[go: up one dir, main page]

WO1999024409A1 - Isoxazole derivatives and their use as herbicides - Google Patents

Isoxazole derivatives and their use as herbicides Download PDF

Info

Publication number
WO1999024409A1
WO1999024409A1 PCT/EP1998/007177 EP9807177W WO9924409A1 WO 1999024409 A1 WO1999024409 A1 WO 1999024409A1 EP 9807177 W EP9807177 W EP 9807177W WO 9924409 A1 WO9924409 A1 WO 9924409A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
phenyl
alkoxy
alkenyl
alkynyl
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/EP1998/007177
Other languages
French (fr)
Inventor
Jürgen Schaetzer
Walter Kunz
Alain De Mesmaeker
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novartis Erfindungen Verwaltungs GmbH, Novartis AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Priority to AU15615/99A priority Critical patent/AU1561599A/en
Publication of WO1999024409A1 publication Critical patent/WO1999024409A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—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
    • 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
    • C07D413/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to novel herbicidally active isoxazole derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Isoxazole derivatives having herbicidal action are described, for example, in
  • Z is S, SO or SO 2 ;
  • Ri is hydrogen, d-C 8 alkyl or C ⁇ -C 8 alkyl substituted by halogen, C ⁇ -C 4 alkoxy, CrC 4 alkylthio, d-dalkylsulfonyl, C C 4 alkylsulfinyl, hydroxy, cyano, nitro, -CHO, -CO 2 R 2 , -COR 3 , -COSR 4 , -NR 5 R 6 , CONR 36 R37 or by phenyl which in turn may be substituted by C ⁇ -C 4 alkyl, C C 6 halo- alkyl, d-dalkoxy, C ⁇ -C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 - alkynyioxy, halogen, nitro, cyano, -COOH, COOC C 4 alkyl, COOpheny
  • NHSO 2 -d-C 4 alkyl NHSO 2 -phenyl, N(d-C 6 alkyl)SO 2 -C ⁇ -C 4 - alkyl, N(C ⁇ -C 6 alkyl)SO 2 -phenyl, N(C 2 -C 6 alkenyl)SO 2 -Ci-C 4 alkyl, N(C 2 -C 6 alkenyl)SO 2 -phenyl, N(C 3 -C 6 alkynyl)SO 2 -Ci-C 4 alkyl, N(C 3 -C 6 alkynyl)SO 2 -phenyl, N(C-3-dcycloalkyl)SO 2 -C 1 -C 4 - alkyl, N(C 3 -C 7 cycloalkyl)SO 2 -phenyl, N(phenyl)SO 2 -Crdalkyl.
  • Ri is C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkyl substituted by Crdalkyl, d-C alkoxy, d-C alkyl- thio, C ⁇ -C alkylsulfinyl, d-C 4 alkylsulfonyl or by phenyl which in turn may be substituted by halogen, nitro, cyano, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, d-C haloalkylthio, C C 4 alkyl or by C ⁇ -C 4 haloalkyl; or Ri is -(CH 2 ) q -C- 3 -C 7 cycloa!kyl, phenyl or phenyl substituted by d-C alkyl, d-C 6 haloalkyl, Crdalkoxy, C ⁇ -C haloalkoxy, C 2
  • R 2 , R 38 , R t and R 6 e are each independently of the others hydrogen, d-C 4 alkyl, phenyl or phenyl substituted by d-dalkyl, C ⁇ -C 6 haloalkyl, d-dalkoxy, d-C 4 haloalkoxy, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C 4 alkyl, COOphenyl, C ⁇ -C 4 alkoxy, phenoxy, (d-C alkoxy)-C C 4 alkyl (C C 4 alkyl- thio)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfon
  • R 3 , R 39 and R 67 are each independently of the others C C alkyl, phenyl or phenyl substituted by d-dalkyl, CrC 6 haloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOC C 4 alkyl, COOphenyl, C C 4 alkoxy, phenoxy, (C C 4 alkoxy)-C ⁇ -C 4 alkyl, (C ⁇ -C 4 alkylthio)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-d-C 4 alkyl, (d-C 4 alkylsulfonyl)-C ⁇ -C 4 alkyl, NHS
  • OSO 2 -C ⁇ -C haloalkyl OSO 2 -phenyl, CrC 4 alkylthio, C ⁇ -C haloalkylthio, phenylthio, C C alkylsulfonyl, C C 4 halo- alkylsulfonyl, phenylsulfonyl, d-C 4 alkylsulfinyl, C ⁇ -C 4 haloalkylsulfinyl, phenylsulfinyl, -(CH 2 ) t - phenyl or by -NR 56 CO 2 R 55 ; R 4 is d-dalkyl;
  • R 5 is hydrogen, C C ⁇ lkyl, C 2 -C 6 alkenyl, Cs-Cealkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by d-C alkyl, CrCehaloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOd-dalkyl, COOphenyl, d-C alkoxy, phenoxy, (C C alkoxy)-C ⁇ -C 4 alkyl, (C ⁇ -C 4 alkylthio)-CrC 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-C ⁇ -C 4 alkyl,
  • R 7 is phenyl, substituted phenyl, d-dalkyl, d-dalkoxy or -NR 8 R 9 ;
  • R is C ⁇ -C 6 alkyl, CrC 6 alkoxy, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkynyl, C 2 -C 6 alkoxyalkenyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by d-C 4 alkyl, d-C 4 haloalkyl or by d-C 4 alkoxy; 3- to 6-membered, saturated heterocyclyl; or phenyl which may be substituted by halogen, d-C alkyl, C C 4 haloalkyl, d-C 4 alkoxy, C ⁇ -C haloalkoxy, nitro, cyano, C C 4 alkylthio, d
  • Ri3, Reg. R70 and R 7 ⁇ are each independently of the others hydrogen, d-C 6 alkyl, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by d-dalkyl, d-C 6 halo- alkyl, C ⁇ -C alkoxy, d-C haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 - alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C 4 alkyl, COOphenyl, C C alkoxy, phenoxy, (d-dalkoxyj-d-dalkyl, (C ⁇ -C 4 alkylthio)-d-C 4 alkyl, (d-C 4 alky
  • R3i > R 4 3 > R48, R52, R ⁇ , Reo, Rw, Res and R 80 are each independently of the others hydrogen, C ⁇ -C 4 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 7 cycloalkyl; n is 0, 1 or 2; m, p, q, s, t, u, v and x are each independently of the others 1 , 2, 3 or 4; R25. 26, R27. R281 R29. R30, R32. 331 R ⁇ ⁇ R35. R40. R 4 i ⁇ 42i R 5. R 4 6. R471 R49, R501 R511 R53.
  • Res. Res, R77, R78 and R 79 are hydrogen, d-C 4 alkyl, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by halogen, nitro, cyano, d-dalkoxy, C C haloalkoxy, C C 4 alkylthio, C C 4 haloalkylthio, d-C 4 alkyl or by d-C halo- alkyl; and agronomically acceptable salts of those compounds.
  • alkyl groups that appear in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals.
  • the alkenyl and alkynyl groups may be mono- or poly-unsaturated.
  • Halogen is generally fluorine, chlorine, bromine or iodine. The same applies also to halogen in connection with other meanings, such as haloalkyl or halophenyl.
  • Haloalkyl groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichlorornethyl, tri- chloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloro- methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichl ⁇ ropropenyl and 4,4,4-trifluoro-but-2-en- 1 -yl.
  • halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichl ⁇ ropropenyl and 4,4,4-trifluoro-
  • haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly- substituted by halogen, halogen being bromine, iodine and, especially, fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trif luoro-but-2-yn-1 -yl.
  • alkynyl groups mono- or poly-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.
  • Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy.
  • Alkyl- carbonyl is preferably acetyl or propionyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy- carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxy- carbonyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl- thio or tert-butylthio, preferably methylthio and ethylthio.
  • Alkylsulfinyl is, for example, methyl- sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.
  • alkoxyalkoxy examples are: methoxymethoxy, methoxyethoxy, methoxy- propoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine.
  • Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n- propylmethylamino, dibutylamino and diisopropylamino.
  • Alkoxyalkyl groups preferably have from 1 to 8 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or iso- propoxyethyl.
  • Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms.
  • Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propyl- thiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butyl- thioethyl or butylthiobutyl.
  • the cycloalkyl groups preferably have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Phenyl also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl or phenoxyalkyl
  • the substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions with respect to the ring linkage site.
  • Heterocyclyl is to be understood as meaning ring systems which contain, in addition to carbon atoms, at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Heterocyclyl ring systems within the scope of the present invention may also be substituted. Examples of suitable substituents are d-C 4 alkyl, d-C haloalkyl, d-d- alkoxy, cyano, nitro, d-C 4 alkylsulfonyl, C ⁇ -C alkylsulfinyl, d-C alkylthio and C 3 -C 6 cyclo- alkyl.
  • substituent Ar is heterocyclyl
  • two adjacent substituents on the heterocyclyl may form a 5- to 7-membered ring which may be substituted by C ⁇ -C alkyl, d-C 4 haloalkyl, d-dalkoxy, cyano, nitro, d-dalkylsulfonyl, C ⁇ -C 4 alkylsulfinyl, C ⁇ -C 4 alkylthio or by C 3 -C 6 - cycloalkyl.
  • Heterocyclyl may be, for example, furyl, thiophenyl, pyrrolidyl, piperidinyl, mo holinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, thiazolyl, pyrazolyl, 1 ,2,4-triazolyl, 1 ,2,3-triazolyl, tetrazolyl, pyrimidyl, pyrazinyl, symmetrical or
  • asymmetrical triazinyl piperazinyl, oxazolinyl (for example: ), oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl, oxetanyl, especially 2-oxetanyl, or phthalimidyl.
  • the invention also includes the salts which the compounds of formula I are capable of forming especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal bases special mention is to be made, as salt-forming agents, of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially those of sodium and potassium.
  • amines suitable for the formation of ammonium salts both ammonia and primary, secondary and tertiary d-C 18 alkylamines, C ⁇ -C 4 hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl- nonylamine, methyl-pentadecylamine, methyl-oc
  • quaternary ammonium bases suitable for the formation of salts are [N(R a R R c R d )] + OH " , wherein R a , R b , R c and R d are each independently of the others C ⁇ -C 4 alkyl.
  • Further suitable tetraalkyl- ammonium bases containing different anions can be obtained, for example, by anion exchange reactions.
  • Preferred compounds of formula I are those wherein Ar is a group
  • R 81 , R 82 , R ⁇ 3, R ⁇ , Res. R ⁇ e, ⁇ 7 and R 88 are each independently of the others hydrogen, halogen, C ⁇ -C 4 alkyl, d-dhaloalkyl, C ⁇ -C alkoxy, d-C 4 haloalkoxy, (d-C 4 alkoxy)- d-dalkyl, (C C 4 alkylthio)-C ⁇ -C 4 alkyl, (d-dalkylsulfony -d-dalkyl, (d-C 4 alkylsulfinyl)- d-C 4 alkyl, d-C alkylthio, C C 4 haloalkylthio, phenylthio, d-C 4 alkylsulfonyl, d-C 4 haloalkyl- sulfonyl, phenylsulfonyl, C C 4 alkylsulfinyl,
  • X L X 2 , X 3) Xt, Y ⁇ , Y 2 , Y 3 and Y are each independently of the others O, S, SO, SO 2 , NR 89 ,
  • R 89 is hydrogen, C ⁇ -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 7 cycloalkyl;
  • R 19 , R 20 and R90 are each independently of the others hydrogen or d-C 4 alkyl.
  • R is hydrogen, d-dalkyl, d-C 4 alkyl substituted by halogen, methoxy, ethoxy, cyano or by COOR 2 , or C 3 -C 6 alkenyl or halo-substituted C 3 -C 6 alkenyl, or C 3 -C 6 alkynyl.
  • T T1 , T2
  • T2 CN, CON(CH 3 )-OCH 3
  • Tx hydrogen, COOH or COO-d-C alkyl
  • M metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
  • Both the keto compound that is used and the nitrile may carry on the ⁇ -carbon atom an additional carboxyl or alkoxycarbonyl group Tx suitable for condensation.
  • Tx is COO-d-C alkyl
  • hydrolysis and decarboxylation can be carried out once the acylation is complete.
  • an acid chloride ArCOCI it may suitably be used with, for example, BuLi as the base at from -60 to -80°C and tetrahydrofuran as the solvent (Synthesis 1983. 308; Synthesis 1984. 1 ; J. Org. Chem. 54, 4229; US 5 545 762; US 5 656 373).
  • the keto compound Pill is then reacted with carbon disulfide in the presence of a base, such as NaH, an alkali alkanolate (e.g. NaOEt) or an alkali carbonate, e.g. potassium carbonate, or a fluoride salt (e.g. KF) that is free or bonded, for example, to aluminium oxide, in an inert solvent at from -20 to +80°C and alkylated using an alkylating agent R XP1 , wherein R. is as defined above and XP1 is Hal (Cl, Br, I) or OS(O)OR ⁇ , to form the ketene dithioacetal Pll (Chem. Ber. 95, 2861 , Z. Chem. 16, 397, 1976).
  • a base such as NaH, an alkali alkanolate (e.g. NaOEt) or an alkali carbonate, e.g. potassium carbonate, or a fluoride salt (e.g. KF) that
  • the intermediates of formula PI are novel and have been developed especially for the preparation of the compounds of formula I, and the present invention therefore relates also thereto.
  • cyano- or amide-substituted isoxazoles are obtained in the cyclisation (step 3), they are subsequently reacted at from -120° to +40°C in an inert solvent, such as hexane, an ether, THF, (if required after transmetallation to, for example, potassium, zinc or cadmium salts) with Grignard (RMgHal)- or alkyl lithium (RLi) to form the compound of formula ly (J. Het. Chem. 12, 413; Tetrahedr. 3 ., 499 (1975)).
  • T T1 , T2
  • T2 CN, CON(Me)-OCH 3
  • M metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
  • an aryl ketone Pill prepared according to Scheme 1
  • an enamine PVI Reaction step 7
  • PVIb nitrite oxides
  • Intermediates PV wherein E is halogen can then be converted, by reaction with mercaptans HSRi, preferably in the presence of an acid acceptor (e.g. bases such as tertiary amines or oxiranes such as propylene oxide) in inert solvents at temperatures of from -20 to 150°C, into the products Ix or PI already obtainable according to Scheme 1.
  • an acid acceptor e.g. bases such as tertiary amines or oxiranes such as propylene oxide
  • Some enamines PVI are known (US-A-5 656 573, EP-A-0 625 505), or they are prepared according to methods known perse, for example by reaction of a keto compound Pill with a secondary amine HN(P 1 )P 2 wherein HN(P 1 )P 2 is an open-chained or cyclic compound such as HNEt 2 , pyrrolidine or morpholine, in the presence of an acid catalyst (acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins, such as Amberlyst IRA 400) and of an inert solvent, with removal of the water of reaction that forms (molecular sieve, azeotropic distillation) at temperatures of from 40 to 200°C (Tetrahedron Letters 1988. 3997).
  • an acid catalyst acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins
  • Pg is a protecting group, such as Si(alkyl) 3 , C(Me) 2 OH, Sn(alkyl) 3)
  • a palladium catalyst such as Pd(Ph 3 P) 4 or Pd(Ph 3 P) 2 CI 2 or Pd(OAc) 2 and Cul
  • an amine e.g. HNEt 2
  • an inert solvent Org. React.
  • a base e.g. NaH, tertiary amine
  • a suitable tin compound e.g. (R 4 ) 3 -SnCI
  • 4-stannyl compounds XII are obtained, which can likewise be reacted with acid chlorides RCO-CI analogously to Heterocycles 43, 1301 (1996) in the presence of palladium catalysts (e.g. Pd(Ph 3 P) 2 CI 2 ) to form the compound of formula I.
  • palladium catalysts e.g. Pd(Ph 3 P) 2 CI 2
  • the compounds of formula I can be prepared also by the direct addition of nitrite oxides PIVb to unsaturated ketones of formula PIX (alkynes) or PXIII (alkenes) in accordance with the following scheme:
  • Suitable oxidising agents for the selective oxidation of the compound of formula PXVIII to the compound of formula KUb, wherein Ar, R and Ri are as defined for formula I, n is 1 or 2 and 'Hal is halogen, preferably chlorine or bromine, are metachloroper- benzoic acid, sodium perborate and tetrabutylammonium perruthenate.
  • the compound of formula KUb is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
  • Alkyl- or aryl-thiomethylnitromethane derivatives of formula PXIII obtainable according to known methods (e.g. J. Org. Chem. 53, 5369 (1988)) are converted into the corresponding nitrile oxides PIVb in the presence of a dehydrating agent, for example an isocyanate of formula PXIV, and of a base, for example a tertiary amine (e.g.
  • the cyclisation is preferably carried out without isolation of the intermediates in a one-pot reaction in one of the mentioned solvents.
  • suitable catalysts are Lewis acids, such as Ti(IV) salts, such as Ti(OisoPr) 4 (J. Am. Chem. Soc. 118, 59; ibid. 111 , 5340; J. Org. Chem. 59, 5687), or complexes such as Ti(OTs) 2 (TADDOL) (Helv.
  • Eu (fod) 3 tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanate-dionato)europium(lll)) (Heterocycles 46, 95), and lanthanide complexes such as Yb(OTf) 3 (Chem. Lett. 1997, 1039).
  • Isoxazolines of formula PXVI can be converted into the end products of formula Iz according to methods known perse by means of aromatising oxidising agents such as, for example, MnO 2 (Synthesis 1976, 133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.
  • aromatising oxidising agents such as, for example, MnO 2 (Synthesis 1976, 133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.
  • the isoxazolines are first converted into the corresponding halides (preferably chlorine or bromine derivatives) PXVIII by means of a halogenating agent, such as Br 2 , Cl 2 , N-bromosuccinimide, if required with the addition of a radical initiator, such as dibenzoyi peroxide, in an inert solvent, for example carbon tetrachioride or a sulfochloride, such as thionyl chloride or trifluoromethane sulfochloride, and the halides are then reacted with a base (preferably a tertiary amine, such as triethylamine or DBU (1 ,8- diazabicyclo-(5.4.0)-undec-7-ene)) in an inert solvent, such as dichloromethane, at from -20°C to +80°C to form the products of formula I.
