x x x x x x x z z z oz oz oz oz oz oz oz oz oz oz oz oz oz zx zx zx zx zx zx zx zx z X zX zX zX zX zX zX
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000070_0003
o o o o o o o o o o o o o ro ro ro ro ro ro ro ro ro ro ro ro ro -t -'
o σ σv σv v σv σv v σ σv σv σv σv σv σv σv σv σv σv σv σv σv σv σ σv v σv σv σv
-o -4 σv σv σv σv σv σv σv σv σv σv Ul Uι Ul i Ul Uι Ui Ul Ul Ui -fc -fc ■fc.
>—* o vo 00 -o σv i -fc. UJ to o O oo v Uι -fc UJ t >-— f 4^ i 4^ o O 00 -o 2 σ σv U^ -c to 9 z%i a. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
o jor jox o2: oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz oz 33
Figure imgf000071_0002
Figure imgf000071_0003
Figure imgf000071_0001
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000071_0004
o o o o o o o o ro io io ro ro ro ro ro ro ro ro ro ro
-J •~J -J v σv σv σv σv σv σv σ σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv σv r-> O o vo o o o o O vo O VO vo 00 00 00 00 00 00 OO 00 00 00 -o -j -j -o -o -o -o o 00 -j σv Ul 4^ J NJ -o
NJ o vo OO - σv Ul 4>. UJ NJ o v 1 o VO 00 -o σ Ul -fc UJ to
Figure imgf000072_0001
ox ox ox ox ox ox ox ox ox ox xo ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X Xo Xo o X o X Xo o X o X o X o X Xo o X Xo Xo Xo o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000072_0002
r ro ro ro ro ro ro ro ro ro ro ro ro o o o o o
o. N o
-J -J -J -J -J -j -4 -J ~j -O -J -J -J -4 -o -o -4 -J -O -O -O - -J -O -O -O ^1 ~J -O ~J ~1
C*J UJ UJ J to to to to NJ to NJ to to to >— * z o
UJ to o vo 00 -0 σv Ul 4^ J NJ •— * o VO 00 -o σv _ Uι _ O 4^^ _U) ^|O _ι—' ^O oVO oOO o-j oσv oui o.fc o UJ o 3
TJ Q. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
O O o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X o o o o
X X X X X X X X X o X o X o o
X X o X o X X X X X X
II II II II II II II II II o II II II II II II II II II II II II II II II II o o o o II o II o o o o o II o o o o o o o X X X X X X X X X X X X o o o o o o 33
X X X X X o o o o o X o X o X o X o II
X o II II X o X o X X X X X X o o o o o o o o o o o o o o
X X X X X X X X X X X X o X o X X X X o X o X o X o X o X o X o X o X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X !
X X X X X X X X X x x x x x x x x x x x x x X X X X X X X X X 33
Figure imgf000073_0001
ro ro ro ro ro o o o O O O O O O O O 3
-o ~o ^J -o -o -o -o . o o σv σv σ σv σv •fc. ■fc. 4^ *» *>. fc * -fc -fc -fc •3
-fc. to o -o σv -fc to o - σv O oo σv 4^ TJ α. x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x o o o o o o o o o o o o o o o o o o o o X X X X X X o X o X o
X X X X X X X X X X X X X X X
II II II II I III II II II II II II II II II o II II II II II II II o o o o o o o o o o o o o o o o o o o o o X o X o o
X X X X X X
II II II II II II II II
X X X X X o X X X X o X X X X o X o X o X o X o o o o o o o o o o o o o o o o X X X X X X o X o o o o o o o o o o o 33 o X X ro ro o o o o o o ro o r oo r oo r oo ro o r oo o o o o o X X X X X X ro o o o o o o o o o o o o o o o o o o o
X o X X X X o X o ω
X X X X X X X o X o ro o roo roo r oo roo roo r oo o o o o o o X X X X X X X X
X o X X X X X X X o X x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Figure imgf000074_0001
o o o O O O O O O O O ro ro ro to ro ro ro
o
-J -J -4 - -O -O -o -o -o ^ι -J -o -J - -J ~J -o -J -J -4 -4 -4 -O ~-4 -J -O -o -J ^1 ^j
VO VO 00 00 oo oo z o vo VO VO oo oo 00 00 00 00 -J -J -J -J -J -J -J -J σv σv σv σv σv
Ul 4^ J NJ -— vo oo -o σv ui 4^- J NJ O vo 00 -o σ ui 4^. UJ NJ - O vo -o σv Ul o 3
TJ Q. o o o o o o o o o o o o o o o _ _ _ _
X X X X X X X X X X X X X X X 1 1 1 1 X X X X X X X X X X X X 33 o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X
II II II II II II II II II II II II II II II II
_ o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o O X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X ,? o o o o o o o o o o o o o o o o ω r Oo r oo r oo o r oo r oo r oo ro o r oo r oo r oo r oo r oo ro o ro o r oo o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33 o CO o CO o o o o O -a c O z o Z O ro τι ^ ° O z 5 8 o o Mo 9 X c ^ r, o c τoι ≤ ^_ φ s, Q z ~ 5 J °1 o ° o X r Oo o o! , 9? o 9 X ? X τι ^ Z w ≤Z o, ro τι o
≤Z. ro
Tl i - Φ r ro ro o Tl ω ^ lo ro ro ro ro ro io ro ro ro ro ro ro -»• -* 3
o uo oo oo ^1 --J o o O σ Ov O VO VO ■ 3 O OO ~θ σ ι - UJ tO *-* O vθ 00 -J o O O O O O VO V
Ui ^ J to vo 00 ^J σv TJ Q.
Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox 33
ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33 o o CO
X o CO o o CO 9 J °i o o -si co o X o CO o o ro τι o ,? ιo o o X X Tl Z <ζ. o
< Φ Q δ S i S S ζ ϊ o o ro φ φ o T| ,? X « CD _Z φ" (D ro ro ro io ro ro ro ro ro ro ro ro ro
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TJ
3" CO Q. ω
Figure imgf000077_0002
Figure imgf000078_0001
o x ox ox ox ox ox ox ox o X o X o X o X o X o X o X o X o X o X o X o X o X o X Xo o X o X o X o X o X o X o X o X o X 33
X X X X X X X X X X X X X X X x x x x x x x x x x X X X X X X X 33
X X X X X X X X X X X X X X X x x x x x x x x x x X X X X X X X 33 o o O CO
CO
CO X CO τι o o o o o o o CO o E?-"θ g§8 g oo o CO
CO
2 o ro Tl o z τ r ~π o o φ i- z X
X o o ι
X z 2
_: φ z o o 33 o 2 o Tl
X ω φ ≤: z φ τι φ τι φ φ o o o o o o o o o o o o o ro ro ro ro ro ro ro ro ro ro ro ro rroo -'- 3 o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
TJ ro O o CL o 03
Figure imgf000079_0001
Figure imgf000079_0002
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33
Xo Xo o X Xo o X Xo Xo Xo Xo o o X o X Xo o X Xo o X Xo Xo Xo o X ox xo ox xo ox xo xo xo ox xo xo ox 33
X X X X X X X X X X X X X X X X X X X x x x x x x x x x x x x 33
X X X X X X X X X X X X X X X X X X X x x x x x x x x x x x x 33
Figure imgf000079_0003
O O o O O O O O O o ro ro ro ro ro ro ro ro ro ro r ro fo -^ -^ -j. -A -' -' -i -i 3
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ω
O
O O to to o O o o o O o o o O o o V VO bvo vo oO ovo o O O o vo Z3 o ov ui UJ to — o VO 00 -J σv Ul ■fc J NJ oo O SO 00 σv Ui -fc UJ v NJ — O Q.
Figure imgf000080_0001
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 33 o X oX oX oX oX oX oX o X oX oX oX oX o ox ox ox ox ox ox ox ox ox ox ox ox ox o o X o X o X o X o X 33
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33
Figure imgf000080_0002
o o o o ro ro ro ro ro io io ro ro ro ro ro ro 3
M M M M -' -' -^ -' -1 -1 -1 -' -' -' -' -' -' 3
TJ
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CΛ Ul Ul Ul ^. -fc * £>. 4^ ^ -fc 4^. J UJ to o O 00 -J σv Ul fc 4^ UJ UJ UJ UJ J UJ NJ to NJ NJ to NJ NJ >~
UJ J to •— . UJ UJ
O VO 00 -J σv Ul 4^ UJ to •— . o vo OO l σv Ul *> UJ w 9r-o3
Figure imgf000081_0001
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 13 o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33
Figure imgf000081_0002
ro ro ro ro ro ro ro ro ro o Z3 ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro io ro ro ro rroo ro
TJ "< 3" α.
0) 0>
o z o
00 00 00 00 00 00 ^j •>4 ^1 -J -^ 4 ->4 ->1 ^sl <n cn σ> Oϊ cn σ> cn cn cn σ> Ul Oi Ol Ul Uι Ui o 3 cn ^ ω ro -— o O 00 ■vl σ> cn -fc. ω ro -«■ o CO 00 - | OJ cn >. ω I o D 00 -4 σv Ul a- T3 Q. o O O O o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X ω X X X X o o O o o o o o o o o o o o o o o o o o o o o o o o
X o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 33
Figure imgf000082_0001
ro ro ro o o o o o o o o o o o o o ro ro ro 3 o o o o o o o o o o o o o o o o o o o o o o o o o o o o o ro ro ro 13 ro
TJ
3" CO α.
0)
Compd. Ri Rs R4 n n2 Phys. data No.
7.186 CH3 CH3 H H SO2Me 2 0
7.187 CH3 CH3 H H SMe 2 0
7.188 CH3 CH3 H H SO2NMe2 2 0
7.189 CH3 CH3 H H CF3 2 0
7.190 CH3 CH3 H H CH3 2 0
7.191 CH3 CH3 H H CH(CH3)2 2 0
7.192 CH3 CH3 H H NO2 2 0
' 7.193 CH3 CH3 H H OCH3 2 0
7.194 CH3 CH3 H H OCF2CF3 2 0
7.195 CH3 CH3 H H CN 2 0
Table 8: A further group of compounds of formula I corresponds to general formula lm
(lm), wherein the meanings of the corresponding
Figure imgf000083_0001
substituents R, to R5 and n are given in Table B, so that 78 specific compounds of formula lm are disclosed.
Table 9: A further group of compounds of formula I corresponds to general formula In
(In), wherein the meanings of the corresponding substituents
Figure imgf000083_0002
R to R5 and n are given in Table B, so that 78 specific compounds of formula In are disclosed. Table 10: A further group of compounds of formula I corresponds to general formula lo
(lo), wherein the meanings of the corresponding
Figure imgf000084_0001
substituents Ri to R5 and n are given in Table B, so that 78 specific compounds of formula lo are disclosed.
Table 1 1 : A further group of compounds of formula I corresponds to general formula Ip
(Ip), wherein the meanings of the corresponding
Figure imgf000084_0002
substituents Ri to R5 and n are given in Table B, so that 78 specific compounds of formula Ip are disclosed.
Table B
Compd. R2 Ri R3 R4 Rs n No.
.001 H CH3 H H Cl 0
.002 H CH3 H H F 0
.003 H CH3 H H Br 0
.004 H CH3 H H SO2Me 0
.005 H CH3 H H SMe 0
.006 H CH3 H H SO2NMe2 0
.007 H CH3 H H CF3 0
.008 H CH3 H H CH3 0
.009 H CH3 H H CH(CH3)2 0
.010 H CH3 H H NO2 0
.011 H CH3 H H OCH3 0
.012 H CH3 H H OCF2CF3 0 o o o o o o o o o o o o o o o o o o o o o o o o
-fc. -fc. -fc *>• CO ω ω ω ω ω ω ω ω ω ro t ro ro ro I ro ro o ro IV} o -i o ->. o -i. o - . o — - o co oo ^j cn cn O
4*. ω ro CD 00 • l cn cn -fc. ω ro — - o CO 00 -NI n n 3
■fc. ω IO ω • zi3
Q.