  • a halogenating agent such as Br 2 , Cl 2 , N-bromos
  • WO 97/43270 using 1 or 2 equivalents of an oxidising agent such as m-chloroperbenzoic acid in an inert solvent, for example dichloromethane, at temperatures of from -20°C to
  • Isoxazolines of formulae PXVI and PXVIII wherein Ar, R and R. are as defined for formula I and 'Hal is halogen, preferably chlorine or bromine, are novel and, as intermediates, the present invention relates also thereto.
  • the compounds of formulae PXVI and PXVIII have herbicidal activity.
  • Enones of formula PXV are either known or can be prepared according to known methods, for example by Wittig or Wittig-Homer condensation of an aldehyde of formula PXXI with a phosphorane PXX obtained from a halide PXIX, in an inert solvent, such as tetrahydrofuran, dioxane or acetonitrile, at temperatures of from 20°C to 160°C (analogously to Tetrahedron Lett. 1974, 2491 , scheme below).
  • enones of formula PXV are obtainable by condensation of aldehydes of formula PXXI with a methyl ketone of formula XXII
  • a bifunctional catalyst such as ammonium acetate, a pyridine/piperidine mixture (analogously to Synthesis 1980, 806), an alkali fluoride (KF, Synthesis 1983, 173), and subsequent removal of the activating group (customary hydrolysis and decarboxylation (-COOalkyl) in the case of a 1 ,3-keto ester).
  • a further process for the preparation of unsaturated ketones of formula PXV comprises the Heck reaction of an aryl halide of formula PXXIIIa
  • a palladium catalyst for example Pd(OAc) 2
  • a base such as triethylamine
  • an inert solvent such as acetonitrile or N,N-dimethylformamide
  • arylaldehydes (PXXI) required for the above-mentioned condensation reactions are either known or can be prepared according to known methods, for example by catalytic reduction of appropriate carboxylic acid halides according to Rosenmund or an analogous variant in the presence of a catalyst, for example Pd/BaSO 4 , and of a pyridine base, such as lutidine.
  • a catalyst for example Pd/BaSO 4
  • a pyridine base such as lutidine.
  • oxidising agent such as cerium(IV)-ammonium nitrate (J. prakt. Chem. 336, 470 (1994)) or phenyl dichlorophosphate/DMSO/NEt 3 (J. Org. Chem. 59, 7704 (1994)) or oxalyl chloride/DMSO (Synth. 1990, 857), to the aldehyde PXXI
  • isoxazoles of formula I are also obtainable from the dihaloformaldoximes PIVa, as shown below, by means of addition to olefins PXV via isoxazolines of formula PXVI.
  • the 3-halo-isoxazoline of formula PXVII may also be isolated.
  • reaction step (1 ) there are added to the olef in PXV in an inert solvent, such as 1 ,2- dimethoxyethane, at a temperature of from 0°C to +60°C, a base, for example an alkali hydrogen carbonate, as well as a small amount of water and the oxime PIVa and then the thiolate RiSMi is introduced in small portions over a prolonged period of about from 1 to 6 hours.
  • an inert solvent such as 1 ,2- dimethoxyethane
  • Ms is an alkali metal, preferably lithium.
  • suitable oxidising agents for the selective oxidation of the compound of formula PXVI to the compound of formula KUa, wherein Ar, R and Ri are as defined for formula I and n is 1 or 2, are metachloroperbenzoic acid, sodium perborate and tetrabutylammonium perruthenate.
  • the compound of formula KUa is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
  • Dihaloformaldehyde oximes and dithioalkylformaldehyde oximes of formula PIVa are known or can be prepared according to known methods, for example Chem. Ber. 43, 3362; Synth. Comm. 12, 601 or according to CH-A-563 967, Chem. and Industry 1979. 826.
  • Dithio-substituted formaldehyde oximes can also be obtained from the dihalo compounds and appropriate thiols in the presence of a base.
  • Substituted aryl derivatives (Ar-P3, A ⁇ -COOP ) are for the most part also known or can be prepared according to known methods (as described, for example, in US-A-5 658 858, US-A-5 656 573, EP-A-0 524 018, EP-A-0 527 037, EP-A-0 609 797, EP-A-0 588 357, WO 97/19076, WO 97/09324, WO 97/09327, WO 97/19071 , WO 96/26192, EP-A-0 768 033, WO 96/26206, WO 97/12885, WO 96/26200 and US-A-0 5 607 898).
  • the reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and can usually be carried out at room temperature.
  • the reaction mixture may if required be heated for a short time up to its boiling point.
  • the reaction times may also be shortened by adding a few drops of a base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diaza- bicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7- ene.
  • bases inorganic bases for example hydrides, such as sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.
  • the compounds of formula I may be isolated in customary manner by concentration and/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.
  • the compounds of formula I or of compositions comprising them there come into consideration any methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as, for example, the controlled release of active ingredient.
  • a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If r equired, a coating may additionally be applied (coated granules), which allows the active in igredient to be released in metered amounts over a specific period of time.
  • the compounds of formula I may be used as herbicides in unmodified form, i.e. as they are formed in the synthesis. Preferably, however, they are processed in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsif iable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wet- table powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485, pages 9 to 13. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and generally one or more solid or liquid formulation adjuvants
  • formulation adjuvants e.g. solvents or solid carriers.
  • surface-active compounds surfactants
  • solvents and solid carriers are given, for example, in WO 97/34485, page 6.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • anionic, non-ionic and cationic surfactants examples include WO 97/34485, pages 7 and 8.
  • Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
  • the herbicidal formulations usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
  • a surfactant e.g. a surfactant.
  • the compositions may also comprise other auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the type of action, on the stage of development of the cultivated plant and of the weed, and also on the application (place, time, method) and, in dependence on those parameters, may vary within wide limits.
  • the compounds of formula I are distinguished by herbicidal and growth inhibiting properties, which render them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, as well as for non-selective weed control. Crops are also to be understood as meaning crops that have been rendered tolerant to herbicides or classes of herbicide by conventional cultivation or genetic engineering methods.
  • the weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida,
  • a solution of 1.27 g of 2-chloro-4-trifluoromethyl-benzoic acid ethyl ester in 3.5 ml of DMF is added at room temperature to a suspension of 0.39 g of sodium ethanethiolate in 3 ml of DMF, and the mixture is heated for 4 hours at a temperature of 50°C.
  • the reaction mixture is then cooled, poured into ice-water and extracted with toluene; the extracts are washed with water and dried.
  • phenyl dichlorophosphate 8.6 g of phenyl dichlorophosphate are added dropwise at a temperature of -60°C to a suspension of 6 g of 4-hydroxymethyl-2-methylsulfonyl benzotrifluoride, 12.1 g of triethylamine and 7.5 g of dimethyl sulfoxide in 120 ml of ethyl acetate, and the mixture is cooled, with stirring, to a temperature of 0°C. After 1.5 hours, 13.5 ml of concentrated hydrochloric acid are added to the brownish suspension, with cooling.
  • Example P1 1 Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehvde via catalytic hvdro ⁇ enation:
  • a solution of 12.3 ml of nitromethane in 200 ml of chloroform is added dropwise at a temperature of -5°C, in the course of 25 minutes, to a solution of 5.7 g of sodium in 200 ml of absolute methanol, whereupon a white suspension forms. After 30 minutes' stirring at that temperature, a solution of 12.3 ml of nitromethane in 200 ml of chloroform is added to the reaction mixture at a temperature of -5°C, and stirring is carried out for a further 30 minutes.
  • Example P14 Preparation of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyll-3-methyl- sulfanyl-4.5-dihvdro-isoxazol-4-yl-cvclopropyl-methanone: a) via methylthiomethylnitromethane
  • 0.5 ml of triethylamine is added in the course of 15 minutes, with stirring and under a nitrogen atmosphere, at a temperature of 20°C to a solution of 1.59 g of 1 -cyclopropyl-3-(2- methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1 -one, 0.643 g of methylthiomethylnitromethane and 1.3 ml of phenyl isocyanate in 40 ml of benzene. Stirring is then carried out for 3 hours at a temperature of 20°C, for one hour at a temperature of 40°C and for 15 hours at a temperature of 20°C.
  • the brownish red suspension is then filtered over a small amount of Hyflo (commercially available) and washed with diethyl ether, and the filtrate is concentrated by evaporation.
  • the residue is filtered first over silica gel (hexane/- ethyl acetate 7:3) and then purified by means of HPLC chromatography (Lichrospher Si60 12 ⁇ * m; hexane/ethyl acetate 9:1 with increasing gradients in respect of the more polar component).
  • a solution of 6 ml of 0.1 M DBU (1 ,8-diazabicyclo(5.4.0)undec-7-ene) in dioxane is added dropwise, with stirring, to a solution of 1.0 g of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoro- methyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone in 60 ml of dioxane, and stirring is carried out for a short time at a temperature of 20°C. A further 3 ml of 0.1 M DBU solution are then added, and stirring is carried out for one hour.
  • the reaction mixture is cooled, neutralised with a few drops of dilute aqueous acetic acid and extracted between dichloromethane and a small amount of water.
  • the extracts are washed with a small amount of water, dried over sodium sulfate and filtered over a small amount of silica gel.
  • the filtrate is concentrated by evaporation and dried in vacuo. 20 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 161 to 162°C are obtained.
  • a solution of 166 mg of m-chloroperbenzoic acid in 2 ml of dichloromethane is added dropwise, while cooling and with stirring at a temperature of from -15 to -18°C, to a solution of 256 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-isoxazol-4-yl- cyclopropyl-methanone in 10 ml of dichloromethane, and stirring is carried out for 4 hours at the same temperature.
  • a further 30 mg of m-chloroperbenzoic acid are then added; after 20 minutes, the mixture is diluted with dichloromethane and washed with sodium hydrogen carbonate solution and water.
  • Example P19 Preparation of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3- methylsulfanyl-4.5-dihvdroisoxazol-4-yl-cvclopropyl-methanone:

Landscapes

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

Abstract

Compounds of formula (I) wherein Z is S, SO or SO2; Q is C=O or CHOH; Ar is phenyl or phenyl substituted by up to four identical or different substituents and agronomically acceptable salts of those compounds, are suitable for use as herbicides.

Description

New herbicides
The present invention relates to novel herbicidally active isoxazole derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
Isoxazole derivatives having herbicidal action are described, for example, in
US-A-5 656 573, EP-A-0 524 018 and EP-A-0 636 622. Novel isoxazole derivatives having herbicidal and growth inhibiting properties have now been found.
Accordingly, the present invention relates to compounds of formula I
Figure imgf000003_0001
wherein
Z is S, SO or SO2;
Ri is hydrogen, d-C8alkyl or Cι-C8alkyl substituted by halogen, Cι-C4alkoxy, CrC4alkylthio, d-dalkylsulfonyl, C C4alkylsulfinyl, hydroxy, cyano, nitro, -CHO, -CO2R2, -COR3, -COSR4, -NR5R6, CONR36R37 or by phenyl which in turn may be substituted by Cι-C4alkyl, C C6halo- alkyl, d-dalkoxy, Cι-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyioxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, Cι-C alkoxy, phenoxy, (Cι-C4alkoxy)-C C4alkyl, (Cι-dalkylthio)-d-C4alkyl, (d-dalkylsulfiny -d-dalkyl, (Cι-C4alkylsulfonyl)-d-C4alkyl, NHSO2-d-C4alkyl, NHSO2-phenyl, N(d-C6alkyl)SO2-d-C4- alkyl, N(CrC6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-Ci-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-Cι-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-Cι-dalkyl, N(phenyl)SO2-phenyl, OSO2- d-C4alkyl, CONR25R26, OSO2-CrC4haloalkyl, OSO2-phenyl, d-C alkylthio, d-dhaloalkyl- thio, phenylthio, d-C alkylsulfonyl, d-dhaloalkylsulfonyl, phenylsulfonyl, CrC^lkylsulfinyl, C C4haloalkylsulfinyl, phenylsulfinyl, -(CH2) -phenyl or by -NR15CO2R27; or R. is C2-C8alkenyl or C2-C8alkenyl substituted by halogen, d-dalkoxy, d-C4alkylthio, d-C4alkylsulfonyl, C C4alkylsulfinyl, -CONR32R33, cyano, nitro, -CHO, -CO2R38, -COR39, -COS-d-C alkyl, -NR34R35 or by phenyl which in turn may be substituted by C C alkyl, d-Cβhaloalkyl, CrC4alkoxy, d-dhaloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOCι-C4alkyl, COOphenyl, d-C4alkoxy, phenoxy, (d-C4alkoxy)-C C4alkyl, (Cι-C4alkylthio)-Cι-C4alkyl, (Crdalkylsulfiny -d-C^lkyl, (d-C4alkylsulfonyl)-d-C4alkyl. NHSO2-d-C4alkyl, NHSO2-phenyl, N(d-C6alkyl)SO2-Cι-C4- alkyl, N(Cι-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-Ci-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-Ci-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C-3-dcycloalkyl)SO2-C1-C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-Crdalkyl. N(phenyl)SO2-phenyl, OSO2- Cι-C4alkyl, CONR40R ι, OSO2-Cι-C4haloalkyl, OSO2-phenyl, C C4alkylthio, d-C4haloalkyl- thio, phenylthio, d-C4alkylsulfonyl, d-C4haloalkylsulfonyl, phenylsulfonyl, C C4alkylsulfinyl, d-dhaloalkylsulfinyl, phenylsulfinyl, -(CH2)p-phenyl or by -NR 3CO R42; or R. is C3-C6alkynyl or C3-C6alkynyl substituted by halogen, d-C4haloalkyl, cyano, -CO2R44 or by phenyl which in turn may be substituted by d-dalkyl, d-C6haloalkyl, C C4alkoxy, d-C haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, C C4alkoxy, phenoxy, (C C4alkoxy)- d-C4alkyl, (d-C4alkylthio)-d-C4alkyl, (C C4alkylsulfinyl)-Cι-C4alkyl. (d-C4alkylsulfonyl)- d-C4alkyl, NHSO2-C C4alkyl. NHSO2-phenyl, N(C1-C6alkyl)SO2-C1-C4alkyl, N(d-C6alkyl)- SO -phenyl, N(C2-C6alkenyl)SO2-Crdalkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)- SO2-Cι-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)Sθ2-CrC4aikyl, N(C3-C7cyclo- alkyl)SO2-phenyl, N(phenyl)SO2-CrC4alkyl, N(phenyl)SO2-phenyl, OSO2-C C4alkyl, CONR28R29, OSO2-C C4ha.oalkyl, OSO2-phenyl, d-C4alkylthio, d-C4haloalkylthio, phenylthio, d-C4alkylsulfonyl, Cι-C4haloalkylsulfonyl, phenylsulfonyl, d-C4alkylsulfinyl, C C4halo- alkylsulfinyl, phenylsulfinyl, -(CH2)x-phenyl or by -NR31CO2R3o; or R. is C3-C7cycloalkyl or C3-C7cycloalkyl substituted by Crdalkyl, d-C alkoxy, d-C alkyl- thio, Cι-C alkylsulfinyl, d-C4alkylsulfonyl or by phenyl which in turn may be substituted by halogen, nitro, cyano, d-C4alkoxy, d-C4haloalkoxy, d-C4alkylthio, d-C haloalkylthio, C C4alkyl or by Cι-C4haloalkyl; or Ri is -(CH2)q-C-3-C7cycloa!kyl, phenyl or phenyl substituted by d-C alkyl, d-C6haloalkyl, Crdalkoxy, Cι-C haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, Cι-C4alkoxy, phenoxy, (CrC4- alkoxy)-d-C alkyl, (C C4alkyithio)-CrC4alkyl, (d-dalkylsulfinyl)-Cι-C4alkyl, (C C4alkyl- sulfonyl)-d-dalkyl, NHSO -Cι-C4alkyl, NHSO2-phenyl, N(Cι-C6alkyl)SO2-C1-C4alkyl> N(d-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-d-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-C1-dalkylI N(C3-C6alkynyl)SO2-phenyl, N(C3-dcycloalkyl)SO2-CrC4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-C1-C alkyl, N(phenyl)SO2-phenyl, OSO2- Cι-C4alkyl, CONR45R46) OSOs-d-dhaloalkyl, OSO2-phenyl, d-C4alkylthio, d-C4haloalkyl- thio, phenylthio, Cι-C4alkylsulfonyl, d-dhaloalkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, Cι-C4haloalkylsulfinyl, phenylsulfinyl or by -NR48CO2R47; or R. is -(CH2)s-phenyl, COR or 4- to 6-membered heterocyclyl;
R2, R38, R t and R6e are each independently of the others hydrogen, d-C4alkyl, phenyl or phenyl substituted by d-dalkyl, Cι-C6haloalkyl, d-dalkoxy, d-C4haloalkoxy, C2-C6- alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C4alkyl, COOphenyl, Cι-C4alkoxy, phenoxy, (d-C alkoxy)-C C4alkyl (C C4alkyl- thio)-d-C4alkyl, (Cι-C4alkylsulfinyl)-d-C4alkyl, (Cι-C4alkylsulfonyl)-C C alkyl, NHSO2-d-C4- alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2-C1-C4alkyl, N(d-C6alkyl)SO2-phenyl, N(C2-C6- alkenyl)SO -Cι-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-CrC4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-Cι-C4alkyl, N(C3-C7cycloalkyl)SO2- phenyl, N(phenyl)SO2-Cι-C4alkyl, N(phenyl)SO2-phenyl, OSO -C C4alkyl, CONR49R5o, OSO2-d-C haloalkyl, OSO2-phenyl, C C4alkylthio, d-dhaloalkylthio, phenylthio, C C4- alkylsulfonyl, d-C haloalkylsulfonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C C haloalkyl- sulfinyl, phenylsulfinyl, -(CH2)t-phenyl or by -NR52CO2R51;