O O O O O _ _
X X X X X ^ ^ x x x x x x x x x x x x x x x x x x x x x x x x x X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X o X JU ω
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
Figure imgf000085_0001
o o o o o ro ro ro ro ro ro ro ro ro ro ro ro ro o J
Figure imgf000085_0002
O o o o o o o o O O O O O O O O O O o o o o o o o o o o o o o o o
^1 ■* ^l -vl ~ ■ j ■ j n σ> n n <n cn cn <n o cn cn cn Ol cn Ol cn cn cn Ui cn k . 4 4a. ^ O z33 n cn ■fc. ω ro — *• O CO 00 -si n cn -fc. ω ro - L o CO 00 -4 n cn -fc. CO ro — *• o CO 00 ^1 en oι • TJ
O O O o o o o o O O O O o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X ιo X ω X X X X X X ω X X X X X o o o o o o o o o o O o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X 33 ω X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
Figure imgf000086_0001
ro ro ro ro ro ro ro ro ro ro ro o o o o o o o o 3
Compd. R2 Ri R3 R4 RE No.
.077 CH3 CH3 H H OCF2CF3 2 .078 CH3 CH3 H H CN 2
Table 12: Compounds of formula iq
Figure imgf000087_0001
Compd. Re (C3) R7 R6 (C5) Rl8 n Phys. data No.
12.001 CH3 CH3 H H 0
12.002 CH3 CH3 CH3 H 0
12.003 CH3 CH3 CH=CH2 H 0
12.004 CH3 CH3 Br H 0
12.005 CH3 CH3 SMe H 0
12.006 CH3 CH3 H H
12.007 CH3 CH3 CH3 H
12.008 CH3 CH3 CH=CH2 H
12.009 CH3 CH3 Br H
12.01 CH3 CH3 SMe H
12.011 CH3 CH3 H H 2 159-161 °C
12.012 CH3 CH3 CH3 H 2 157-159°C
12.013 CH3 CH3 CH=CH2 H 2
12.014 CH3 CH3 Br H 2
12.015 CH3 CH3 SMe H 2
12.016 CH3 CH3 CH3 CH3 0
12.017 CH3 CH3 CH=CH2 CH3 0
12.018 CH3 CH3 Br CH3 0 Compd. Re (C3) R7 R6 (C5) Rl8 n Phys. data No.
12.019 CH3 CH3 SMe CH3 0
12.02 CH3 CH3 H CH3
12.021 CH3 CH3 CH3 CH3
12.022 CH3 CH3 CH=CH2 CH3
12.023 CH3 CH3 Br CH3
12.024 CH3 CH3 SMe CH3
12.025 CH3 CH3 H CH3 2
12.026 CH3 CH3 CH3 CH3 2
12.027 CH3 CH3 CH=CH2 CH3 2
12.028 CH3 CH3 Br CH3 2
12.029 CH3 CH3 SMe CH3 2
'Re (C3)' in Table 12 above means that the substituent R6 is bonded to carbon atom 3 in the compound of formula Iq; and accordingly 'R6 (C5)' means that the substituent R6 is bonded to carbon atom 5 in the compound of formula Iq.
Table 13: Compounds of formula lr
Figure imgf000088_0001
Compd. Re Re R7 R7 Rl8 n Phys. data No.
13.001 H H H H CH3 0 viscous oil
13.002 H H H H CF3 0
13.003 H H H H CO2CH2CH3 0 viscous oil
13.004 H H H H CH3 1
13.005 H H H H CF3 1
13.006 H H H H CO2CH2CH3 1 Compd. Re Re R7 R7 Rl8 n Phys. data No.
13.007 H H H H CH3 2 129-132°C
13.008 H H H H CF3 2
13.009 H H H H CO2CH2CH3 2 viscous oil
13.010 CH3 H H H H 0
13.01 1 CH3 H H H CH3 0
13.012 CH3 H H H CF3 0
13.013 CH3 H H H CO2CH2CH3 0
13.014 CH3 H H H H 1
13.015 CH3 H H H CH3 1
13.016 CH3 H H H CF3 1
13.017 CH3 H H H CO2CH2CH3 1
13.018 CH3 H H H H 2
13.019 CH3 H H H CH3 2
13.020 CH3 H H H CF3 2
13.021 CH3 H H H CO2CH2CH3 2
13.022 CH3 H CH3 H H 0 139-140°C
13.023 CH3 H CH3 H CH3 0
13.024 CH3 H CH3 H CF3 0
13.025 CH3 H CH3 H CO2CH2CH3 0
13.026 CH3 H CH3 H H 1
13.027 CH3 H CH3 H CH3 1
13.028 CH3 H CH3 H CF3 1
13.029 CH3 H CH3 H CO2CH2CH3 1
13.030 CH3 H CH3 H H 2 179-180°C
13.031 CH3 H CH3 H CH3 2
13.032 CH3 H CH3 H CF3 2
13.033 CH3 H CH3 H CO2CH2CH3 2
13.034 CH3 CH3 CH3 H H 0 viscous oil
13.035 CH3 CH3 CH3 H CH3 0
13.036 CH3 CH3 CH3 H CF3 0
13.037 CH3 CH3 CH3 H CO2CH2CH3 0
13.038 CH3 CH3 CH3 H H 1 amorphous ω CO ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω CO ω ω ω ω ω CO ω CO ω ω ω o b b b b b b b b b b b b b cn b en O b cn cn n cn b
• l ) O) c bn cn n b cn b b cn cn c bn cn cn n b cn cn b -fc. b -fc. b b 4k b -fc. bk b 4k bk b 4k b
-fc. CO zi o CO 00 -si cn n k ω ro o CO 00 cn n 4k ω ro o CD 00 •-4 cn cn -fc. ω ro o CD P-l α.