R3, R39 and R67 are each independently of the others C C alkyl, phenyl or phenyl substituted by d-dalkyl, CrC6haloalkyl, d-C4alkoxy, d-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, C C4alkoxy, phenoxy, (C C4alkoxy)-Cι-C4alkyl, (Cι-C4alkylthio)-d-C4alkyl, (Cι-C4alkylsulfinyl)-d-C4alkyl, (d-C4alkylsulfonyl)-Cι-C4alkyl, NHSO2-d-C4alkyl, NHSO2- phenyl, N(C1-C6alkyl)SO2-C1-C4alkyl, N(d-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-CrC4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-Cι-C4alkyl, N(C3-C6alkynyl)SO2- phenyl, N(C3-C7cycloalkyl)SO2-d-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2- Cι-C4alkyl, N(phenyl)SO2-phenyl, OSO∑-CrC^lkyl, CONR53RM. OSO2-Cι-C haloalkyl, OSO2-phenyl, CrC4alkylthio, Cι-C haloalkylthio, phenylthio, C C alkylsulfonyl, C C4halo- alkylsulfonyl, phenylsulfonyl, d-C4alkylsulfinyl, Cι-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)t- phenyl or by -NR56CO2R55; R4 is d-dalkyl;
R5 is hydrogen, C C^lkyl, C2-C6alkenyl, Cs-Cealkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by d-C alkyl, CrCehaloalkyl, d-C4alkoxy, d-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-dalkyl, COOphenyl, d-C alkoxy, phenoxy, (C C alkoxy)-Cι-C4alkyl, (Cι-C4alkylthio)-CrC4alkyl, (Cι-C4alkylsulfinyl)-Cι-C4alkyl, (Cι-C4alkylsulfonyl)-d-C4alkyl, NHSO2-Cι-C4alkyl, NHSO2- phenyl, N(C1-C6alkyl)SO2-Ci-C4alkyl, N(CrC6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-Cι-C4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2H, N(C3-C6alkynyl)SO2-Cι-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2H, N(C3-C7cycloalkyl)SO2-CrC4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2-C C4- alkyl, CONR57R58, OSO2-C1-C4haloalkyl, OSO2-phenyl, CrC4alkylthio, Cι-C4haloalkylthio, phenylthio, d-dalkylsulfonyl, d-C haloalkylsulfonyl, phenylsulfonyl, d-C4alkylsulfinyl, Cι-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)u-phenyl or by -NR60CO2R59; R6 is hydrogen, d-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by d-C4alkyl, Cι-C6haioalkyl, d-dalkoxy, d-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C alkyl, COOphenyl, C C4alkoxy, phenoxy, (Cι-C4alkoxy)-Cι-C4alkyl, (d-C4alkylthio)-CrC4alkyl, (Cι-C4alkylsulfinyl)-d-C4alkyl, (Cι-C4alkylsulfonyl)-d-C4alkyl, NHSO2-d-C4alkyl, NHSO2- phenyl, N(Cι-C6alkyl)Sθ2-CrC4alkyl, N(CrC6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-Cι-C4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-d-C4alkyl, N(C3-C6alkynyl)SO2- phenyl, N(C3-C7cycloalkyl)SO2-d-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2- d-C4alkyl, N(phenyl)SO2-phenyl, OSO2-C C4alkyl, CONR61R62, OSO2-d-C4haloalkyl, OSO2-phenyl, d-C4alkylthio, Cι-C4haloalkylthio, phenylthio, d-dalkylsulfonyl, d-C4halo- alkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)v-phenyl or by -NR64CO2R63;
R7 is phenyl, substituted phenyl, d-dalkyl, d-dalkoxy or -NR8R9; R8 and R9 are each independently of the other d-C alkyl, phenyl or phenyl substituted by halogen, nitro, cyano, d-C alkyl, d-C4alkoxy, d-dthioalkyl, -CO2R66, -COR67, d-C4alkyl- sulfonyl, d-C4alkylsulfinyl or by d-C haloalkyl; or R8 and R9 together form a 5- or 6- membered ring which may be interrupted by oxygen, NR65 or by S; Q is C=O or CHOH;
R is Cι-C6alkyl, CrC6alkoxy, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C2-C6alkoxyalkynyl, C2-C6alkoxyalkenyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by d-C4alkyl, d-C4haloalkyl or by d-C4alkoxy; 3- to 6-membered, saturated heterocyclyl; or phenyl which may be substituted by halogen, d-C alkyl, C C4haloalkyl, d-C4alkoxy, Cι-C haloalkoxy, nitro, cyano, C C4alkylthio, d-C4alkylsulfonyl, d-C alkyl- sulfinyl, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio; Ar is phenyl or phenyl substituted by up to four identical or different substituents selected from halogen, d-C4alkyl, d-C haloalkyl, Cι-C alkoxy, d-C4haloalkoxy, (C C alkoxy)- d-C4alkyl, (d-C4alkylthio)-d-C4alkyl, (d-dalkylsulfony -Ci-dalkyl, (C1-C4alkylsulfinyl)- Cι-C4alkyl, Cι-C4alkylthio, Cι-C4haloalkylthio, phenylthio, C C4alkylsulfonyl, Cι-C4haloalkyl- sulfonyl, phenylsulfonyl, d-C alkylsulfinyl, Cι-C haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (C1-C4alkoxy)-C C4alkoxy, -COOH, COOd-C4alkyl, COOphenyl, Cι-C alkoxy, phenoxy, -C(=NOR68), -NR13SO2-d-C4alkyl, -NR69SO2-CrC4alkyl, -NR70SO2-phenyl, -NR7ιR72. C3-C6alkenyloxy, C3-C6alkynyloxy and S(O)n-Cι-C haloalkyl; it being possible for two adjacent substituents on the aromatic ring, together with the two atoms to which they are bonded, to form a 5- to 7-membered ring;
Ri3, Reg. R70 and R7ι are each independently of the others hydrogen, d-C6alkyl, C2-C6- alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by d-dalkyl, d-C6halo- alkyl, Cι-C alkoxy, d-C haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C4alkyl, COOphenyl, C C alkoxy, phenoxy, (d-dalkoxyj-d-dalkyl, (Cι-C4alkylthio)-d-C4alkyl, (d-C4alkylsulfinyl)-CrC4alkyl, (d-C4alkylsulfonyl)-Cι-C4alkyl, NHSO2-C C4alkyl, NHSO2-phenyl, N d-dalky SOjrd-d- alkyl, N(Cι-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-d-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-CrC4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C1-C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-d-C4alkyl, N(phenyl)SO2-phenyl, OSO2- d-C4alkyl, CONR^R^, OSO2-d-C4haloalkyl, OSO2-phenyl, d-C4alkylthio, d-C4haloalkyl- thio, phenylthio, d-C alkylsulfonyl, d-C haloalkylsulfonyl, phenylsulfonyl, Cι-C alkylsulfinyl, d-dhaloalkylsulfinyl, phenylsulfinyl, -(CH2)u-phenyl or by -NR80CO2R79; R72 is -COOH, COOCι-C4alkyl, COOphenyl, d-C4alkoxy or phenoxy, or COOphenyl or phenoxy each substituted by halogen, C C alkyl, C C4haloalkyl, d-C alkoxy, d-dhalo- alkoxy, d-C alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio;
R15. R3i> R43> R48, R52, Rδθ, Reo, Rw, Res and R80 are each independently of the others hydrogen, Cι-C4alkyl, C2-C6alkenyl, C3-C6alkynyl or C3-C7cycloalkyl; n is 0, 1 or 2; m, p, q, s, t, u, v and x are each independently of the others 1 , 2, 3 or 4; R25. 26, R27. R281 R29. R30, R32. 331 Rβ ι R35. R40. R4i ι 42i R 5. R46. R471 R49, R501 R511 R53. Rw, R55, R57, R58, R59, Rβι, Rβ2, Res. Res, R77, R78 and R79 are hydrogen, d-C4alkyl, C2-C6- alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by halogen, nitro, cyano, d-dalkoxy, C C haloalkoxy, C C4alkylthio, C C4haloalkylthio, d-C4alkyl or by d-C halo- alkyl; and agronomically acceptable salts of those compounds. The alkyl groups that appear in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated.
Halogen is generally fluorine, chlorine, bromine or iodine. The same applies also to halogen in connection with other meanings, such as haloalkyl or halophenyl.
Haloalkyl groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichlorornethyl, tri- chloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloro- methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
As haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichlόropropenyl and 4,4,4-trifluoro-but-2-en- 1 -yl. Of the C3-C20alkenyl groups mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.
As haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly- substituted by halogen, halogen being bromine, iodine and, especially, fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trif luoro-but-2-yn-1 -yl. Of the alkynyl groups mono- or poly-substituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.
Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkyl- carbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy- carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxy- carbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl- thio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methyl- sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxy- propoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n- propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have from 1 to 8 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or iso- propoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propyl- thiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butyl- thioethyl or butylthiobutyl. The cycloalkyl groups preferably have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Phenyl (also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl or phenoxyalkyl) may be substituted. The substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions with respect to the ring linkage site. Heterocyclyl is to be understood as meaning ring systems which contain, in addition to carbon atoms, at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Heterocyclyl ring systems within the scope of the present invention may also be substituted. Examples of suitable substituents are d-C4alkyl, d-C haloalkyl, d-d- alkoxy, cyano, nitro, d-C4alkylsulfonyl, Cι-C alkylsulfinyl, d-C alkylthio and C3-C6cyclo- alkyl. When the substituent Ar is heterocyclyl, two adjacent substituents on the heterocyclyl may form a 5- to 7-membered ring which may be substituted by Cι-C alkyl, d-C4haloalkyl, d-dalkoxy, cyano, nitro, d-dalkylsulfonyl, Cι-C4alkylsulfinyl, Cι-C4alkylthio or by C3-C6- cycloalkyl.
Heterocyclyl may be, for example, furyl, thiophenyl, pyrrolidyl, piperidinyl, mo holinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, thiazolyl, pyrazolyl, 1 ,2,4-triazolyl, 1 ,2,3-triazolyl, tetrazolyl, pyrimidyl, pyrazinyl, symmetrical or
asymmetrical triazinyl, piperazinyl, oxazolinyl (for example: ),
Figure imgf000010_0001
oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl, oxetanyl, especially 2-oxetanyl, or phthalimidyl.
The invention also includes the salts which the compounds of formula I are capable of forming especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Of the alkali metal and alkaline earth metal bases, special mention is to be made, as salt-forming agents, of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially those of sodium and potassium. There come into consideration as examples of amines suitable for the formation of ammonium salts both ammonia and primary, secondary and tertiary d-C18alkylamines, Cι-C4hydroxyalkylamines and C2-C4- alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl- nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl- heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethyl- amine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamyl- amine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso- propanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allyl- amine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2- amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propyl- amine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amyl- amine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and di-isopropylamine. Examples of quaternary ammonium bases suitable for the formation of salts are [N(Ra R R c R d)]+ OH" , wherein Ra, Rb, Rc and Rd are each independently of the others Cι-C4alkyl. Further suitable tetraalkyl- ammonium bases containing different anions can be obtained, for example, by anion exchange reactions.
Preferred compounds of formula I are those wherein Ar is a group
Figure imgf000011_0001
wherein R81, R82, Rβ3, Rβ , Res. Rβe, β7 and R88 are each independently of the others hydrogen, halogen, Cι-C4alkyl, d-dhaloalkyl, Cι-C alkoxy, d-C4haloalkoxy, (d-C4alkoxy)- d-dalkyl, (C C4alkylthio)-Cι-C4alkyl, (d-dalkylsulfony -d-dalkyl, (d-C4alkylsulfinyl)- d-C4alkyl, d-C alkylthio, C C4haloalkylthio, phenylthio, d-C4alkylsulfonyl, d-C4haloalkyl- sulfonyl, phenylsulfonyl, C C4alkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (d-C4alkoxy)-d-C4alkoxy, -COOH, COOC C alkyl, COOphenyl, phenoxy, -C(=NOR68), -NR13SO2-d-C4alkyl, -NR69SO2-d-C4alkyl, -NR7oSO2-phenyl, -NR71R72, C3-C6- alkenyloxy, C3-C6alkynyloxy or S(O)n-C1-C4haloalkyl;
XL X2, X3) Xt, Yι, Y2, Y3 and Y are each independently of the others O, S, SO, SO2, NR89,
C=O, C=N-O-Cι-C4alkyl, -C=N-O-d-C4alkenyl, CR19-O-d-C4alkyl or CR90R20;
R89 is hydrogen, Cι-C4alkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C7cycloalkyl;
R19, R20 and R90 are each independently of the others hydrogen or d-C4alkyl.
Preference is given also to those compounds of formula I wherein R is cyclopropyl, 1- methylcyclopropyl, tert-butyl or isopropyl.
Special preference is given to compounds of formula I wherein Q is C=O. Special mention is also to be made of compounds of formula I wherein Z is sulfur or SO.
Also of special importance are those compounds of formula I wherein R, is hydrogen, d-dalkyl, d-C4alkyl substituted by halogen, methoxy, ethoxy, cyano or by COOR2, or C3-C6alkenyl or halo-substituted C3-C6alkenyl, or C3-C6alkynyl.
Compounds of formula I can be prepared by various methods which are known perse:
Preparation method 1 : Scheme 1 :
Figure imgf000013_0001
PIV PHI Pll
NH2OH
(3)
Figure imgf000013_0002
(4) |χ (T= T1 = COR) PI (T= T2)
T = T1 , T2
T1 = COR
T2 = CN, CON(CH3)-OCH3
Tx = hydrogen, COOH or COO-d-C alkyl
M = metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
Reaction step (1 ):
Benzoic acid esters or acid chlorides are condensed with a keto compound Tx-CH2-T (T=T1=COR) or with a methylnitrile (T2=CN) or with an acetamide (T2=CON(CH3)-OCH3), in the presence of a base, such as NaH, in accordance with known methods in an inert solvent at from -100 to +100°C to form keto derivatives PHI.
Both the keto compound that is used and the nitrile may carry on the α-carbon atom an additional carboxyl or alkoxycarbonyl group Tx suitable for condensation. When Tx is COO-d-C alkyl, hydrolysis and decarboxylation can be carried out once the acylation is complete. Where an acid chloride ArCOCI is used, it may suitably be used with, for example, BuLi as the base at from -60 to -80°C and tetrahydrofuran as the solvent (Synthesis 1983. 308; Synthesis 1984. 1 ; J. Org. Chem. 54, 4229; US 5 545 762; US 5 656 373).
Reaction step (2):
The keto compound Pill is then reacted with carbon disulfide in the presence of a base, such as NaH, an alkali alkanolate (e.g. NaOEt) or an alkali carbonate, e.g. potassium carbonate, or a fluoride salt (e.g. KF) that is free or bonded, for example, to aluminium oxide, in an inert solvent at from -20 to +80°C and alkylated using an alkylating agent R XP1 , wherein R. is as defined above and XP1 is Hal (Cl, Br, I) or OS(O)ORι, to form the ketene dithioacetal Pll (Chem. Ber. 95, 2861 , Z. Chem. 16, 397, 1976).
Reaction step (3):
Cyclisation is then carried out with hydroxylamine or its hydrochloride, if desired with the addition of an alkali acetate in an inert solvent at from -20 to +120°C to form the isoxazoles of formula Ix (T=T1=COR) or PI (T=T2=CN or CON(CH3)OCH3) (J. fur prakt. Ch. 320, 585).
The intermediates of formula PI are novel and have been developed especially for the preparation of the compounds of formula I, and the present invention therefore relates also thereto.
Reaction step (4):
If the cyano- or amide-substituted isoxazoles are obtained in the cyclisation (step 3), they are subsequently reacted at from -120° to +40°C in an inert solvent, such as hexane, an ether, THF, (if required after transmetallation to, for example, potassium, zinc or cadmium salts) with Grignard (RMgHal)- or alkyl lithium (RLi) to form the compound of formula ly (J. Het. Chem. 12, 413; Tetrahedr. 3 ., 499 (1975)). Preparation method 2:
Figure imgf000015_0001
T = T1 , T2
T1 = COR
T2 = CN, CON(Me)-OCH3
M = metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
E, G = Hal (Cl, Br, I) or -SR!
Reaction steps (6) and (7):
In the manner indicated in Preparation Method 2, an aryl ketone Pill (prepared according to Scheme 1 ) can also be reacted either directly (Reaction step 6) or via an enamine PVI (Reaction step 7) with dihaloformaldehyde oximes (E=G=Hal) or their dithio derivatives (E=G=SRι; PVIa) or their nitrite oxides (PVIb), with or without the addition of a base, such as a tertiary amine (e.g. NEt3), in inert solvents at temperatures of from -20° to +160°C, to form isoxazoles of formula I or PV (EP-A-0 503 410; EP-A-0 524 018; Heterocycles 34, 1703).
Reaction step (8):
Intermediates PV wherein E is halogen can then be converted, by reaction with mercaptans HSRi, preferably in the presence of an acid acceptor (e.g. bases such as tertiary amines or oxiranes such as propylene oxide) in inert solvents at temperatures of from -20 to 150°C, into the products Ix or PI already obtainable according to Scheme 1.
It is also possible to carry out the reaction of PVa according to Chem. Pharm. Bull. 27, 2398; ibid. 2415. In that case, PVa (E=Hal) is converted using an alkylating agent R XP1 into an intermediate PVIa which is quatemised at the nitrogen; that intermediate is substituted under the above-mentioned conditions by a mercaptan HSRT in the presence of an acid acceptor to form the quatemised thioether PVIIb, and the latter is converted by heating at from 60 to 220°C, with the removal of R XP1 , into the products of formula Ix or PI.
Figure imgf000016_0001
PVa PVIa PVIIb Ix (T= CO-R)
PI (T=T1)
Intermediates of formula PIVa wherein E and G are halogen or S-R^ but E and G are not simultaneously halogen, with the exception of those compounds wherein E and G are methylthio, ethylthio or benzylthio, and the intermediates of formulae PVIa and PVIIb wherein Ar and Ri are as defined for formula I, T is CO-R wherein R is as defined for formula I and XP1 is halogen, are novel and have been developed especially for the preparation of the compounds of formula I, and the present invention therefore relates also thereto.
Reaction step (5):
Some enamines PVI are known (US-A-5 656 573, EP-A-0 625 505), or they are prepared according to methods known perse, for example by reaction of a keto compound Pill with a secondary amine HN(P1)P2 wherein HN(P1)P2 is an open-chained or cyclic compound such as HNEt2, pyrrolidine or morpholine, in the presence of an acid catalyst (acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins, such as Amberlyst IRA 400) and of an inert solvent, with removal of the water of reaction that forms (molecular sieve, azeotropic distillation) at temperatures of from 40 to 200°C (Tetrahedron Letters 1988. 3997).
According to other variants (scheme below), enamines PVI are obtainable either (Reaction step 5a) by reacting enamines of formula PVIII with acid chlorides RCO-CI (T=T1=COR) in the presence of a base at from -30 to +80°C (US-A-5 656 573), or (Reaction step 5b) by the addition of secondary amines HN(P1)P2 (wherein HN(P1)P2 may be open-chain or cyclic, such as HNEt2, pyrrolidine or morpholine) to acetylenes PIX:
Figure imgf000017_0001
(5b)
PIX
Starting materials (PIX) required therefor are in some cases known, or they can be prepared according to known methods, for example by synthesis by means of the Heck reaction of Ar-P3, wherein Ar is as defined above and P3 is halogen (Cl, Br, I), or OSO2-perfluoroalkyl, such as OSO2CF3, with protected acetylenes
H^≡≡ — Pg
wherein Pg is a protecting group, such as Si(alkyl)3, C(Me)2OH, Sn(alkyl)3)
in the presence of a palladium catalyst, such as Pd(Ph3P)4 or Pd(Ph3P)2CI2 or Pd(OAc)2 and Cul, and of an amine (e.g. HNEt2) at from 0 to 120°C in an inert solvent (Org. React. 27, 345; Synlett 1995, 1115; WO 96/26193) to form a compound of formula PX, and subse- quent introduction of an acyl group CO-R, for example by means of a Grignard reaction, to a nitrile R-CN, or by acylation of a trialkyltin acetylide prepared as indicated above, in the presence of a palladium catalyst, such as Pd(Ph3P)2CI2 (Heterocycles 41, 817 (1995); Org. React. 50, 1 (1997)) with an acid halide R-COCI:
Ar— P *• Ar — ≡≡≡ — Pg ^ Ar — ==≡ — COR
P3 = Hal, OS02CF3 PX PIX
Preparation method 3:
Analogously to Gazz. Chim. Ital. 91 , 47 (1961 ), 4-H-substituted isoxazoles PXIa (E=Hal) or PXIb (E=S-Rι) can be prepared from aryl-acetylenes PXa by metallation to corresponding Grignard or lithium compounds and direct reaction with dihalo- or dithio-formaldehyde oximes PIVa, with or without the addition of a base (e.g. NaH, tertiary amine). Gentle deprotonisation, for example with a lithium base at from -30 to -120°C, and reaction with an acid chloride RCO-CI yield the compounds of formula I. If a suitable tin compound (e.g. (R4)3-SnCI) is used as the electrophile instead of an acid chloride 4-stannyl compounds XII are obtained, which can likewise be reacted with acid chlorides RCO-CI analogously to Heterocycles 43, 1301 (1996) in the presence of palladium catalysts (e.g. Pd(Ph3P)2CI2) to form the compound of formula I.
1) metallation (e.g. BuLi) -120 to -30°C
Figure imgf000019_0001
PXII
Preparation method 4:
Analogously to other methods of synthesis known from the literature (e.g. J. Org. Chem. 48, 1796 (1983); ibid. 45, 2945, (1980); Tetrahedron 40, 601 (1984); A. Katritzky, C. Rees, Compendium of Het. Chem. Vol. 6, p. 2 ff., Oxford 1984; Houben Weyl Vol. E8 a, p. 45 ff.), the compounds of formula I can be prepared also by the direct addition of nitrite oxides PIVb to unsaturated ketones of formula PIX (alkynes) or PXIII (alkenes) in accordance with the following scheme:
Figure imgf000020_0001
PXVI PXVIII
Examples of suitable oxidising agents for the selective oxidation of the compound of formula PXVIII to the compound of formula KUb, wherein Ar, R and Ri are as defined for formula I, n is 1 or 2 and 'Hal is halogen, preferably chlorine or bromine, are metachloroper- benzoic acid, sodium perborate and tetrabutylammonium perruthenate. The compound of formula KUb is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
Reaction steps (1 ). (2) and (4):
Alkyl- or aryl-thiomethylnitromethane derivatives of formula PXIII obtainable according to known methods (e.g. J. Org. Chem. 53, 5369 (1988)) are converted into the corresponding nitrile oxides PIVb in the presence of a dehydrating agent, for example an isocyanate of formula PXIV, and of a base, for example a tertiary amine (e.g. triethylamine), in an inert solvent, such as cyclohexane, toluene, benzene, or halogenated solvents, such as dichloro- methane, and reacted with an alkyne PIX or an alkene PXV, if required in the presence of a catalyst, at temperatures of from -20°C to +80°C to form the isoxazole derivatives of formula I or the isoxazolines of formula PXVI, respectively.
The cyclisation is preferably carried out without isolation of the intermediates in a one-pot reaction in one of the mentioned solvents. Examples of suitable catalysts are Lewis acids, such as Ti(IV) salts, such as Ti(OisoPr)4 (J. Am. Chem. Soc. 118, 59; ibid. 111 , 5340; J. Org. Chem. 59, 5687), or complexes such as Ti(OTs)2(TADDOL) (Helv. 77, 2071 ); or Eu (fod)3 (= tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanate-dionato)europium(lll)) (Heterocycles 46, 95), and lanthanide complexes such as Yb(OTf)3 (Chem. Lett. 1997, 1039).
Reaction step (5):
Isoxazolines of formula PXVI can be converted into the end products of formula Iz according to methods known perse by means of aromatising oxidising agents such as, for example, MnO2 (Synthesis 1976, 133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.
Reaction steps (6) and (7):
According to a further variant, the isoxazolines are first converted into the corresponding halides (preferably chlorine or bromine derivatives) PXVIII by means of a halogenating agent, such as Br2, Cl2, N-bromosuccinimide, if required with the addition of a radical initiator, such as dibenzoyi peroxide, in an inert solvent, for example carbon tetrachioride or a sulfochloride, such as thionyl chloride or trifluoromethane sulfochloride, and the halides are then reacted with a base (preferably a tertiary amine, such as triethylamine or DBU (1 ,8- diazabicyclo-(5.4.0)-undec-7-ene)) in an inert solvent, such as dichloromethane, at from -20°C to +80°C to form the products of formula I. The halogenation and the subsequent reaction to form the compound of formula Iz are preferably carried out in the same reaction vessel. Reaction step (3):
The oxidation of the isoxazoles of formula Iz to the corresponding sulfoxides of formula Iw
(formula I n=1 ) or sulfones (n=2) can be carried out, for example, analogously to
WO 97/43270 using 1 or 2 equivalents of an oxidising agent such as m-chloroperbenzoic acid in an inert solvent, for example dichloromethane, at temperatures of from -20°C to
+100°C.
Isoxazolines of formulae PXVI and PXVIII, wherein Ar, R and R. are as defined for formula I and 'Hal is halogen, preferably chlorine or bromine, are novel and, as intermediates, the present invention relates also thereto. The compounds of formulae PXVI and PXVIII have herbicidal activity.
Starting materials
(Details regarding acetylene ketones of formula PIX are given above.)
Enones of formula PXV are either known or can be prepared according to known methods, for example by Wittig or Wittig-Homer condensation of an aldehyde of formula PXXI with a phosphorane PXX obtained from a halide PXIX, in an inert solvent, such as tetrahydrofuran, dioxane or acetonitrile, at temperatures of from 20°C to 160°C (analogously to Tetrahedron Lett. 1974, 2491 , scheme below). According to another process, enones of formula PXV are obtainable by condensation of aldehydes of formula PXXI with a methyl ketone of formula XXII
T-CH3 (XXII)
or with an activated keto ester XXIII
T-CH2-COOalkyl (XXIII),
in the presence of a bifunctional catalyst, such as ammonium acetate, a pyridine/piperidine mixture (analogously to Synthesis 1980, 806), an alkali fluoride (KF, Synthesis 1983, 173), and subsequent removal of the activating group (customary hydrolysis and decarboxylation (-COOalkyl) in the case of a 1 ,3-keto ester).
Figure imgf000023_0001
PXX
PXIX
(Hal = Cl, Br, I)
Ar-CHO (PXXI)
Ar — = COR
PXV
A further process for the preparation of unsaturated ketones of formula PXV comprises the Heck reaction of an aryl halide of formula PXXIIIa
Ar-Hal (Hal = Cl, Br, I) (PXXIIIa)
or of a trifluoromethylsulfonate PXXIIIb
Ar-OTf (PXXIIIb)
with an unsaturated vinyl ketone PXXIV
Figure imgf000023_0002
(PXXIV)
in the presence of a palladium catalyst, for example Pd(OAc)2, and of a base, such as triethylamine, in an inert solvent, such as acetonitrile or N,N-dimethylformamide, at temperatures of from 0°C to 180°C (analogously to R. Heck in Org. React. 27, 345 ff (1982)).
The arylaldehydes (PXXI) required for the above-mentioned condensation reactions are either known or can be prepared according to known methods, for example by catalytic reduction of appropriate carboxylic acid halides according to Rosenmund or an analogous variant in the presence of a catalyst, for example Pd/BaSO4, and of a pyridine base, such as lutidine.
According to a further variant, known carboxylic acid esters (US-A-5 656 573, EP-A-0 625 505) of the formula
Ar— COOalkyl
can be reduced by means of complex hydrides, for example NaBH4, in a short-chain aliphatic alcohol as solvent (for example analogously to Angew. 92, 1067 (1980)) to form the primary alcohol PXXV
Ar— CH2OH (PXXV)
and then oxidised with an oxidising agent, such as cerium(IV)-ammonium nitrate (J. prakt. Chem. 336, 470 (1994)) or phenyl dichlorophosphate/DMSO/NEt3 (J. Org. Chem. 59, 7704 (1994)) or oxalyl chloride/DMSO (Synth. 1990, 857), to the aldehyde PXXI
Figure imgf000024_0001
Preparation method 5:
Finally, the isoxazoles of formula I are also obtainable from the dihaloformaldoximes PIVa, as shown below, by means of addition to olefins PXV via isoxazolines of formula PXVI. In that reaction, the 3-halo-isoxazoline of formula PXVII may also be isolated. To that end, in reaction step (1 ) there are added to the olef in PXV in an inert solvent, such as 1 ,2- dimethoxyethane, at a temperature of from 0°C to +60°C, a base, for example an alkali hydrogen carbonate, as well as a small amount of water and the oxime PIVa and then the thiolate RiSMi is introduced in small portions over a prolonged period of about from 1 to 6 hours.
Figure imgf000025_0001
Ms is an alkali metal, preferably lithium. Examples of suitable oxidising agents for the selective oxidation of the compound of formula PXVI to the compound of formula KUa, wherein Ar, R and Ri are as defined for formula I and n is 1 or 2, are metachloroperbenzoic acid, sodium perborate and tetrabutylammonium perruthenate. The compound of formula KUa is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
Other starting materials:
Dihaloformaldehyde oximes and dithioalkylformaldehyde oximes of formula PIVa are known or can be prepared according to known methods, for example Chem. Ber. 43, 3362; Synth. Comm. 12, 601 or according to CH-A-563 967, Chem. and Industry 1979. 826.
Dithio-substituted formaldehyde oximes can also be obtained from the dihalo compounds and appropriate thiols in the presence of a base. Substituted aryl derivatives (Ar-P3, AΓ-COOP ) are for the most part also known or can be prepared according to known methods (as described, for example, in US-A-5 658 858, US-A-5 656 573, EP-A-0 524 018, EP-A-0 527 037, EP-A-0 609 797, EP-A-0 588 357, WO 97/19076, WO 97/09324, WO 97/09327, WO 97/19071 , WO 96/26192, EP-A-0 768 033, WO 96/26206, WO 97/12885, WO 96/26200 and US-A-0 5 607 898).
The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and can usually be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, the reaction mixture may if required be heated for a short time up to its boiling point. The reaction times may also be shortened by adding a few drops of a base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diaza- bicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7- ene. However, it is also possible to use as bases inorganic bases, for example hydrides, such as sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate. The compounds of formula I may be isolated in customary manner by concentration and/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.
For the use, according to the invention, of the compounds of formula I or of compositions comprising them there come into consideration any methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose, a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If r equired, a coating may additionally be applied (coated granules), which allows the active in igredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used as herbicides in unmodified form, i.e. as they are formed in the synthesis. Preferably, however, they are processed in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsif iable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wet- table powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485, pages 9 to 13. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and generally one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485, page 6.
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 mixtures of surfactants having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485, pages 7 and 8.
Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981. The herbicidal formulations usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and 0 to 25 % by weight, preferably 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 other auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients.
The compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the type of action, on the stage of development of the cultivated plant and of the weed, and also on the application (place, time, method) and, in dependence on those parameters, may vary within wide limits.
The compounds of formula I are distinguished by herbicidal and growth inhibiting properties, which render them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, as well as for non-selective weed control. Crops are also to be understood as meaning crops that have been rendered tolerant to herbicides or classes of herbicide by conventional cultivation or genetic engineering methods. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The Examples which follow further illustrate, but do not limit, the invention. Preparation Examples:
Example P1 : Preparation of dithiomethylformaldehvde oxime:
Figure imgf000029_0001
A solution of 2.03 g of dibromoformaldehyde oxime in 10 ml of anhydrous tetrahydrofuran is added dropwise at room temperature to a stirred suspension of 1.4 g of sodium methane- thiolate in 15 ml of tetrahydrofuran, and stirring is carried out for 16 hours. The reaction mixture is then poured into ice-water, adjusted to pH 5 by the addition of 1 N HCI and extracted with ethyl acetate, and the extracts are then dried over sodium sulfate, filtered and concentrated by evaporation in vacuo. The yellow residue that remains is filtered over silica gel (hexane/ethyl acetate 8:2). Dithiomethylformaldehyde oxime having a melting point of 71 -73°C is obtained.
Example P2: Preparation of 2-chloro-4-trifluoromethylbenzoic acid ethyl ester by carbonylation:
Figure imgf000029_0002
68.3 mg of palladium acetate, 125.5 mg of 1 ,1-bis(diphenylphosphino)ferrocene and 1.87 ml of triethylamine which has been dried over KOH are added to 2.0 g of 3-chloro-4-tri- fluorosulfonyloxy benzotrifluoride in an autoclave in a mixture of 25 ml of DMF and 10 ml of ethanol, and the mixture is then heated overnight (about 20 hours) at 82°C in the presence of carbon monoxide, the carbon monoxide pressure being 8 bar. The mixture is then concentrated by evaporation in vacuo, and the residue is partitioned between ethyl acetate and water; the organic extract is washed with saturated sodium chloride solution, dried over sodium sulfate and filtered, and concentration by evaporation is carried out. The residue (1.1 g), which according to NMR is already pure, is rapidly distilled in a bulb tube, yielding a virtually colourless oil having a refractive index (nD20) of 1.4664.
Example 3: Preparation of 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester:
Figure imgf000030_0001
A solution of 1.27 g of 2-chloro-4-trifluoromethyl-benzoic acid ethyl ester in 3.5 ml of DMF is added at room temperature to a suspension of 0.39 g of sodium ethanethiolate in 3 ml of DMF, and the mixture is heated for 4 hours at a temperature of 50°C. The reaction mixture is then cooled, poured into ice-water and extracted with toluene; the extracts are washed with water and dried. Filtration over a small amount of silica gel and concentration by evaporation in vacuo yield 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester having a refractive index (nD20) of 1.5052 in a yield of 85 % of the theoretical yield.
Example P4: Preparation of 2-(2-methylthio-4-trifluoromethyl)-benzoylacetonitrile:
Figure imgf000030_0002
Under a nitrogen atmosphere and with stirring, 54 mg of acetonitrile are added at a temperature of 0°C to 87 mg of sodium hydride (60 % dispersion in oil) in 3 ml of dimethyl sulfoxide, and stirring is carried out for 10 minutes. 264 mg of 2-methylthio-4-trifluoromethyl- benzoic acid ethyl ester are then added, and the reaction mixture is stirred for a further 4 hours at a temperature of 20°C, whereupon dissolution takes place. The reaction mixture is then poured into ice-water, acidified with 0.1 N HCI and extracted with ethyl acetate, and the extracts are washed with water and brine. The solid residue that remains after drying and concentration by evaporation is purified on silica gel (hexane/ethyl acetate 9:1 ). The 2- (2-methylthio-4-trifluoromethyl)-benzoylacetonitrile so obtained has a melting point of 149-150°C. Example P5: Preparation of 2-(2-methylthio-4-trifluorobenzoyl)-3.3-dimethyldithio-acrylo- nitrile:
Figure imgf000031_0001
To a mixture of 130 mg of 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester in 2 ml of absolute DMF there are added, under a nitrogen atmosphere and with stirring at a temperature of 0°C, 360 mg of potassium fluoride (40 %) on aluminium oxide and, after stirring for a further 10 minutes, 0.05 ml of carbon disulfide. Stirring is then carried out for 2 hours at a temperature of 0°C; 0.1 ml of methyl iodide is then added and the yellow suspension is stirred for 4 hours at a temperature of 20°C. The solid precipitate is then filtered off, washed with DMF and concentrated by evaporation in vacuo, and the residue is partitioned between water and dichloromethane. The organic phase is washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. 2-(2-Methyl- thio-4-trifluorobenzoyl)-3,3-dimethyldithio-acrylonitrile having a melting point of 91-92°C is obtained.
Example P6: Preparation of 5-(2-methylthio-4-trifluoromethylphenyl)-4-cvano-3-methylthio- isoxazole:
Figure imgf000031_0002
90 mg of 2-(2-methylthio-4-trifluoromethylbenzoyl)-3,3-dimethyldithio-acrylonitrile are added to a stirred suspension of 27 mg of hydroxylamine hydrochloride and 31 mg of sodium acetate, and stirring is carried out for 6 hours at room temperature. The mixture is then poured into ice-water and extracted with ethyl acetate. The extracts are washed with saturated sodium chloride solution, dried and filtered; a small amount of hexane is added to the filtrate, and filtration is carried out over silica gel. The 5-(2-methylthio-4-trifluoromethyl- phenyl)-4-cyano-3-methylthioisoxazole that remains after concentration by evaporation and drying in vacuo has a melting point of 85-86°C.