CO O CO CO CO CO CO CO CO CO CO CO CO O O O O O O O O O O O ro o O O O O o O O O O o O o O O o O O O O O
X X X X X X X X X X X o X X X X X X X X X X X X X X X X X X X X
X
X X X X X X X X X X X X X o o o o o o o o o o o o o o o o o o o
X X ω X X X X X X X X X X X X X X X X X
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X τ^ ox ox ox ox ox ox ox ox ox ox ox ox τx τx X X X X X
Figure imgf000090_0001
ro ro ro ro ->■ o o ro ro ro ro -j- -^ -' -' ro ro ro ro -»• 3
< TJ co' ιo 3- o cn o φ CO c CO
CO ro oo 3' X 03
~ O 03
CO ω CO ω CO o o o b CO b CO ro o CO 00
CO CO CO CO CO O o o o o
X X X X X
Figure imgf000091_0001
o o o o o o X X X X X X X X o o o o o o o o o o o o o
X X X X X X X X X X o
X X X X X X X X X X X X X X X
o o o o o o o o o o o o o o o o o O o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ^^ ^^. x x x x x x x x x x x x X
Figure imgf000091_0002
_i _ O o ro ro ro ro -'- -' -* o o lo ro ro ro ro ro -' -'- ^
< <
CO CO o o o o
— c ro
CO CO -fc TJ
3" o o φ ><
— — ιo CO ro
4k
N m cn 3 CX
CO o 0 ^*3 o o O o 03
3 3
Φ Φ
co co co co co ω co co co co ω co co ω co ω ω co co co co ω ω co co co ω ω co ω co co -yO ω co co co co ro ro ro ro ro ro ro ro ro ro -' -' -' -i -'. -^ -^ -' -' -'- o o o o o o o - TJ 4k co ro -i o co oo --4 cn cn 4k co ro -' O co oo -si cn cn 4k C ro -^ o cD Oo -sj cn cn -fc. co x o CO CO CO CO CO CO CO CO CO CO CO O CO CO CO CO CO CO CO CO CO ω CO CO CO CO ro O O ω ro o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o X
T X T X X X X X X X X X X X X X X X X X X X X X X X T T T T T T
CO O CO CO CO O O CO CO O O CO O CO CO CO CO CO CO CO CO CO O CO CO
X o o o o o o o o o o o o o o o o o o o o o o o o o o X o X o X o X o X X o X
X X X X X X X X X X X X X X X X X X X X X X X X X
JL o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X J. _L -L JL JL J. JL _L J. _L _L JL X X X X X X X
ox ox ox ox ox ox ox ox ox ox ox ox ox x x x x x x x x x x x x o o o o o o
X X X X X X
Figure imgf000092_0001
ro ro ro r ro -^ -' -* -* ro ro ro ro -^ -^ -^ ro ro ro ro -»■ 3
00
CO m
-— sii ro
TJ ιo o o 3" o o O
CO m 3 CX Φ 0)
CO CO o o 0>
3
CD o
3
Compd. Re Re R7 R7 R18 n Phys. data No.
13.135 OCH3 H H H CH3 0
Figure imgf000093_0001
13.137 OCH3 H H H CO2CH2CH3 0
13.138 OCH3 H H H H 1
13.139 OCH3 H H H CH3 1
13.140 OCH3 H H H CF3 1
13.141 OCH3 H H H CO2CH2CH3 1
13.142 OCH3 H H H H 2
13.143 OCH3 H H H CH3 2
13.144 OCH3 H H H CF3 2
13.145 OCH3 H H H C02CH2CH3 2
13.146 OCH3 H CH3 H H 0
13.147 OCH3 H CH3 H CH3 0
13.148 OCH3 H CH3 H CF3 0
13.149 OCH3 H CH3 H CO2CH2CH3 0
13.150 OCH3 H CH3 H H 1
13.151 OCH3 H CH3 H CH3 1
13.152 OCH3 H CH3 H CF3 1
13.153 OCH3 H CH3 H CO2CH2CH3 1
13.154 OCH3 H CH3 H H 2
Figure imgf000093_0002
13.157 OCH3 H CH3 H CO2CH2CH3 2
13.158 OCH3 CH3 CH3 H H 0 resin (E isomer)
13.159 OCH3 CH3 CH3 H H 0 104-105°C (Z isomer)
13.160 OCH3 CH3 CH3 H CH3 0
13.161 OCH3 CH3 CH3 H CF3 0
13.162 OCH3 CH3 CH3 H CO2CH2CH3 0
13.163 OCH3 CH3 CH3 H H 1
13.164 OCH3 CH3 CH3 H CH3 1
13.165 OCH3 CH3 CH3 H CF3 1
13.166 OCH3 CH3 CH3 H CO2CH2CH3 1 Compd. Re Re R7 R7 R18 n Phys. data No.
13.167 OCH3 CH3 CH3 H H 2 resin (Z isomer)
13.168 OCH3 CH3 CH3 H H 2 resin (E isomer)
13.169 OCH3 CH3 CH3 H CH3 2
13.170 OCH3 CH3 CH3 H CF3 2
13.171 OCH3 CH3 CH3 H CO2CH2CH3 2
13.172 OCH3 CH3 CH3 CH3 H 0
13.173 OCH3 CH3 CH3 CH3 CH3 0
13.174 OCH3 CH3 CH3 CH3 CF3 0
13.175 OCH3 CH3 CH3 CH3 CO2CH2CH3 0
13.176 OCH3 CH3 CH3 CH3 H 1
13.177 OCH3 CH3 CH3 CH3 CH3 1
13.178 OCH3 CH3 CH3 CH3 CF3 1
13.179 OCH3 CH3 CH3 CH3 C02CH2CH3 1
13.180 OCH3 CH3 CH3 CH3 H 2
13.181 OCH3 CH3 CH3 CH3 CH3 2
13.182 OCH3 CH3 CH3 CH3 CF3 2
13.183 OCH3 CH3 CH3 CH3 CO2CH2CH3 2
Figure imgf000094_0001
13.186 OCH3 H OCH3 H CF3 0
13.187 OCH3 H OCH3 H CO2CH CH3 0
Figure imgf000094_0002
13.191 OCH3 H OCH3 H Cθ2CH2CH3 1
13.192 OCH3 H OCH3 H H 2
Figure imgf000094_0003
13.195 OCH3 H OCH3 H CO2CH2CH3 2
13.196 OCH3 CH3 OCH3 CH3 H 0
13.197 OCH3 CH3 OCH3 CH3 CH3 0
13.198 OCH3 CH3 OCH3 CH3 CF3 0 CO ro
CO o
Figure imgf000095_0001
CO CO CO CO CO CO CO CO CO CO O CO CO CO CO CO CO CO CO CO O O CO O O O O O o O O O O o O O O o o O O O O O o o o o o o o
O o o o
O O O O O O O O O X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
o o o o o o o o o o o O o o o O o o o o o o o o O o o
X X X X X X X X X o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X
o o o o o o o o o o o O o o o O o o o o o o o o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X o o o o o X
X X X X X X X X ω X X X X X X X X X X X X X X X X X X
ox ox ox ox ox ox ox ox ox ox ox x x x x x x x x x x x x ox ox ox ox ox ox ox ox ox X
Figure imgf000095_0002
M M M -' -' -' -' O ro ro ro ro -' -' -* -* ro ro ro ro -' -'. -' -i
0) en TJ en 3 3" o
CO en oo o o CX 3
O c 0
CO 03
CO CO CO O CO CO CO CO CO ω CO ω CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO ω CO o lo io ro ro io io io io io io io io io io io io io ho io io ro ro io ro io ho io io o
Ul cn cn Ul n cn Ul Ul cn n -fc. 4k 4k k 4k k 4a. 4k CO ω ω CO CO O CO CO CO z • TiJ
CO 00 -si en cn 4k CO ro —^ o CO 00 - cn Ul 4k CO ro —* o CD 00 - l en Ul 4k CO ro Q.