Example P7: Preparation of 3-cvclopropyl-2-(bis(methylthio)methylene)-1 -(2.4-dichloro- phenyl)-propane-1.3-dione:
4.9 g (0.019 mol) of 3-cyclopropyl-1 -(2,4-dichlorophenyl)-propane-1 ,3-dione are dissolved at 20°C in 50 ml of DMF. The clear solution is cooled to -3°C. 17.3 g (0.095 mol) of KF/AI2O3 (20 %) are then added in portions in the course of 5 minutes. 1.8 ml of CS are added dropwise with cooling (0°C), and stirring is carried out for 3 hours at 0°C. 3.4 ml (0.055 mol) of methyl iodide are pipetted into the resulting suspension. The mixture is heated to a temperature of 20°C and stirred for 18 hours. When the reaction is complete, excess KF/AI2O3 is filtered off and the solvent is distilled off in vacuo. The oily residue is subjected to flash chromatography on silica gel with ethyl acetate/hexane (1 :8) as eluant. 2.2 g of 3- cyclopropyl-2-(bis(methylthio)methylene)-1 -(2,4-dichlorophenyl)-propane-1 ,3-dione are isolated in the form of a yellow oil.
1H-NMR (CDCI3) : 0.9-1.0 (m, 2H); 1.1-1.2 (m, 2H); 2.2-2.4 (m, 1 H); 2.2-2.4 (s, 6H); 7.3 (d, 1 H); 7.4 (s, 1 H); 7.6 (d, 1 H).
Example P8: Preparation of 4-cvclopropylcarbonyl-3-thiomethyl-5-(2.4-dichlorophenvD- isoxazole:
0.52 g (7.5 mmol) of hydroxylamine hydrochloride and 0.55 g (6.7 mmol) of anhydrous sodium acetate are added to a solution of 2.2 g (6.1 mmol) of 3-cyclopropyl-2-(bis(methyl- thio)-methylene)-1 -(2,4-dichlorophenyl)-propane-1 ,3-dione in 50 ml of ethanol. The reaction mixture is stirred for 48 hours at 20°C. Insoluble portions are then filtered off and the filtrate is concentrated to dryness by evaporation. The partially crystalline crude product is pre- purified on silica gel with ethyl acetate/hexane (1 :9) as eluant. The pre-purified product is then chromatographed again by means of preparative HPLC. 60 mg of 4-cyclopropyl- carbonyl-3-thiomethyl-5-(2,4-dichlorophenyl)-isoxazole are obtained.
M.p.: 105-107°C.
1H-NMR (CDCI3) : 0.78-0.83 (m, 2H); 1.18-1.2 (m, 2H); 1.7-1.75 (m, 1H); 2.6 (s, 3H);
7.42-7.46 (dd, 1 H); 7.48-7.51 (d, 1 H); 7.59-7.6 (d, 1 H). Preparation of the preliminary products:
Example P9: Preparation of 1 -cyclopropyl-2-triphenylphosphoranylidene-ethanone:
Figure imgf000033_0001
A solution of 32.6 g of bromomethyl cyclopropyl ketone in 30 ml of toluene is added dropwise at a temperature of 20°C to a suspension of 52.3 g of triphenylphosphine in 300 ml of toluene, and the reaction mixture is then stirred at the same temperature for 15 hours. Filtration is then carried out, and the precipitate is washed with toluene and taken up in dichloromethane; the solution is washed twice with 2N sodium hydroxide solution, concentrated sodium carbonate solution and concentrated sodium chloride solution. After drying over sodium sulfate, filtration is carried out and the filtrate is then concentrated by evaporation. 1-Cyclopropyl-2-triphenylphosphoranylidene-ethanone having a melting point of 170-172°C is obtained.
Example P10: Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehvde:
Figure imgf000033_0002
8.6 g of phenyl dichlorophosphate are added dropwise at a temperature of -60°C to a suspension of 6 g of 4-hydroxymethyl-2-methylsulfonyl benzotrifluoride, 12.1 g of triethylamine and 7.5 g of dimethyl sulfoxide in 120 ml of ethyl acetate, and the mixture is cooled, with stirring, to a temperature of 0°C. After 1.5 hours, 13.5 ml of concentrated hydrochloric acid are added to the brownish suspension, with cooling. After extraction with ethyl acetate and water, the organic extract is washed twice with sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated by evaporation; there remain 5.8 g of unpurified 2-methylsulfonyl-4-trifluoromethyl-benzaldehyde, which is used further in the next reaction step in that form.
The product purified on silica gel (hexane/ethyl acetate) is a white solid having a melting point of 86-88°C. Example P1 1 : Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehvde via catalytic hvdroαenation:
Figure imgf000034_0001
Hydrogen is introduced at 20°C, under reduced pressure, into a solution of 4.4 g of 2-methylsulfonyl-4-trifluoromethyl-benzoic acid chloride in 80 ml of tetrahydrofuran, with the addition of 1.74 g of 2,6-lutidine and 3.5 g of palladium-BaSO4 (5 %), until the reaction is complete. The catalyst is then filtered off, and ethyl acetate is added; the lutidine hydro- chloride that has precipitated is filtered off, and the filtrate is washed with water and concentrated sodium chloride solution, dried and filtered over a small amount of silica gel (hexane/ethyl acetate). 2-Methylsulfonyl-4-trifluoromethyl-benzaldehyde having a melting point of 66-88°C is obtained.
Example P12: Preparation of 1 -cvclopropyl-3-(2-methylsulfonyl-4-trifluoromethyl)-phenyl-2- propen-1-one:
Figure imgf000034_0002
A solution of 1.26 g of 2-methylsulfonyl-4-trifluoromethylbenzaldehyde and 1.9 g of 1-cyclo- propyl-2-triphenylphosphoranylidene-ethanone in 15 ml of dioxane is stirred for 15 hours overnight under a nitrogen atmosphere at a temperature of 70°C. The mixture is then concentrated by evaporation, digested with ethyl acetate and a small amount of hexane and filtered, and the filtrate is purified over silica gel (hexane/ethyl acetate). 1 -Cyclopropyl-3-(2- methylsulf onyl-4-trif luoromethyl)-phenyl-2-propen-1 -one having a melting point of 114-116°C is obtained. Example P13: Preparation of methylthiomethyl-nitromethane:
Figure imgf000035_0001
A solution of 12.3 ml of nitromethane in 200 ml of chloroform is added dropwise at a temperature of -5°C, in the course of 25 minutes, to a solution of 5.7 g of sodium in 200 ml of absolute methanol, whereupon a white suspension forms. After 30 minutes' stirring at that temperature, a solution of 12.3 ml of nitromethane in 200 ml of chloroform is added to the reaction mixture at a temperature of -5°C, and stirring is carried out for a further 30 minutes. There are then added dropwise in succession, at the same temperature, a solution of 23.5 g of S-methylmethanethiosulfone in 100 ml of chloroform, and 13 ml of concentrated acetic acid, and the mixture is stirred until the reaction is complete. The reaction mixture is then poured into ice-water, the resulting mixture is extracted with chloroform, and the extracts are washed with water and then dried. After filtration, concentration by evaporation is carried out and the residue is purified on silica gel (hexane/ethyl acetate 7:3). Methylthiomethyl-nitromethane is obtained in the form of a yellow oil.
Example P14: Preparation of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyll-3-methyl- sulfanyl-4.5-dihvdro-isoxazol-4-yl-cvclopropyl-methanone: a) via methylthiomethylnitromethane
0.5 ml of triethylamine is added in the course of 15 minutes, with stirring and under a nitrogen atmosphere, at a temperature of 20°C to a solution of 1.59 g of 1 -cyclopropyl-3-(2- methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1 -one, 0.643 g of methylthiomethylnitromethane and 1.3 ml of phenyl isocyanate in 40 ml of benzene. Stirring is then carried out for 3 hours at a temperature of 20°C, for one hour at a temperature of 40°C and for 15 hours at a temperature of 20°C. The brownish red suspension is then filtered over a small amount of Hyflo (commercially available) and washed with diethyl ether, and the filtrate is concentrated by evaporation. The residue is filtered first over silica gel (hexane/- ethyl acetate 7:3) and then purified by means of HPLC chromatography (Lichrospher Si60 12μ*m; hexane/ethyl acetate 9:1 with increasing gradients in respect of the more polar component). 0.50 g of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 190 to 191 °C is obtained. b) via dibromoformaldehyde oxime
2.2 g of potassium hydrogen carbonate and 10 drops of water are added, with stirring, to a solution of 1.59 g of 1 -cyclopropyl-3-(2-methylsulfonyl-4-trif luoromethyl)-phenyl-2-propen-1 - one in 25 ml of 1 ,2-dimethoxyethane. There are then introduced at hourly intervals a total of 425 mg of dibromoformaldehyde oxime and, at the same time, 158 mg of sodium methane- thiolate, and the yellowish suspension is stirred for 15 hours at a temperature of 20°C. Filtration over Hyflo and intensive washing with dimethoxyethane are then carried out; the filtrate is dried over sodium sulfate and concentrated by evaporation. The resin that remains is separated by means of HPLC chromatography (Lichrospher Si60 12μ*m; hexane/ethyl acetate 85:15 to 50:50). In addition to unreacted starting material and 5-(2-methanesulfonyl- 4-trifluoromethyl-phenyl)-3-bromo-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone of nD (40°C) = 1.5191 , there is obtained 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3- methyisulfanyl-4,5-dihydro-isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 190 to 191 °C.
Example P15: Preparation of 5-(2-methanesulfonyl-4-triftuoromethyl-phenyl)-3-methyl- sulfanyl-isoxazol-4-yl-cyclopropyl-methanone:
Figure imgf000036_0001
(a) via 1 -(4-bromo-5-(2-methanesulfonyl-4-trif luoromethyl-phenyl)-3-methylsulfanyl-4,5- dihydroisoxazol-4-yl-cyclopropyl-methanone
A solution of 6 ml of 0.1 M DBU (1 ,8-diazabicyclo(5.4.0)undec-7-ene) in dioxane is added dropwise, with stirring, to a solution of 1.0 g of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoro- methyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone in 60 ml of dioxane, and stirring is carried out for a short time at a temperature of 20°C. A further 3 ml of 0.1 M DBU solution are then added, and stirring is carried out for one hour. The mixture is then diluted with ethyl acetate, washed with ice-water and dried over sodium sulfate. Filtra- tion over a small amount of silica gel, concentration by evaporation and purification yield 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-isoxazol-4-yl-cyclopropyl- methanone having a melting point of from 160 to 161°C.
(b) via 1 -(4-chloro-5-(2-methanesulfonyl-4-trif luoromethyl-phenyl)-3-methylsulf anyl-4,5- dihydroisoxazol-4-yl-cyclopropyl-methanone
A solution of 41 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone in 2 ml of dichloromethane is cooled to -16°C, with stirring and under a nitrogen atmosphere, and 2.4 ml of a 0.1 M solution of 1 ,8-diaza- bicyclo(5.4.0)undec-7-ene (1.5-5) (=DBU) are added. 1.2 ml of a 0.1 M solution of trifluoro- methane sulfochloride in dichloromethane are then added dropwise, the supply of nitrogen is cut off, the cooling bath is removed, and the still slightly yellowish solution is stirred at a temperature of 20°C. After about 20 minutes TLC analysis indicates almost complete conversion into the slightly less polar 4-chloro compound which, in the course of a total of 5 hours and with the further addition of a small amount of DBU solution, is converted into 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-isoxazol-4-yl-cyclopropyl- methanone. For working up, the reaction mixture is cooled, neutralised with a few drops of dilute aqueous acetic acid and extracted between dichloromethane and a small amount of water. The extracts are washed with a small amount of water, dried over sodium sulfate and filtered over a small amount of silica gel. The filtrate is concentrated by evaporation and dried in vacuo. 20 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 161 to 162°C are obtained.
(c) wa 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol- 4-yl-cyclopropyl-methanone
A solution of 41 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone in 10 ml of benzene is heated for 15 hours, under reflux and under a nitrogen atmosphere, with 48 mg of manganese dioxide. After cooling and filtration over a small amount of Hyflo, concentration by evaporation is carried out and the residue is purified by means of HPLC chromatography (Lichrospher Si60, hexane/ethyl acetate). 5-(2-Methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 159 to 161°C is obtained.
Example P16: Preparation of 3,4-dibromo-5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)- 4.5-dihydroisoxazol-4-yl-cvclopropyl-methanone:
393 mg of potassium hydrogen carbonate and 0.2 ml of water are added to a solution of 318 mg of 1-cyclopropyl-3-(2-methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1-one in 5 ml of 1 ,2-dimethoxyethane. In the course of 2 hours, 255 mg of dibromoformaldehyde oxime in 15 ml of dimethoxyethane are added dropwise thereto, with stirring. When the addition is complete, stirring is carried out for 2 hours; the suspension is filtered over a small amount of Hyflo and washed with ethyl acetate. The filtrate is dried over sodium sulfate and concentrated by evaporation, and the residue is purified by means of HPLC chromato- graphy (Lichrospher Si60, hexane/ethyl acetate). 3,4-Dibromo-5-(2-methanesulfonyl-4-tri- fluoromethyl-phenyl)-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone is obtained in the form of a slightly yellowish resin of nD (40°C) = 1.5319.
3,4-Dibromo-5-(2,4-dichloro-phenyl)-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone having a melting point of from 88 to 90°C is obtained in an analogous manner.
Example P17: Preparation of 3-methanesulfinyl-5-(2-methanesulfonyl-4-trifluoromethyl- phenyl)-isoxazol-4-yl-cvclopropyl-methanone:
Figure imgf000038_0001
A solution of 166 mg of m-chloroperbenzoic acid in 2 ml of dichloromethane is added dropwise, while cooling and with stirring at a temperature of from -15 to -18°C, to a solution of 256 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-isoxazol-4-yl- cyclopropyl-methanone in 10 ml of dichloromethane, and stirring is carried out for 4 hours at the same temperature. A further 30 mg of m-chloroperbenzoic acid are then added; after 20 minutes, the mixture is diluted with dichloromethane and washed with sodium hydrogen carbonate solution and water. Filtration over a small amount of silica gel, concentration by evaporation and purification by chromatography (silica gel, ethyl acetate/hexane 1 :1→ 2:1 ) are then carried out. 3-Methanesulfinyl-5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 143 to 145°C is obtained.
Example P18: Preparation of 3-methanesulfonyl-5-(2-methanesulfonyl-4-trifluorormethyl- phenyl)-isoxazol-4-yl-cvclopropyl-methanone:
Figure imgf000039_0001
100 mg of 3-methanesulf inyl-5-(2-methanesulf onyl-4-trif luoromethyl-phenyl)-isoxazol-4-yl- cyclopropyl-methanone that already contains small amounts of 3-methanesulfonyl-5-(2- methanesulfonyl-4-trifluoromethyl-phenyl)-isoxazol-4-yl-cyclopropyl-methanone is placed in 5 ml of dichloromethane at 0°C; a solution of 65 mg of 70 % m-chloroperbenzoic acid in 2 ml of dichloromethane is added dropwise, and stirring is carried out for 15 hours at a temperature of 20°C. The mixture is then diluted with dichloromethane, washed with sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated by evaporation; the residue is purified on silica gel (hexane/ethyl acetate). 3-Methanesulfonyl-5-(2-methane- sulfonyl-4-trifluoromethyl-phenyl)-isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 178 to 180°C is obtained.
Example P19: Preparation of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3- methylsulfanyl-4.5-dihvdroisoxazol-4-yl-cvclopropyl-methanone:
Figure imgf000040_0001
10 mg of sodium hydrogen carbonate are added to a solution of 41 mg of 5-(2-methane- sulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol-4-yl-cyclopropyl- methanone in 20 ml of carbon tetrachioride, and then 1 ml of 0.1 M bromine in carbon tetrachioride is added dropwise thereto. After in each case one hour or two hours, a further 10 mg of sodium hydrogen carbonate and 0.5 ml of 0.1 M bromine solution are added. The reaction mixture is then heated for 2 hours under reflux and subsequently left to stand for 15 hours. The residue that remains after washing with ice-water, drying over sodium sulfate, filtering over a small amount of silica gel and concentrating by evaporation is purified by means of HPLC chromatography (Lichrospher Si60, hexane/ethyl acetate). 1 -(4-Bromo-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol-4-yl- cyclopropyl-methanone is obtained in the form of a viscous resin of nD (40°C) = 1.5399.
The compounds listed in the following Tables 1 to 19 can be prepared analogously to the above Examples and the information given in the description. In the Tables, Ph represents the phenyl group and Cp represents cyclopropyl:
Table 1 : Compounds of formula la:
No. R91 z R92 R93 R94 R95 M.p.(°C) /n
1.001 CH3 0 Cl H Cl H 105-107
Figure imgf000041_0002
1.003 CH3 0 NO2 H OCHF2 H
1.004 CH3 0 NO2 H OSO2CH3 H
1.005 CH3 0 NO2 H Cl H
1.006 CH3 0 NO2 H SCH3 H
1.007 CH3 0 NO2 H SO2CH3 H
1.008 CH3 0 NO2 H OCF2-CHCIF H
1.009 CH3 0 NO2 H OCF2-CH2F-CF3 H
1.010 CH3 0 NO2 H OCF3 H
1.011 CH3 0 NO2 H H H
1.012 CH3 NO2 H CF3 H
1.013 CH3 NO2 H SOCH3 H
1.014 CH3 NO2 H OCHF2 H
1.015 CH3 NO2 H OSO2CH3 H
1.016 CH3 NO2 H Cl H
1.017 CH3 NO2 H SCH3 H
1.018 CH3 NO2 H SO2CH3 H
1.019 CH3 NO2 H OCF2-CHCIF H
1.020 CH3 NO2 H OCF2-CH2F-CF3 H
Figure imgf000041_0003
1.022 CH3 0 SO2CH3 H Br H No. ^91 »92 R93 RΘ R95 M.p.(°C)
Figure imgf000042_0001
1.023 CH3 0 SO2CH3 H CF3 H 159-161
1.024 CH3 0 SO2CH3 Cl Cl H
1.025 CH3 0 SO2CH3 H Cl H
1.026 CH3 0 SO2CH3 H NO2 H
1.027 CH3 0 SO2CH3 H SO2CH3 H
1.028 CH3 0 SO2C2H5 H Cl H
1.029 CH3 0 SO2-isoC3H7 H Cl H
1.030 CH3 0 SO2Ph H CF3 H
1.031 CH3 0 SO2-isoC3H7 H OCF2-CH2F H
1.032 CH3 0 SO2-isoC3H7 H OCF2-CHBr2 H
1.033 CH3 2 NO2 H CF3 H
Figure imgf000042_0002
1.035 CH3 2 NO2 H OCHF2 H
1.036 CH3 2 NO2 H OSO2CH3 H
1.037 CH3 2 NO2 H Cl H
1.038 CH3 2 NO2 H SCH3 H
1.039 CH3 2 NO2 H SO2CH3 H
1.040 CH3 0 NO2 H CF3 H
1.041 CH3 0 Cl H F H
1.042 CH3 0 Cl H SO2CH3 H 154-15:
1.043 CH3 0 Cl H OCHF2 H
1.044 CH3 0 Cl H SCH3 H
1.045 CH3 0 Cl H Br H
1.046 CH3 0 Cl H NO2 H
1.047 CH3 0 Cl H SC2H5 H
1.048 CH3 0 Cl H OSO2CH3 H
Figure imgf000042_0003
1.050 CH3 0 Cl H S-nC3H7 H
1.051 CH3 0 Cl H SO2nC3H7 H
1.052 C2H5 0 CF3 H SCH3 H
1.053 C2Hs 0 CF3 H Cl H No. ^91 R92 I93 Rg4 R95 M.p.(°C)
Figure imgf000043_0001
1.054 C2Hδ 0 CF3 H F H
1.055 C2Hδ 0 CF3 H Br H
1.056 C2H5 0 CF3 H SO2CH3 H
1.057 C2H5 0 CF3 H CF3 H
1.058 CH3 0 NO2 H SO2CF3 H
1.059 CH3 0 NO2 H SO2CHF2 H
1.060 CH3 0 NO2 H F H
1.061 CH3 0 NO2 H Br H
1.062 CH3 0 NO2 Cl H H
1.063 CH3 0 NO2 CH3 H H
1.064 CH3 0 NO2 H SC2Hs H
1.065 CH3 0 NO2 H CH3 H
1.066 CH3 0 NO2 H SO2C2Hs H
1.067 CH3 1 SO2CH3 H Br H
1.068 CH3 1 SO2CH3 H CF3 H 143-14J
1.069 CH3 1 SO2CH3 Cl Cl H
1.070 CH3 1 SO2CH3 H Cl H
1.071 CH3 1 SO2CH3 H NO2 H
1.072 CH3 1 SO2CH3 H SO2CH3 H
1.073 CH3 1 SO2C2H5 H Cl H
1.074 CH3 1 SO2-isoC3H7 H Cl H
1.075 CH3 1 SO2Ph H CF3 H
1.076 CH3 1 SO2-isoC3H7 H OCF2-CH2F H
1.077 CH3 1 SO2-isoC3H7 H OCF2-CHBr2 H
1.078 CH3 0 CF3 H SCH3 H
1.079 CH3 0 CF3 H Cl H
1.080 CH3 0 CF3 H F H
1.081 CH3 0 CF3 H Br H
1.082 CH3 0 CF3 H SO2CH3 H
1.083 CH3 0 CF3 H CF3 H 145-14
1.084 CH3 0 NO2 H NO2 H No. "191 R 92 R93 RΘ4 R95 M.p.(°C)
Figure imgf000044_0001
1.085 CH3 0 NO2 H OH H
Figure imgf000044_0002
1.087 CH3 0 NO2 H OSO2Ph H
1.088 CH3 0 NO2 H OSO2C2H5 H
1.089 CH3 0 NO2 H OSO2-isoC3H7 H
1.090 CH3 0 NO2 CH3 H H
1.091 CH3 0 NO2 H OSO2CF3 H
1.092 CH3 0 NO2 H SO2CH2-CF3 H
1.093 CH3 0 NO2 H SO2CF2-CF3 H
1.094 CH3 0 NO2 H S-nC4H9 H
1.095 CH3 0 NO2 H S-nC3H7 H
1.096 C2H5 0 NO2 H OSO2CF3 H
1.097 C2H5 0 NO2 H SO2CH2-CF3 H
1.098 C2H5 0 NO2 H SO2CF2-CF3 H
1.099 C2Hs 0 NO2 H S-nC4H9 H
1.100 C2Hs 0 NO2 H S-nC3H7 H
1.101 CH3 CF3 H SCH3 H
1.102 CH3 CF3 H Cl H
1.103 CH3 CF3 H F H
1.104 CH3 CF3 H Br H
1.105 CH3 CF3 H SO2CH3 H
1.106 CH3 CF3 H CF3 H 127-128
1.107 CH3 2 CF3 CH3 H H
1.108 CH3 2 CF3 H SC2H5 H
1.109 CH3 2 CF3 H CH3 H
1.110 CH3 2 CF3 H SO2C2Hδ H
1.111 CH3 2 CF3 H Br H
1.112 CH3 2 CF3 H CF3 H
1.113 CH3 1 Cl H Cl H
1.114 CH3 1 Cl H F H
1.115 CH3 1 Cl H SO2CH3 H 186-188 No. R91 z R92 R93 RΘ R95 M.p.(°C)
/no
Figure imgf000045_0001
1.117 CH3 Cl H SCH3 H
1.118 CH3 Cl H Br H
1.119 CH3 Cl H NO2 H
1.120 CH3_ Cl H SC2Hδ H
1.121 CH3 Cl H OSO2CH3 H
1.122 CH3 Cl H SOCH3 H
1.123 CH3 Cl H S-nC3H7 H
1.124 CH3 Cl H SO2nC3H7 H
1.125 CH3 0 F H Br H
1.126 CH3 0 F H Cl H
1.127 CH3 0 F H CF3 H
1.128 CH3 0 CH3 Cl SO2CH3 H
1.129 CH3 0 CH3 OCH3 SO2CH3 H 146-148
1.130 CH3 0 CH3 OC2H5 SO2CH3 H
1.131 CH3 0 CH3 H SO2CH3 CH3
1.132 CH3 0 CH3 CH3 OSO2CH3 CH3
1.133 CH3 0 CH3 OC2H5 Br H
1.134 CH3 0 CH3 OC2H5 SO2CH2CI H
1.135 CH3 0 CH3 Cl SCH3 H
1.136 CH3 0 CH3 OCH2CF3 Br H
1.137 CH3 0 CH3 OCH3 Br H
1.138 CH3 0 CH3 OC2H4OCH3 Br H
1.139 CH3 0 CH3 CO2CH3 SO2CH3 H
Figure imgf000045_0002
1.141 CH3 0 CH3 OCH3 Br CH3
1.142 CH3 0 CH3 OCH3 SO2CH3 CH3
1.143 CH3 0 CH3 OCH2CCH Br H
1.144 CH3 0 CH3 OCH2Ph Br H
1.145 CH3 0 CH3 OCH2CH=CH2 Br H
1.146 CH3 0 CH3 C(CH3)=NOCH3 SO2CH3 H No. R91 z R92 R93 Rg4 R95 M.p.(°C)
/ Irnso 35
1.147 CH3 0 CH3 O-C2H4-SCH3 Br H
1.148 CH3 0 CH3 O-isoC3H7 Br H
1.149 CH3 0 CH3 OCH2-SCH3 Br H
1.150 CH3 0 CH3 CH2OCH3 SO2CH3 H
1.151 CH3 0 CH3 CO2CH3 SCH3 H
1.152 CH3 0 Cl Cl SO2CH3 H
1.153 CH3 0 Cl OCH3 SO2CH3 H
1.154 CH3 0 Cl OC2H5 S02C2H5 H
1.155 CH3 0 Cl OC2H5 SO2CH3 H
1.156 CH3 0 Cl CH2OPh Cl H
1.157 CH3 0 Cl COPh Cl H
1.158 CH3 0 Cl CO2CH3 SO2CH3 H
1.159 CH3 0 Cl Cl Cl H
Figure imgf000046_0001
1.161 CH3 0 Cl Cl OSO2CH3 H
1.162 CH3 0 Cl H OSO2C2H5 H
Figure imgf000046_0002
1.164 CH3 0 Cl H Cl H
1.165 CH3 0 Cl H SO2CH3 H
1.166 CH3 0 Cl H SO2CH3 H
1.167 CH3 0 Cl H SO2CH3 H
Figure imgf000046_0003
1.169 CH3 0 SCH3 COCH3 SCH3 H
1.170 CH3 0 SCH3 CH2OPh SCH3 H
1.171 CH3 0 SCH3 COCH3 S2CHδ H
1.172 C2Hδ 0 CH3 Cl SO2CH3 H
1.173 C2Hs 0 CH3 OCH3 SO2CH3 H
1.174 C2Hδ 0 CH3 OC2H5 SO2CH3 H
1.175 C2Hδ 0 CH3 H SO2CH3 CH3
1.176 C2Hs 0 CH3 CH3 OSO2CH3 CH3
1.177 C2Hδ 0 CH3 OC2H5 Br H No. R91 z R92 R93 RΘ4 R95 M.p.(°C)
/nD 35
1.178 C2Hδ 0 CH3 OC2H5 SO2CH2CI H
1.179 C2Hs 0 CH3 Cl SCH3 H
1.180 C2Hs 0 CH3 OCH2CF3 Br H
Figure imgf000047_0001
1.182 C2Hs 0 CH3 OC2H4OCH3 Br H
1.183 C2H5 0 CH3 CO2CH3 SO2CH3 H
Figure imgf000047_0002
1.185 C2H5 0 CH3 OCH3 Br CH3
1.186 C2H5 0 CH3 OCH3 SO2CH3 CH3
1.187 C2Hδ 0 CH3 OCH2CCH Br H
1.188 C2Hs 0 CH3 OCH2Ph Br H
1.189 C2Hδ 0 CH3 OCH2CH=CH2 Br H
1.190 C2H5 0 CH3 C(CH3)=NOCH3 SO2CH3 H
1.191 C2H5 0 CH3 O-C2H4-SCH3 Br H
1.192 C2H5 0 CH3 O-isoC3H7 Br H
1.193 C2H5 0 CH3 OCH2-SCH3 Br H
1.194 C2Hs 0 CH3 CH2OCH3 SO2CH3 H
1.195 C2H5 0 CH3 CO2CH3 SCH3 H
1.196 C2Hδ 0 Cl Cl SO2CH3 H
1.197 C2H5 0 Cl OCH3 SO2CH3 H
1.198 C2H5 0 Cl OC2H5 SO2C2H5 H
1.199 C2Hδ 0 Cl OC2H5 SO2CH3 H
1.200 C2H5 0 Cl CH2OPh Cl H
Figure imgf000047_0003
1.202 C2H5 0 Cl CO2CH3 SO2CH3 H
Figure imgf000047_0004
1.205 C2H5 0 Cl Cl OSO2CH3 H
1.206 C2H5 0 Cl H OSO2C2H5 H
Figure imgf000047_0005
Figure imgf000048_0001
1.212 C2H5 0 SCH3 Cl Cl H
1.213 C2H5 0 SCH3 COCH3 SCH3 H
1.214 C2H5 0 SCH3 CH2OPh SCH3 H
1.215 C2H5 0 SCH3 COCH3 S2CH5 H
1.216 CH3 CH3 H Br H
1.217 CH3 CH3 H SCH3 H
Figure imgf000048_0002
1.219 CH3 CH3 H Cl H
1.220 CH3 CH3 H CH3 H
1.221 CH3 CH2SO CH3 H Br H
1.222 CH3 0 CH3 H Br H
1.223 CH3 0 CH3 H SCH3 H
1.224 CH3 0 CH3 H SO2CH3 H
1.225 CH3 0 CH3 H Cl H
1.226 CH3 0 CH3 H CH3 H
1.227 CH3 0 CH2SO CH3 H Br H
1.228 C2Hδ 0 CH3 H Br H
1.229 C2Hδ 0 CH3 H SCH3 H
1.230 C2H5 0 CH3 H SO2CH3 H
1.231 C2H5 0 CH3 H Cl H
1.232 C2Hδ 0 CH3 H CH3 H
1.233 C2Hδ 0 CH2SO2CH3 H Br H
1.234 C2H5 CH3 H Br H
1.235 C2H5 CH3 H SCH3 H
1.236 C2H5 CH3 H SO2CH3 H
1.237 C2H5 CH3 H Cl H
1.238 C2H5 CH3 H CH3 H
1.239 C2H5 CH2SO2CH3 H Br H No. R91 z R92 R93 RΘ4 R95 M.p.(°C)
Irs 35
1.240 C2H5 0 NO2 H SO2CF3 H
1.241 C2H5 0 NO2 H SO2CHF2 H
1.242 C2Hs 0 NO2 H F H
1.243 C2Hs 0 NO2 H Br H
Figure imgf000049_0001
1.248 C2Hs 0 NO2 H SO2C2H5 H
1.249 C2Hδ 0 SO2CH3 H Br H
1.250 C2Hs 0 SO2CH3 H CF3 H
1.251 C2H5 0 SO2CH3 Cl Cl H
1.252 C2Hs 0 SO2CH3 H Cl H
1.253 C2Hs 0 SO2CH3 H NO2 H
1.254 C2H5 0 SO2CH3 H SO2CH3 H
1.255 C2Hδ 0 SO C2Hs H Cl H
1.256 C2H5 0 SO2-isoC3H7 H Cl H
Figure imgf000049_0002
1.258 C2H5 0 : SO2-isoC3H7 H OCF2-CH2F H
1.259 C2H5 0 : SO2-isoC3H7 H OCF2-CHBr2 H
1.260 CH3 0 OCH3 H SO2CH3 H 167-169
1.261 CH3 1 OCH3 H SO2CH3 H 176-177
1.262 CH3 2 OCH3 H SO2CH3 H resin
1.263 CH3 2 SO2CH3 H CF3 H 178-180
1.264 isoC3H7 0 SO2CH3 H CF3 H 120-121
1.265 CH3 1 CH3 OCH3 SO2CH3 H
1.266 CH3 1 CH3 CH2OCH3 SO2CH3 H
1.267 CH3 1 Cl CO2CH3 SO2CH3 H
1.268 CH2CO2CH3 * 0 SO2CH3 H CF3 H
1.269 CH2CO2C2H5 0 SO2CH3 H CF3 H
1.270 C2H4CO2CH3 0 SO2CH3 H CF3 H Table 2: Compounds of formula lb:
Figure imgf000050_0001
1 -CH3-Cp = 1 -methylcyclopropyl
No. R z R92 R93 RΘ R95 Phys data
2.001 tert-C4Hg 0 Cl H SO2CH3 H
2.002 tert-C4H9 0 CH3 Cl SO2CH3 H
2.003 tert-C Hg 0 CH3 H Cl H
2.004 tert-C4H9 0 CH3 OC2H5 SO2CH3 H
2.005 tert-C4H9 0 SO2CH3 H Cl H
2.006 tert-C4H9 0 CF3 H SO2CH3 H
2.007 tert-C4H9 0 CH3 Cl SCH3 H
2.008 tert-C4Hg 0 CH3 OC2H5 Br H
2.009 tert-C4H9 0 CH3 OCH2CF3 Br H
2.010 tert-C4Hg 0 CH3 H SO2CH3 H
2.011 tert-C4H9 0 Cl H SO2CH3 H
2.012 tert-C4H9 0 SO2CH3 H CF3 H
2.013 tert-C4Hg 0 CH3 OCH3 SO2CH3 H
2.014 tert-C4Hg 0 NO2 H CF3 H
2.015 tert-C4H9 0 NO2 H SO2CH3 H
2.016 tert-C4H9 0 CF3 H F H
2.017 tert-C4H9 0 F H CF3 H
2.018 tert-C4Hg 0 Cl O-C2H4-SCH3 Br H No. R z R92 R93 R94 R95 Phys data
2.019 tert-C4H9 0 Cl H SCH3 H
2.020 tert-C4Hg 0 slCH3-SO2CH3 H Cl H
Figure imgf000051_0001
2.022 tert-C4Hg 0 Cl H NCH3-SO2CH3 H
2.023 tert-C4H9 0 Cl OCH3 SO2CH3 H
2.024 1-CH3-Cp 0 Cl H SO2CH3 H
2.025 1 -CH3-Cp 0 CH3 Cl SO2CH3 H
2.026 1 -CH3-Cp 0 CH3 H Cl H
2.027 1-CHa-Cp 0 CH3 OC2H5 SO2CH3 H
2.028 1 -CH3-Cp 0 SO2CH3 H Cl H
2.029 1-CH3-Cp 0 CF3 H SO2CH3 H
2.030 1 -CH3-Cp 0 CH3 Cl SCH3 H
2.031 1-CH3-Cp 0 CH3 OC2H5 Br H
2.032 1 -CH3-Cp 0 CH3 OCH2CF3 Br H
2.033 1-CH3-Cp 0 CH3 H SO2CH3 H
2.034 1 -CH3-Cp 0 Cl H SO2CH3 H
2.035 1-CH3-Cp 0 SO2CH3 H CF3 H
2.036 1 -CH3-Cp 0 CH3 OCH3 SO2CH3 H
2.037 1 -CH3-Cp 0 NO2 H CF3 H
2.038 1 -CH3-Cp 0 NO2 H SO2CH3 H
2.039 1-CH3-Cp 0 CF3 H F H
2.040 1 -CH3-Cp 0 F H CF3 H
2.041 1-CH3-Cp 0 Cl O-C2H4-SCH3 Br H
2.042 1 -CH3-Cp 0 Cl H SCH3 H
2.043 1-CH3-Cp 0 NCH3-SO2CH3 H Cl H
2.044 1 -CH3-Cp 0 NCH3-SO2CH3 H CF3 H
2.045 1-CH3-Cp 0 Cl OCH3 SO2CH3 H
Figure imgf000052_0001
O V) X O x o O x x x x x x x x Ω ^i x x £ X X X
Q) 3"