O O O O O o O O O O O O O O O o o O O o O O O O O O O O CO
X X X X X X X X X X X X X X X X X X X X X X X X X X ω X X O X
X σ>
o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X o
X X σ>
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X X X o X
X
Figure imgf000096_0001
ro ro ro ro -•• o ro ro ro ro -J. -I - o ro
< TJ
3" o o o o CO c c
CX o
Compd. Re Re R7 R7 Rl8 n Phys. data No.
13.260 CH3 CH3 CH3 CH2CH=CH2 H 1
13.261 CH3 CH3 CH3 CH2CH=CH2 CH3 1
13.262 CH3 CH3 CH3 CH2CH=CH2 CF3 1
13.263 CH3 CH3 CH3 CH2CH=CH2 CO2CH2CH3 1
13.264 CH3 CH3 CH3 CH2CH=CH2 H 2
13.265 CH3 CH3 CH3 CH2CH=CH2 CH3 2
13.266 CH3 CH3 CH3 CH2GH=CH2 CF3 2
13.267 CH3 CH3 CH3 CH2CCH CO2CH2CH3 2
13.268 CH3 CH3 CH3 CH2CCH H 0
13.269 CH3 CH3 CH3 CH2CCH CH3 0
13.270 CH3 CH3 CH3 CH2CCH CF3 0
13.271 CH3 CH3 CH3 CH2CCH CO2CH2CH3 0
13.272 CH3 CH3 CH3 CH2CCH H 1
13.273 CH3 CH3 CH3 CH2CCH CH3 1
13.274 CH3 CH3 CH3 CH2CCH CF3 1
13.275 CH3 CH3 CH3 CH2CCH C02CH2CH3 1
13.276 CH3 CH3 CH3 CH2CCH H 2
13.277 CH3 CH3 CH3 CH2CCH CH3 2
13.278 CH3 CH3 CH3 CH2CCH CF3 2
13.279 CH3 CH3 CH3 CH2CCH CO2CH2CH3 2
Table C: Physico -chemical data for prepared comp ounds in the above
6 and A, and also 8-11 and B. The figure before the point indicates the number of the Table, e.g. 1.027 indicates in Table 1 compound No. 027 of Table A, and 11.027 indicates in Table 11 compound No. 027 of Table C.
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Examples of specific formulations for compounds of formula I, such as emulsifiable concentrates, solutions, wettable powders, coated granules, extruder granules, dusts and suspension concentrates, are described on pages 9 to 13 of WO 97/34485.
Biological Examples
Example B1 : Herbicidal action prior to emergence of the plants (pre-emerαence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension or emulsion prepared from a 25 % wettable powder (Example F3, b), as described, for example, in WO 97/34485, or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate (Example F1 , c), as described, for example, in WO 97/34485), are applied by spraying in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Cyperus, Sinapis, Solanum
The compounds according to the invention exhibit good herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B1. Table B1 : Pre-emerαence action:
Test plant: Cyp<srus Siiαapis Solanum Cone, [g a.i./ha] Compound No.
2.001 6 2 2 2000
2.003 1 1 1 2000
2.027 3 2 2 2000
2.029 1 1 1 2000
2.034 3 5 3 2000
2.807 2 2 5 2000
3.027 3 1 1 2000
6.029 3 2 2 2000
9.001 3 2 1 2000
10.001 4 5 3 2000
10.027 3 3 2 2000
11.027 4 4 1 2000
12.012 3 7 3 2000
13.007 2 2 2 2000
13.022 3 2 2 2000
13.030 4 4 2 2000
13.038 3 2 2 2000
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 to F8, as described, for example, in WO 97/34485.
Example B2: Post-emeroence herbicidal action
In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastics pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension or emulsion of the test compounds of formula I, prepared from a 25 % wettable powder (Example F3, b), as described, for example, in WO 97/34485, or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate (Example F1 , c), as described, for example, in WO 97/34485), in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Sinapis, Solanum, Stellaria
In this test too, the compounds of formula I exhibit strong herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B2.
Table B2: Post-emergence action
Test plant: Setaria Sinapis Solanum Stellaria Cone, [g a.i./ha] Compd. Nc >.
2.001 3 1 2 4 2000
2.002 6 2 1 4 2000
2.003 4 2 2 3 2000
2.005 4 2 2 3 2000
2.008 5 2 2 2 2000
2.027 3 1 2 3 2000
2.028 3 2 2 3 2000
2.029 5 2 2 2 2000
2.030 5 2 2 2 2000
2.034 3 2 2 3 2000
2.807 3 2 1 2 2000
3.027 4 1 1 4 2000
3.029 5 2 2 2 2000
5.027 3 2 1 2 2000
6.005 2 2 2 2 2000
6.027 5 1 4 3 2000
6.029 7 1 1 2 2000
7.027 8 2 2 4 2000
9.001 4 1 1 3 2000
9.027 3 2 2 4 2000
10.001 3 1 1 3 2000 10.003 3 1 2 3 2000
10.016 3 2 3 3 2000
10.027 3 1 2 4 2000
10.029 3 3 2 3 2000
11.001 2 1 2 3 2000
11.027 2 2 2 2 2000
11.040 1 2 2 2 2000
11.066 2 1 2 2 2000
12.012 3 1 1 3 2000
13.001 4 1 1 3 2000
13.007 3 1 2 2 2000
13.022 5 1 1 2 2000
13.030 5 1 1 2 2000
13.034 3 1 1 3 2000
13.038 3 1 1 2 2000
13.042 4 1 1 2 2000
13.058 6 2 2 3 2000
13.059 7 3 2 4 2000
13.071 7 2 1 2 2000
13.079 4 1 1 3 2000
13.080 6 1 1 2 2000
13.158 2 1 1 2 2000
13.159 3 3 3 3 2000
13.167 2 1 1 2 2000
13.168 2 2 2 2 2000
13.216 6 2 4 2 2000
13.240 3 1 2 3 2000
13.252 3 3 2 3 2000
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 to F8, as described, for example, in WO 97/34485.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000103_0001
wherein
Ri is C Calkyl, d-Chaloalkyl, Cι-C4alkoxy-CrC4alkyl, C C4alkoxycarbonyl, cyano, cyano-
C C4alkyl, hydroxy-C C4alkyl, amino-C C4alkyl, CHO, C C4alkyl-ON=CH, C2-C6alkenyl,
Cι-C4alkoxycarbonyl-C2-C6alkenyl or a group — CH(OR20)OR21 ;
R2o and R21 are each independently of the other CrCalkyl; or R20 and R2ι together are -(CH2)nι-;
Figure imgf000103_0002
R2 is hydrogen or CrCalkyl;
R3 and R4 are each independently of the other hydrogen, Cι-C4alkyl or halogen; n isO, 1 or 2;
R5 is C Calkyl, CrC4haloalkyl, C2-C6alkenyl, C2-Cealkynyl, C Calkoxy, CrChaloalkoxy, Cι-C4alkyl-S(O)n2, (Cι-C4alkyl)2NS(O)2, Cι-Calkyl-S(O)2O, halogen, nitro or cyano; n2 is 0, 1 or 2;
Q is OH, halogen or a group (Q2),
Figure imgf000103_0003
Figure imgf000103_0004
Figure imgf000104_0001
R6 and R7 are each independently of the other hydrogen, OH, Cι-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C C4alkoxycarbonyl, C C4alkyl-S(O)n2, C C alkyl-NHS(O)2, phenyl or phenyl substituted by CrC alkyl, d-C4haloalkyl, Cι-C4alkoxy, C C4haloalkoxy, CrC4alkylcarbonyl, CrC alkoxycarbonyl, amino, Cι-C alkylamino, di-C C4alkylamino, CrC4alkyl-S(O)n2, C C4alkyl-S(O)2O, CrC4haloalkyl-S(O)n2, Cι-C4haloalkyl-S(O)2O, C C4alkyl-S(O)2NH, Cι-C4alkyl-S(O)2N(C C4alkyl), halogen, nitro, COOH or cyano; or R6 and R7 are each independently of the other CrC haloalkyl, -NH-C C4alkyl, -N(C1-C4alkyl)2, Cι-C6alkoxy, cyano, nitro or halogen; or adjacent R6 and R7 together are -(CH2)n3-; n3 is 2, 3, 4, 5 or 6;
W is oxygen, sulfur, -C(R18)2- or -N(R22)- ; n6 is 0 or 1 , or when W is -C(R18)2- , n6 may additionally be 2 or 3; each R18 independently of the other is hydrogen, d-dalkyl, C C4haloalkyl or d-C4alkoxy- carbonyl; or
R18 together with one of the adjacent substituents R7 forms a single bond when n6 is 1 , and the remaining geminal R6 and R7 are other than hydrogen;
R22 is hydrogen, d-C4alkyl or C C alkoxycarbonyl;
R8 is OH, d-C4alkoxy, CrC4alkylcarbonyloxy, d-C4alkoxycarbonyloxy, R23R24N-C(O)O, phenylthio, d-C4alkylthio, C C4alkyl-S(O)2O, (C C4alkoxy)2P(O)O, Cι-C4alkyl(d-C - alkoxy)P(O)O, H(d-C4alkoxy)P(O)O or benzoyloxy;
R23 and R2 are each independently of the other hydrogen or d-C4alkyl;
Y is oxygen, sulfur or -(CH2)ns-; n5 is 0, 1 , 2, 3 or 4;
R9 is hydrogen, Cι-C6alkyl, Cι-C4alkylcarbonyl, C C4alkoxycarbonyl, (C C4alkyl)NHCO or (d-C4alkyl)2NCO; R10, Rn and R12 are each independently of the others hydrogen, d-C4alkyl, d-C4alkoxy- carbonyl, phenyl or phenyl substituted by d-C alkyl, C C haloalkyl, d-C4a!koxy, C C4- haloalkoxy, C C4alkylcarbonyl, d-C alkoxycarbonyl, amino, d-C4alkylamino, di-d-C4alkyl- amino, d-C4alkyl-S(O)n2, d-C4alkyl-S(O)2O, CrC4haloalkyl-S(O)n2, Cι-C4haloalkyl-S(O)2O, d-C4alkyl-S(O)2NH, d-C4alkyl-S(O)2N(Cι-C4alkyl), halogen, nitro, COOH or cyano;