Q) co
No. 191 192 193 194 ^95 Phys data
3.022 CH3 0 NO2 OCH2CH=CH2 Cl H -
3.023 CH3 0 NO2 O(CH2)5CH3 Cl H -
3.024 CH3 0 NO2 OCH2Ph Cl H -
3.025 C2H5 0 Br OCH3 SO2C2Hs H -
3.026 C2H5 0 Br OCH3 CH3 H -
3.027 C2H5 0 Br OC2H4OCH3 Br H -
3.028 C2H5 0 Br OCH3 Br H -
3.029 C2H5 0 Br OCH2SCH3 Br H -
3.030 C2Hδ 0 Br OC2H4OCH3 Br H -
3.031 C2Hδ 0 Br OCH2SO2CH3 Br H -
3.032 C2H5 0 Br OCH2SOCH3 Br H -
3.033 CH3 1 Br OCH3 SO2C2H5 H -
3.034 CH3 1 Br OCH3 CH3 H -
3.035 CH3 1 Br OC2H4OCH3 Br H -
3.036 CH3 1 Br OCH3 Br H -
3.037 CH3 1 Br OCH2SCH3 Br H -
3.038 CH3 1 Br OC2H4OCH3 Br H -
3.039 CH3 1 Br OCH2SO2CH3 Br H -
3.040 CH3 1 Br OCH2SOCH3 Br H -
3.041 CH3 2 SCH3 COCH3 SCH3 H -
3.042 CH3 2 SCH3 CH2OPh SCH3 H -
3.043 CH3 2 SCH3 COCH3 S2CHs H -
3.044 CH3 2 SCH3 Cl H H .
Table 4: Compounds of formula Ic:
Figure imgf000054_0001
No. Phenyl z R92 R93 R94 R95 Phys, data
4.001 2-NO2 0 Cl H SO2CH3 H
4.002 2-CI 0 CH3 Cl SO2CH3 H
4.003 2-CH3 0 NO2 H SO2CH3 H
Figure imgf000054_0002
4.005 2-SO2CH3 0 SO2CH3 H CF3 H
4.006 2-CF3 0 CF3 H SO2CH3 H
4.007 2-NH2 0 CH3 Cl SCH3 H
4.008 2-O-isoC3H7 0 SO2CH3 OC2H5 CF3 H
4.009 2-CI-4- 0 NO2 H H H SO2CH3
4.010 2-NO2-4-SO2CH3 0 Cl H H H
4.011 2-NO2-4-CF3 0 CH3 H H H
4.012 2-SO2CH3-4-CF3 0 SCH3 H H H
4.013 2-CF3-4-SO2CH3 0 SO2CH3 H H H
Table 5: Compounds of formula Id:
Figure imgf000055_0001
No. Phenyl z R92 R93 R94 R95 M.p. (°C)
5.001 2-NO2 0 Cl H SO2CH3 H
5.002 2-CI 0 CH3 Cl SO2CH3 H
5.003 2-CH3 0 NO2 H SO2CH3 H
5.004 2-SCH3 0 NO2 H CF3 H
5.005 2-SO2CH3 0 SO2CH3 H CF3 H
5.006 2-CF3 0 CF3 H SO2CH3 H
5.007 2-NH2 0 CH3 Cl SCH3 H
5.008 2-O-isoC3H7 0 SO2CH3 OC2H5 CF3 H
5.009 2-CI-4-SO2CH3 0 NO2 H H H
5.010 2-NO2-4-SO2CH3 0 Cl H H H
5.011 2-NO2-4-CF3 0 CH3 H H H
5.012 2-SO2CH3-4-CF3 0 SCH3 H H H
5.013 2-CF3-4-SO2CH3 0 SO2CH3 H H H
5.014 4-CI 0 SO2CH3 H CF3 H 72-75
Table 6: Compounds of formula le:
Figure imgf000056_0001
data
6.001 CH3 0 Cl H O O
6.002 CH3 0 NO2 H O O
6.003 CH3 0 CH3 H O O
6.004 CH3 0 SCH3 H O O
6.005 CH3 0 SOCH3 H O O
6.006 CH3 0 SO2CH3 H O O
6.007 CH3 0 CH3 CH3 O O
6.008 CH3 0 Cl CH3 O O
6.009 CH3 0 CH3 Br O O
6.010 C2Hδ 0 Cl H O O
6.01 1 C2Hδ 0 NO2 H O O
6.012 C2Hs 0 CH3 H O O
6.013 C2Hs 0 SCH3 H O O
Figure imgf000056_0002
6.016 C2Hs 0 CH3 CH3 O O
6.017 C2Hδ 0 Cl CH3 O O
Figure imgf000056_0003
6.019 CH3 Cl H S02CH3 O
6.020 CH3 NO2 H S02CH3 O
Figure imgf000056_0004
6.023 CH3 SOCH3 H S02CH3 O No. Ri "85 ~»86 Phys. data
6.024 CH3 SO2CH3 H S02CH3 O 6.025 CH3 CH3 CH3 S02CH3 O 6.026 CH3 Cl CH3 SO2CH3 O 6.027 CH3 CH3 Br S02CH3 O
Figure imgf000057_0001
6.029 C2Hs NO2 H O SO2CH3
Figure imgf000057_0002
6.031 C2Hδ SCH3 H O SO2CH3 6.032 C2Hδ SOCH3 H O SO2CH3 6.033 C2H5 SO2CH3 H O SO2CH3 6.034 C2Hδ CH3 CH3 O SO2CH3 6.035 C2Hδ Cl CH3 O SO2CH3 6.036 C2Hδ CH3 Br O SO2CH3
Table 7: Compounds of formula If:
Figure imgf000057_0003
No. R. z R, 87 R, 88 X4 Phys. data
7.001 CH3 0 Cl H O O
7.002 CH3 0 NO2 H O O
7.003 CH3 0 CH3 H O O
7.004 CH3 0 SCH3 H O O
Figure imgf000057_0004
7.006 CH3 0 SO2CH3 H O O
7.007 CH3 0 CH3 CH3 O O No. R, 187 188 χ4 Y4 Phys. data
7.008 CH3 0 Cl CH3 O O
7.009 CH3 0 CH3 Br O O
7.010 C2H5 0 Cl H O O
7.011 C2H5 0 NO2 H O O
7.012 C2H5 0 CH3 H O O
7.013 C2H5 0 SCH3 H O O
7.014 C2H5 0 SOCH3 H O O
7.015 C2H5 0 SO2CH3 H O O
7.016 C2H5 0 CH3 CH3 O O
7.017 C2H5 0 Cl CH3 O O
7.018 C2H5 0 CH3 Br O O
7.019 CH3 1 Cl H SO2CH3 O
7.020 CH3 1 NO2 H SO2CH3 O
7.021 CH3 1 CH3 H SO2CH3 O
7.022 CH3 1 SCH3 H SO2CH3 O
7.023 CH3 1 SOCH3 H SO2CH3 O
7.024 CH3 1 SO2CH3 H SO2CH3 O
7.025 CH3 1 CH3 CH3 SO2CH3 O
7.026 CH3 1 Cl CH3 SO2CH3 O
7.027 CH3 1 CH3 Br SO2CH3 O
7.028 C2H5 1 Cl H O SO2CH3
7.029 C2H5 1 NO2 H O SO2CH3
7.030 C2H5 1 CH3 H O SO2CH3
7.031 C2H5 1 SCH3 H O SO2CH3
7.032 C2H5 1 SOCH3 H O SO2CH3
7.033 C2H5 1 SO2CH3 H O SO2CH3
7.034 C2H5 1 CH3 CH3 O SO2CH3
7.035 C2H5 1 Cl CH3 O SO2CH3
7.036 C2H5 1 CH3 Br O SO2CH3 CD ∞ ∞ Cα CXJ OO OO CO ∞ ∞ OO ∞ Cβ OO OO OO ∞ OO OO OO OO OO o o o o o o o o o o o o o o o o o o o to ro ι - - _l _k _L O o o z ro -^ o co oo -j cn cn ^ CO ro -i o co 00 o -vl o O) oW o^ (oΛ Mo o-
Figure imgf000059_0001
0> O
Figure imgf000060_0001
ro ιo ro ro ro ro ro N
x O Ox Ox Ox Ox Ox Ox Ox Ox Ox xO xO xO xO oZ ^Ω o X oX Xo oX Xo X
ox ox ox ox ox _x _x ox ox ox ox ox _x _x _x _x ox ox ox ox ox
Figure imgf000060_0002
0) CO
5 ~ X oX oX oX o1 δ oX O υ X oX oX
Figure imgf000061_0001
c
Figure imgf000061_0002
CO CO CO CD CO CO CD CD CD CO CO CO CO CO CO CO CO CD CO o o o O O o o o o o o o o
4o o 4- o CO CoO CoO ω CO CO CO CO CO CoO ro ro ro ro ro ro ro o z O CO 00 en en 4>. CO ro o CD 00 -v| en en 4- CO
Xo oX Xo oX Xo pX pX pX p p p p p p o o o o o X ω co c o co _ιr n zr Xr ϋXr ύXr ύXr ύXr tXr uX> ωX ωX ωX ωX ro ro ro N
S * o __ _r O _ 0 0 0 0 _ X X x X Ω x x x x X o S n Ω O x x O X
x x x Ω x x x x x x x x x x x x x x x X
Figure imgf000062_0001
CO CO CO co o o 0 o
° 8 o o O O O o o
X o co O O o O O O o - o 1 x x x X X
Figure imgf000062_0002
Figure imgf000063_0001
o o T- CM CO in CO oo en o T- CM CO Tf in CO r-» oo en o T- CM CO
_ϋ O O O o o o o o O T- ι- ro- -oI- CoM O O O o o o o q o o o δ CM o δ o o o -- CoM CoM o
CO o b b b o o o o o o
Figure imgf000064_0001
P P P 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
ro ro to ro ro ro ro o N
Figure imgf000064_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 Ω X
Figure imgf000064_0003
x x x x x x x x 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_0004
No. R91 z R92 R93 R94 R95 M.p.(°C)/
-, 35
10.055 C2Hs 0 CF3 H Br H
10.056 C2Hs 0 CF3 H SO2CH3 H
10.057 C2Hs 0 CF3 H CF3 H
10.058 CH3 0 NO2 H SO2CF3 H
10.059 CH3 0 NO2 H SO2CHF2 H
10.060 CH3 0 NO2 H F H
10.061 CH3 0 NO2 H Br H
10.062 CH3 0 NO2 Cl H H
10.063 CH3 0 NO2 CH3 H H
10.064 CH3 0 NO2 H SC2Hδ H
10.065 CH3 0 NO2 H CH3 H
10.066 CH3 0 NO2 H SO2C2H5 H
10.067 CH3 SO2CH3 H Br H
10.068 CH3 SO2CH3 H CF3 H
10.069 CH3 SO2CH3 Cl Cl H
10.070 CH3 SO2CH3 H Cl H
10.071 CH3 SO2CH3 H NO2 H
10.072 CH3 SO2CH3 H SO2CH3 H
10.073 CH3 SO2C Hδ H Cl H
10.074 CH3 SO2-isoC3H7 H Cl H
10.075 CH3 SO2Ph H CF3 H
10.076 CH3 SO2-isoC3H7 H OCF2-CH2F H
10.077 CH3 SO2-isoC3H7 H OCF2-CHBr2 H
10.078 CH3 0 CF3 H SCH3 H
10.079 CH3 0 CF3 H Cl H
10.080 CH3 0 CF3 H F H
10.081 CH3 0 CF3 H Br H
10.082 CH3 0 CF3 H SO2CH3 H
10.083 CH3 0 CF3 H CF3 H
10.084 CH3 0 NO2 H NO2 H
10.085 CH3 0 NO2 H OH H
Figure imgf000066_0001
H υa. X X X X X X X 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 imgf000066_0002
x X X X X
~ - ~ x x x x x x x x x x x x x x g x x x x x x x x x co
Figure imgf000066_0003
o o o o o o o
Figure imgf000066_0004
O q o o z
4- 4- 4^. 4- 4^. 4- 4- 4 CO CO CO CO CO CO ro ro ro ro ro ro ro ro ro ro __ _-. o
^l en cn 4*. co to o- CO CO CO CO
CD 00 --J en en 4*. CO ro -— o CO 00 -j σ> en 4- CO ro o CO 00 ^J
Figure imgf000067_0001
o o o o N
O O O O O O O O O O O O O O O O O O O O -π O O O O O O O O cXo cXo cXo cXo coX cXo cXo cXo cXo cXo coX cXo cXo cXo cXo cXo cXo ωX cXo c!o
Figure imgf000067_0002
X X X X X X X X X X X X X X x .,. 0x 0x x
Figure imgf000067_0003
No. R91 z R92 R93 R94 R95 M.p.(°C)/
., 35
10.148 CH3 0 CH3 O-isoC3H7 Br H
10.149 CH3 0 CH3 OCH2-SCH3 Br H
10.150 CH3 0 CH3 CH2OCH3 SO2CH3 H
10.151 CH3 0 CH3 CO2CH3 SCH3 H
10.152 CH3 0 Cl Cl SO2CH3 H
10.153 CH3 0 Cl OCH3 SO2CH3 H
10.154 CH3 0 Cl OC2H5 SO2C2H5 H
10.155 CH3 0 Cl OC2H5 SO2CH3 H
10.156 CH3 0 Cl CH2OPh Cl H
10.157 CH3 0 Cl COPh Cl H
10.158 CH3 0 Cl CO2CH3 SO2CH3 H
10.159 CH3 0 Cl Cl Cl H
Figure imgf000068_0001
10.161 CH3 0 Cl Cl OSO2CH3 H
10.162 CH3 0 Cl H OSO2C2H5 H
10.163 CH3 0 Cl H OCH3 H
10.164 CH3 0 Cl H Cl H
10.165 CH3 0 Cl H SO2CH3 H
10.166 CH3 0 Cl H SO2CH3 H
10.167 CH3 0 Cl H SO2CH3 H
10.168 CH3 0 SCH3 Cl Cl H
10.169 CH3 0 SCH3 COCH3 SCH3 H
10.170 CH3 0 SCH3 CH2OPh SCH3 H
10.171 CH3 0 SCH3 COCH3 S2CHs H
10.172 C2H5 0 CH3 Cl SO2CH3 H
10.173 C2Hδ 0 CH3 OCH3 SO2CH3 H
10.174 C2Hδ 0 CH3 OC2H5 SO2CH3 H
10.175 C2Hs 0 CH3 H SO2CH3 CH3
10.176 C2Hδ 0 CH3 CH3 OSO2CH3 CH3
10.177 C2Hδ 0 CH3 OC2H5 Br H
10.178 C2Hs 0 CH3 OC2H5 SO2CH2CI H o o o o o o o o o ro io to ro ro IV) fo ro iv> ho o o o o o o o o o o co CD co co co co CO CO CD CO 00 00 00 00 oo oo oo oo oo oo -sl oz to oo O) en 4k ω ro o co oo en en *. CO ro o CO 00 en en 4- co ro o co
Figure imgf000069_0001
o o o o o o o o o N
Q o n o π o g o o o o o o cSo cS cSo cSo cSo c5o c?o cSo c5o cSo c5o co5 c?o cSo c5o cSo cSo
Figure imgf000069_0002
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 _ X _ X _ X X
σ
O
No. 191 R 92 193 R94 R95 M.p.(°C)/
„ 35
10.210 C2H5 0 Cl H SO2CH3 H
10.211 C2Hδ 0 Cl H SO2CH3 H
10.212 C-.H5 0 SCH3 Cl Cl H
10.213 C2Hδ 0 SCH3 COCH3 SCH3 H
10.214 C2H5 0 SCH3 CH2OPh SCH3 H
10.215 C2H5 0 SCH3 COCH3 S2CHs H
10.216 CH3 CH3 H Br H
10.217 CH3 CH3 H SCH3 H
10.218 CH3 CH3 H SO2CH3 H
10.219 CH3 CH3 H Cl H
10.220 CH3 CH3 H CH3 H
10.221 CH3 CH2SO2CH3 H Br H
10.222 CH3 0 CH3 H Br H
10.223 CH3 0 CH3 H SCH3 H
10.224 CH3 0 CH3 H SO2CH3 H
10.225 CH3 0 CH3 H Cl H
10.226 CH3 0 CH3 H CH3 H
10.227 CH3 0 CH2SO2CH3 H Br H
Figure imgf000070_0001
10.229 C2Hs 0 CH3 H SCH3 H
10.230 C2Hs 0 CH3 H SO2CH3 H
10.231 C2Hs 0 CH3 H Cl H
10.232 C2H5 0 CH3 H CH3 H
10.233 C2H5 0 CH2SO2CH3 H Br H
10.234 C2H5 CH3 H Br H
10.235 C2H5 CH3 H SCH3 H
10.236 C2Hδ CH3 H SO2CH3 H
10.237 C2H5 CH3 H Cl H
10.238 C2H5 CH3 H CH3 H
10.239 C2H5 CH2SO2CH3 H Br H
10.240 C2H5 0 NO2 H SO2CF3 H No. R91 z R92 R93 R94 R95 M.p.(°C)/ rs 35 no
10.241 C2H5 0 NO2 H SO2CHF2 H
10.242 C2Hs 0 NO2 H F H
Figure imgf000071_0001
10.246 C2H5 0 NO2 H SC2Hδ H
10.247 C2Hδ 0 NO2 H CH3 H
10.248 C2Hδ 0 NO2 H SO2C2Hs H
10.249 C2H5 0 SO2CH3 H Br H
10.250 C2H5 0 SO2CH3 H CF3 H
10.251 C2H5 0 SO2CH3 Cl Cl H
10.252 C2Hδ 0 SO2CH3 H Cl H
10.253 C2Hδ 0 SO2CH3 H NO2 H
10.254 C2Hδ 0 SO2CH3 H SO2CH3 H
10.255 C2Hs 0 SO2C2Hs H Cl H
10.256 C2H5 0 SO2-isoC3H7 H Cl H
10.257 C2Hs 0 SO2Ph H CF3 H