R13 is hydrogen; halogen; Cι-C4alkyl; C C alkyl substituted by unsubstituted or R17- substituted phenyl; Cι-C4haloalkyl; C2-C6alkenyl; C2-C6alkenyl substituted by unsubstituted or R17-substituted phenyl; C2-C6alkynyl; C2-C6alkynyl substituted by unsubstituted or R17- substituted phenyl; C3-C6haloalkenyl; C3-C6haloalkynyl; C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, R15 or COOR16; COOR16; CORι5; cyano; nitro; CONH2; (d-C4- alkyl)NHCO; (d-C4alkyl)2NCO; (d-C4haloalkyl)NHCO; (d-C4haloalkyl)2NCO; d-C4alkyl- S(O)n2; Cι-C4alkyl-S(O)n2 substituted by unsubstituted or R17-substituted phenyl; d-C4- alkoxy-C2-C6alkyl-S(O)n2; C2-C6alkenyl-S(O)n2; C2-C6alkenyl-S(O)n2 substituted by unsubstituted or Rι7-substituted phenyl; C2-C6alkynyl-S(O)n2; or C2-C6alkynyl-S(O)n2 substituted by unsubstituted or R17-substituted phenyl;
R15 is d-C4alkyl, d-C4haioalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6halo- alkynyl, phenyl or Rι -substituted phenyl;
R16 is hydrogen, d-C4alkyl or Cι-C haloalkyl;
R17 is halogen, d-C alkyl, C C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, Cι-C4alkoxy-d-C4alkyl, d-C4alkoxy-C3-C6alkenyl, d-C4alkoxy-C3-C6- alkynyl, cyano, nitro, COOH, d-C4alkoxycarbonyl, C C haloalkoxycarbonyl, d-C4alkyl- S(O)n2, Cι-C haloalkyl-S(O)n2, phenyl-S(O)n2; phenyl-S(O)n2 substituted on the phenyl ring by halogen, d-C4alkyl, C C haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, Cι-C - alkoxycarbonyl, d-C4alkyl-S(O)n2, C C4haloalkyl-S(O)n2, CrC4alkylcarbonyl, di-d-C4alkyl- amino, C C alkoxy, d-C4haloalkoxy, d-C4alkyl-S(O) O or C C4haloalkyl-S(O)2O; d-C4- alkylcarbonyl, di-Cι-C4alkylamino, Cι-C4alkyl-S(O)2NH, CrC4alkyl-S(O)2N(Cι-C4alkyl), d-C4haloalkyl-S(O)2NH, d-C4haloalkyl-S(O)2N(d-C4alkyl), NH2S(O)2, (Cι-C4alkyl)NHS(O)2, (d-C4alkyl)2NS(O)2, CONH2, (C C4alkyl)NHCO, (d-C4alkyl)2NCO, NH2CS, (d-C4alkyl)NHCS, (Cι-C4alkyl)2NCS, d-C4alkoxy, d-d aloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C4alkyl-S(O)2O, d-C4haloalkyl-S(O)2O, phenyl-S(O)2O or phenyl- S(O)2O substituted on the phenyl ring by halogen, d-C alkyl, d-C haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, Cι-C4alkoxycarbonyl, d-C4alkyl-S(O)n2, Cι-C haloalkyl- S(O)n2, C C4alkylcarbonyl, di-C C4alkylamino, d-C4alkoxy, CrC4haloalkoxy, C C4alkyl- S(O)2O or d-C4haloalkyl-S(O)2O; and
R14 is d-C4alkyl, C C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C8halo- alkynyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by halogen, d-C4alkyl, Cι-C4halo- alkyl, C3-C6alkenyl, C3-Cehaloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, phenyl or phenyl substituted by halogen, d-C4alkyl, C1-C haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, C C4alkoxycarbonyl, d-C alkyl-S(O)n2, C C4haloalkyl-S(O)n2, d-C4alkylcarbonyl, di-Cι-C4alkylamino, C C4alkoxy, d-C haloalkoxy, d-C4alkyl-S(O)2O or d-C4haloalkyl- S(O)2O, or an agrochemically acceptable salt or a stereoisomer of such a compound of formula I.
2. A compound according to claim 1 , wherein R is Cι-C4alkyl, d-C4haloalkyl, d-C4alkoxy- d-dalkyl, C C alkoxycarbonyl, cyano, cyano-C C4alkyl, CHO, C C4alkyl-ON=CH,
C2-C6alkenyl, d-C4alkoxycarbonyl-C2-C6alkenyl or a group — CH(OR20)OR21 ;
W is oxygen, sulfur, -C(R18)2- or -N(R22)-; each R18 independently of the other is hydrogen, d-C4alkyl or Cι-C4alkoxycarbonyl; and R22 is hydrogen, C C alkyl or Cι-C alkoxycarbonyl.
3. A process for the preparation of a compound of formula I
Figure imgf000106_0001
wherein Ri to R5 and n are as defined in claim 1 ; Q is a group (Qi),
Figure imgf000107_0001
Figure imgf000107_0002
R7, R9, Rio, W, n8 and Y are as defined in claim 1 , which comprises either
a) reacting a compound of formula III
Figure imgf000107_0003
wherein Ri to R5 and n are as defined and X is a leaving group, in an inert organic solvent in the presence of a base with a compound of formula IV
Figure imgf000107_0004
wherein
Zi is C(R6)R7, Z2 is (W)n6, Z3 is C(R6)R7 and n4 is 0 (= group CU);
Zi is CH, Z2 is oxygen, sulfur or -(CH2)n5- (=Y), Z3 is CH and n4 is 2 (= group Q2);
Zi is CH2, Z2 is CHNHRg, Z3 is CH2 and n4 is 0 (= group Q3); or
Zi is NR10, Z2 is oxygen, Z3 is C(R6)R7 and n4 is 0 (= group Q4), and R6, R7, Rg, Rio, W, n6 and n5 are as defined in claim 1 , to form a compound of formula Ic
Figure imgf000108_0001
and then isomerising that compound; or
b) reacting a compound of formula Id
Figure imgf000108_0002
wherein Ri to R5 and n are as defined, with a compound of formula IV
Figure imgf000108_0003
wherein Z Z2, Z3 and n4 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula Ic
Figure imgf000108_0004
and then isomerising that compound.
4. A compound of formula V
Figure imgf000109_0001
wherein Ri to R5, Rι4 and n are as defined in claim 1.
5. A compound of formula VII
Figure imgf000109_0002
wherein Ri to R5, Rι4 and n are as defined in claim 1 ; R25 is d-C4alkyl, d-C alkyl substituted by unsubstituted or R17-substituted phenyl, CrC alkoxy-C2-C6alkyl, C2-C6alkenyl, C2-C6alkenyl substituted by unsubstituted or Rι7-substituted phenyl, C2-C6alkynyl or C2-C6- alkynyl substituted by unsubstituted or R17-substituted phenyl; R17 is halogen, Cι-C alkyl, C C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C C4alkoxy- d-dalkyl, C1-C4alkoxy-C3-C6alkenyl, d-C4alkoxy-C3-C6alkynyl, cyano, nitro, COOH, d- C alkoxycarbonyl, Cι-C4haloalkoxycarbonyl, d-C4alkyl-S(O)n2, C C4haloalkyl-S(O)n2, phenyl-S(O)n2; phenyl-S(O)n2 substituted on the phenyl ring by halogen, d-C alkyl, d-C - haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, Cι-C4alkoxycarbonyl, Cι-C4alkyl- S(O)n2, Cι-C haloalkyl-S(O)n2, d-C4alkylcarbonyl, di-Cι-C alkylamino, C C4alkoxy, CrC4- haloalkoxy, C C4alkyl-S(O)2O or C C4haloalkyl-S(O)2O; d-C4alkylcarbonyl, di-C C4alkyl- amino, d-C4alkyl-S(O)2NH, d-C4alkyl-S(O)2N(d-dalkyl), d-C4haloalkyl-S(O)2NH, Cι-C4- haloalkyl-S(O)2N(Cι-C4-alkyl), NH2S(O)2, (C C4alkyl)NHS(O)2, (d-dalkyl)2NS(O)2l CONH2, (d-C4alkyl)NHCO, (C C4alkyl)2NCO, NH2CS, (d-C4alkyl)NHCS, (C C4alkyl)2NCS, CrC4- alkoxy, d-C4haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C4alkyl-S(O)2O, C C halo- alkyl-S(O)2O, phenyl-S(O)2O or phenyl-S(O) O substituted on the phenyl ring by halogen, d-C4alkyl, d-C haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, C C alkoxy- carbonyl, Cι-C4alkyl-S(O)n2, Cι-C4haloalkyl-S(O)n2, d-C4alkylcarbonyl, di-C C alkylamino, d-C4alkoxy, Cι-C4haloalkoxy, d-C4alkyl-S(O)2O or d-C4haloalkyl-S(O)2O; and n2 is 0, 1 or 2.
6. A compound of formula IX
Figure imgf000110_0001
wherein Ri to R5, R and n are as defined in claim 1 ; R 3 is hydrogen, d-C4alkyl, CrC alkyl substituted by unsubstituted or R17-substituted phenyl, d-C4haloalkyl, C2-C6alkenyl, C2-C6- alkenyl substituted by unsubstituted or R17-substituted phenyl, C2-C6alkynyl, C2-C6alkynyl substituted by unsubstituted or R17-substituted phenyl, C3-C6haloalkenyl, C3-C6haloalkynyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by halogen, R15 or COOR16; Rι7 is halogen, d-dalkyl, d-C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyI, d-C4alkoxy-Cι-C4alkyl, Cι-C4alkoxy-C3-C6alkenyl, Cι-C4alkoxy-C3-C6alkynyl, cyano, nitro, COOH, d-dalkoxycarbonyl, C C4haloalkoxycarbonyl, Cι-C4alkyl-S(O)n2, d-C4haloalkyl- S(O)n2, phenyl-S(O)n2; phenyl-S(O)n2 substituted on the phenyl ring by halogen, d-C alkyl, d-dhaloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, Cι-C alkoxycarbonyl, Cι-C4alkyI-S(O)n2, d-C4haloalkyl-S(O)n2, C C4alkylcarbonyl, di-C C4alkylamino, d-C alkoxy, C C4haloalkoxy, d-C alkyl-S(O)2O or d-C4haloalkyl-S(O)2O; C C alkyl- carbonyl, di-C C alkylamino, C C alkyl-S(O)2NH, Cι-C4alkyl-S(O)2N(d-C4alkyl), d-C4- haloalkyl-S(O)2NH, Cι-C4haloalkyl-S(O)2N(Cι-C4alkyl), NH2S(O)2, (C C4alkyl)NHS(O)2, (Cι-C4alkyl)2NS(O)2, CONH2, (C C4alkyl)NHCO, (C C4alkyl)2NCO, NH2CS, (d-C4alkyl)- NHCS, (Cι-C4alkyl)2NCS, Cι-C4alkoxy, d-C4haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C alkyl-S(O)2O, C C4haloalkyl-S(O)2O, phenyl-S(O)2O or phenyl-S(O)2O substituted on the phenyl ring by halogen, d-C alkyl, C C haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro, COOH, C C4alkoxycarbonyl, Cι-C4alkyl-S(O)n2, C C4haloalkyl-S(O)n2, CrC4alkyl- carbonyl, di-Cι-C4alkylamino, C C4alkoxy, Cι-C4haloalkoxy, Cι-C alkyl-S(O)2O or C C4halo- alkyl-S(O)2O; n2 is 0, 1 or 2; Rι5 is d-C4alkyl, Cι-C4haloalkyl, C3-C6alkenyl, C3-C6- haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, phenyl or Rι -substituted phenyl; R16 is hydrogen, d-C4alkyl or C C haloalkyl; and R27 is d-C alkyl.
7. A herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective content of a compound of formula I, and an inert carrier.
8. A method of controlling undesired plant growth, wherein a compound of formula I, or a composition comprising such a compound, is applied in a herbicidally effective amount to the crops of useful plants or to the locus thereof.
9. The use of a composition according to claim 7 in controlling undesired plant growth.
PCT/EP1998/005247 1997-08-20 1998-08-18 Benzothiophene derivates as herbicides Ceased WO1999009023A1 (en)

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CN112430228B (en) * 2020-11-25 2021-09-07 四川大学 A kind of chiral 2,3-dihydrobenzo[b]thiophene 1,1-dioxide, derivative and preparation method

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WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives

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