10.258 C2Hs 0 SO2-isoC3H7 H OCF2-CH2F H
10.259 C2Hs 0 SO2-isoC3H7 H OCF2-CHBr2 H
10.260 CH3 0 OCH3 H SO2CH3 H 126-128
10.261 CH3 1 OCH3 H SO2CH3 H
10.262 CH3 2 OCH3 H SO2CH3 H
10.263 CH3 2 SO2CH3 H CF3 H
10.264 isoC3H7 0 SO2CH3 H CF3 H
10.265 CH3 1 CH3 OCH3 SO2CH3 H
10.266 CH3 1 CH3 CH2OCH3 SO2CH3 H
10.267 CH3 1 Cl CO2CH3 SO2CH3 H
10.268 CH2CO2CH3 0 SO2CH3 H CF3 H
10.269 CH2CO2C2H5 0 SO2CH3 H CF3 H
10.270 C2H4CO2CH3 0 SO2CH3 H CF3 H Table 11 : Compounds of formula lib:
Figure imgf000072_0001
1-CH3-Cp = 1 -methylcyclopropyl
No. R z R92 R93 RΘ4 R95 Phys data
1 1.001 tert-C Hg 0 Cl H SO2CH3 H
11.002 tert-C4H9 0 CH3 Cl SO2CH3 H
11.003 tert-C4Hg 0 CH3 H Cl H
11.004 tert-C4H9 0 CH3 OC2H5 SO2CH3 H
11.005 tert-C H9 0 SO2CH3 H Cl H
11.006 tert-C4H9 0 CF3 H SO2CH3 H
11.007 tert-C4Hg 0 CH3 Cl SCH3 H
11.008 tert-C4Hg 0 CH3 OC2H5 Br H
11.009 tert-C4H9 0 CH3 OCH2CF3 Br H
11.010 tert-C H9 0 CH3 H SO2CH3 H
11.011 tert-C4Hg 0 Cl H SO2CH3 H
11.012 tert-C4Hg 0 SO2CH3 H CF3 H
11.013 tert-C4H9 0 CH3 OCH3 SO2CH3 H
11.014 tert-C4Hg 0 NO2 H CF3 H
11.015 tert-C4H9 0 NO2 H SO2CH3 H
11.016 tert-C4H9 0 CF3 H F H
11.017 tert-C4H9 0 F H CF3 H
11.018 tert-C4H9 0 Cl O-C2H4-SCH3 Br H
11.019 tert-C4H9 0 Cl H SCH3 H
11.020 tert-C4H9 0 NCH3-SO2CH3 H Cl H No. R z R92 Rg3 Rg4 R95 Phys. data
11.021 tert-C4H9 0 NCH3-SO2CH3 H CF3 H
11.022 tert-C4H9 0 Cl H NCH3-SO2CH3 H
11.023 tert-C4Hg 0 Cl OCH3 SO2CH3 H
11.024 1-CH3-Cp 0 Cl H SO2CH3 H
11.025 1-CH3-Cp 0 CH3 Cl SO2CH3 H
11.026 1-CH3-Cp 0 CH3 H Cl H
11.027 1-CH3-Cp 0 CH3 OC2H5 SO2CH3 H
11.028 1-CHg-Cp 0 SO2CH3 H Cl H
11.029 1-CH3-Cp 0 CF3 H SO2CH3 H
11.030 1-CH3-Cp 0 CH3 Cl SCH3 H
11.031 1-CH3-Cp 0 CH3 OC2H5 Br H
11.032 1-CH3-Cp 0 CH3 OCH2CF3 Br H
11.033 1-CH3-Cp 0 CH3 H SO2CH3 H
11.034 1-CH3-Cp 0 Cl H SO2CH3 H
11.035 1-CH3-Cp 0 SO2CH3 H CF3 H
11.036 1-CH3-Cp 0 CH3 OCH3 SO2CH3 H
11.037 1-CH3-Cp 0 NO2 H CF3 H
11.038 1-CH3-Cp 0 NO2 H SO2CH3 H
11.039 1-CH3-Cp 0 CF3 H F H
11.040 1-CH3-Cp O F H CF3 H
11.041 1-CH3-Cp 0 Cl O-C2H4-SCH3 Br H
11.042 1-CH3-Cp 0 Cl H SCH3 H
11.043 1-CH3-Cp 0 NCH3-SO2CH3 H Cl H
11.044 1-CH3-Cp 0 NCH3-SO2CH3 H CF3 H
11.045 1-CH3-Cp 0 Cl OCH3 SO2CH3 H Table 12 : Compounds of formula lla
Figure imgf000074_0001
No. R91 z R92 R93 R94 R95 Phys data
12.001 CH3 0 NO2 OCH3 OCH3 H
12.002 CH3 0 NO2 OCH3 Cl H
12.003 CH3 0 NO2 OC2H4OCH3 Cl H
12.004 CH3 0 NO2 CH3 SO2CH3 CH3
12.005 CH3 0 NO2 OCH3 OSO2CH3 H
12.006 CH3 0 NO2 OCH3 OCHF2 H
12.007 CH3 0 NO2 OisoC3H7 Cl H
12.008 CH3 0 NO2 H Cl Cl
12.009 CH3 0 Br OCH3 SO2C2Hs H
12.010 CH3 0 Br OCH3 CH3 H
12.011 CH3 0 Br OC2H4OCH3 Br H
12.012 CH3 0 Br OCH3 Br H
12.013 CH3 0 Br OCH2SCH3 Br H
12.014 CH3 0 Br OC2H4OCH3 Br H
12.015 CH3 0 Br OCH2SO2CH3 Br H
12.016 CH3 0 Br OCH2SOCH3 Br H
12.017 CH3 0 NO2 H Cl OisoC3H7
12.018 CH3 0 NO2 OCH2CCH Cl H
12.019 CH3 0 NO2 H Cl OCH3
12.020 CH3 0 NO2 OH Cl H
12.021 CH3 0 NO2 OC2H5 Cl H ro ro ro ro ro ro ro ro ro to ro ro ro ro lo io ro io ro ro ro ro ro o O O O O b b b o b co co eo CO o o o o
4- 4- 4*. 4- 4- eo eo bco eo o 4 Q M - O CD 00 en en 4 co t ω co oro to ro o o o o o
-- o co oo ro eron eron ro r k co ro '
Xo pX Xp Xo pX oX Xo
Figure imgf000075_0001
to to to ro o o N
co co co co o X oX oX oX o-o. ro-, ro ro ro ro ro ro-, ro-, ro-, ro-, o-o, o-o, ro-- ro-. ro z z -, - -, -, -, -, O O O
Figure imgf000075_0002
CO CO
P co co x o O O ro ro ro ro r o r oo ro ro ro ro ro oo o ro o x O O -i -i -. -c o O
-r. X __E -! ro-. V-- r oo ro 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 en
n TJ
0 3"
•—) * ø) CO
Table 13: Compounds of formula He:
Figure imgf000076_0001
No. Phenyl z R92 R93 R94 R95 Phys data
13.001 2-NO2 0 Cl H SO2CH3 H
13.002 2-CI 0 CH3 Cl SO2CH3 H
13.003 2-CH3 0 NO2 H SO2CH3 H
13.004 2-SCH3 0 NO2 H CF3 H
13.005 2-SO2CH3 0 SO2CH3 H CF3 H
13.006 2-CF3 0 CF3 H SO2CH3 H
13.007 2-NH2 0 CH3 Cl SCH3 H
13.008 2-O-isoC3H7 0 SO2CH3 OC2H5 CF3 H
13.009 2-CI-4- 0 NO2 H H H SO2CH3
13.010 2-NO2-4-SO2CH3 0 Cl H H H
13.011 2-NO2-4-CF3 0 CH3 H H H
13.012 2-SO2CH3-4-CF3 0 SCH3 H H H
13.013 2-CF3-4-SO2CH3 0 SO2CH3 H H H
Table 14: Compounds of formula lid:
Figure imgf000077_0001
No. Phenyl z R92 R93 R94 R95 M.p. (°C)
14.001 2-NO2 0 Cl H SO2CH3 H
14.002 2-CI 0 CH3 Cl S02CH3 H
14.003 2-CH3 0 NO2 H SO2CH3 H
14.004 2-SCH3 0 NO2 H CF3 H
14.005 2-SO2CH3 0 SO2CH3 H CF3 H
14.006 2-CF3 0 CF3 H S02CH3 H
14.007 2-NH2 0 CH3 Cl SCH3 H
14.008 2-0-isoC3H7 0 SO2CH3 OC2H5 CF3 H
14.009 2-CI-4-SO2CH3 0 NO2 H H H
14.010 2-NO2-4-SO2CH3 0 Cl H H H
14.011 2-NO2-4-CF3 0 CH3 H H H
14.012 2-SO2CH3-4-CF3 0 SCH3 H H H
14.013 2-CF3-4-SO2CH3 0 SO2CH3 H H H
14.014 4-CI 0 SO2CH3 H CF3 H 209- 210 Table 15: Compounds of formula lie:
Figure imgf000078_0001
No. Ri z R 85 Rβ6 X3 Phys. data
15.001 CH3 0 Cl H O O
15.002 CH3 0 NO2 H O O
15.003 CH3 0 CH3 H O O
15.004 CH3 0 SCH3 H O O
15.005 CH3 0 SOCH3 H O O
15.006 CH3 0 SO2CH3 H O O
15.007 CH3 0 CH3 CH3 O O
15.008 CH3 0 Cl CH3 O O
15.009 CH3 0 CH3 Br O O
15.010 C2H5 0 Cl H O O
15.011 C2H5 0 NO2 H O O
15.012 C2Hδ 0 CH3 H O O
Figure imgf000078_0002
15.014 C2H5 0 SOCH3 H O O
15.015 C2H5 0 SO2CH3 H O O
15.016 C2H5 0 CH3 CH3 O O
15.017 C2Hδ 0 Cl CH3 O O
Figure imgf000078_0003
15.019 CH3 Cl H SO2CH3 O
15.020 CH3 NO2 H S02CH3 O
15.021 CH3 CH3 H S02CH3 O
15.022 CH3 SCH3 H S02CH3 O
15.023 CH3 SOCH3 H S02CH3 O No. Ri 2 : Res Rβ6 X3 Y3 Phys data
15.024 CH3 1 SO2CH3 H SO2CH3 O
15.025 CH3 1 CH3 CH3 SO2CH3 O
15.026 CH3 1 Cl CH3 SO2CH3 O
15.027 CH3 1 CH3 Br S02CH3 O
15.028 C2Hs Cl H O SO2CH3
15.029 C2Hδ NO2 H O SO2CH3
15.030 C2H5 1 CH3 H O SO2CH3
15.031 C2H5 1 SCH3 H O SO2CH3
15.032 C2H5 1 SOCH3 H O SO2CH3
15.033 C2H5 1 SO2CH3 H O SO2CH3
15.034 C2H5 1 CH3 CH3 O SO2CH3
15.035 C2H5 1 Cl CH3 O SO2CH3
15.036 C2H5 1 CH3 Br O SO2CH3
Table 16: Compounds of fc >rmula llf:
Figure imgf000079_0001
No. R1 187 188 Phys. data
16.001 CH3 0 Cl H O O
16.002 CH3 0 NO2 H O O
16.003 CH3 0 CH3 H O O
16.004 CH3 0 SCH3 H O O
16.005 CH3 0 SOCH3 H O O
16.006 CH3 0 SO2CH3 H O O
16.007 CH3 0 CH3 CH3 O O en en en en en en en en en en en en en en en en o o o o o o o b o o o o oo o o o o ω ω eo eo CO CO to ro ro ro ro rroo ro ro rroo ro en en eo ro o CO 00 • I en eenn 4k rroo
Figure imgf000080_0001
t Oo rOo tOo tOo toO rOo rOo toO rOo x x x x x x x x x
Figure imgf000080_0002
O O O O O O O O O N co co co CO w co o CO o O P O CO o o o o o o P o CO o o o o o o P o o o
X o o ¥ -L c xo to o > t o o x x o y X ej t i o o x o - o-' 5 Ω
X ,? X c?
00 o o
X X x x x x x x ro o o _ _ x x x x x x x __ ra ro o x o x __ x _ X X X X 00 o c Xα
0 0 0 0 0 0 0 0 0
Figure imgf000080_0003
O 0 0 0 0 0 0 0 0 0 O O co co co c o cxo cxo cxo
Figure imgf000080_0004
e ~-
» co
Table 17: Compounds of formula llq:
Figure imgf000081_0001
data
17.001 CH3 0 Cl H O SO2CH3
17.002 CH3 0 NO2 H O O
17.003 CH3 0 CH3 H O SO2CH3
Figure imgf000081_0002
17.005 CH3 0 CH3 CH3 C=NOCH3 SO2CH3
17.006 CH3 0 CH3 CH3 C(CH3)2 SO2CH3
17.007 CH3 0 CH3 CH3 O O
17.008 CH3 0 CH3 CH3 OCH3 SO2CH3
17.009 CH3 0 CH3 CH3 OC2H5 SO2CH3
17.010 C2H5 0 Cl H O SO2CH3
Figure imgf000081_0003
17.012 C2H5 0 CH3 H O SO2CH3
Figure imgf000081_0004
17.014 C2H5 0 CH3 CH3 C=NOCH3 SO2CH3
17.015 C2H5 0 CH3 CH3 C(CH3)2 SO2CH3
Figure imgf000081_0005
17.017 C2H5 0 CH3 CH3 OCH3 SO2CH3
17.018 C2H5 0 CH3 CH3 OC2H5 SO2CH3
17.019 CH3 1 Cl H O SO2CH3
17.020 CH3 1 NO2 H O O
17.021 CH3 1 CH3 H O SO2CH3
17.022 CH3 1 CH3 H O S No. Ri z R81 R82 Xi Yi Phys. data
17.023 CH3 1 CH3 CH3 C=NOCH3 SO2CH3
17.024 CH3 1 CH3 CH3 C(CH3)2 SO2CH3
17.025 CH3 1 CH3 CH3 O O
17.026 CH3 1 CH3 CH3 OCH3 SO2CH3
17.027 CH3 1 CH3 CH3 OC2H5 SO2CH3
17.028 C2H5 1 Cl H O SO CH3
17.029 C2H5 1 NO2 H O O
17.030 C2H5 1 CH3 H O SO2CH3
17.031 C2H5 1 CH3 H O S
17.032 C2H5 1 CH3 CH3 C=NOCH3 SO2CH3
17.033 C2H5 1 CH3 CH3 C(CH3)2 SO2CH3
17.034 C2H5 1 CH3 CH3 O O
17.035 C2H5 1 CH3 CH3 OCH3 SO2CH3
17.036 C2H5 1 CH3 CH3 OC2H5 SO2CH3
17.037 CH3 2 CH3 H O SO2CH3
17.038 CH3 2 CH3 H O S
17.039 CH3 2 CH3 CH3 C=NOCH3 SO2CH3
17.040 CH3 2 CH3 CH3 C(CH3)2 SO2CH3
17.041 CH3 2 CH3 CH3 O O
17.042 CH3 2 CH3 CH3 OCH3 SO2CH3
17.043 CH3 2 CH3 CH3 OC2H5 SO2CH3
Table 18: Compounds of formula llh:
Figure imgf000083_0001
No. Ri z R83 Rβ4 X2 Y2 Phys. data
18.001 CH3 0 Cl H SO2CH3 O
18.002 CH3 0 H H SO2CH3 :::NOCH3
18.003 CH3 0 CH3 H SO2CH3 O
18.004 CH3 0 CH3 H O S
18.005 CH3 0 CH3 H O SO2CH3
18.006 CH3 0 CH3 H SO2CH3 CH2
18.007 CH3 0 Cl H S O
18.008 CH3 0 H H S O
18.009 CH3 0 CH3 H S O
18.010 C2Hs 0 Cl H SO2CH3 O
18.011 C2Hs 0 H H SO2CH3 :::NOCH3
18.012 C2Hs 0 CH3 H SO2CH3 O
18.013 C2H5 0 CH3 H O S
18.014 C2H5 0 CH3 H O SO2CH3
18.015 C2Hδ 0 CH3 H SO2CH3 CH2
18.016 C2Hs 0 Cl H S O
18.017 C2Hδ 0 H H S O
18.018 C2Hδ 0 CH3 H S O
18.019 CH3 1 Cl H SO2CH3 O
18.020 CH3 1 H H SO2CH3 :::NOCH3
18.021 CH3 1 CH3 H SO2CH3 O
18.022 CH3 1 CH3 H O S 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 o o o o o o o o o o o Z
4- o 4- o CO o CO o CO CO CO eo o CO CO o o
CO ro ro ro ro ro ro ro o O ω o
CO 00 -sj en en k CO ro o CO 00 -si en en 4>. CO o X oX oX oX oX p p pX pX pX p p p pX oX o oX o oX ro ro ro N
O X -p o X T X -r O X - Xr O o o o o _. x x x x x Ω S n Ω O x O x X
X X Ω S x x x x x x x x x x x x x X
Figure imgf000084_0001
CO CO CO CO
O O
° 8 o o O o o o o o X 0 co θ Q θ O O O o o X O X o
X X X X
L υ rn —r
£■ •<
~> co
Table 19: Compounds of formula Hi:
Figure imgf000085_0001
No. R92 R93 Rθ4 R96 R97 M.p.(°C)/
„ 35 nD
19.001 Cl H Cl Cl SCH3
19.002 Cl H Cl Br SCH3 1.5904
19.003 Cl H SO2CH3 Cl SCH3
19.004 Cl H SO2CH3 Br SCH3
19.005 Cl H SO2CH3 Cl SOCH3
19.006 Cl H SO2CH3 Br SOCH3
19.007 SO2CH3 H CF3 Cl SCH3
„ 40
19.008 SO2CH3 H CF3 Br SCH3 nD = 1.5399
19.009 SO2CH3 H CF3 Cl SOCH3
19.010 SO2CH3 H CF3 Br SOCH3
19.011 SO2CH3 H CF3 Cl SO2CH3
19.012 SO2CH3 H CF3 Br SO2CH3
19.013 CH3 OCH3 SO2CH3 Cl SCH3
19.014 CH3 OCH3 SO2CH3 Br SCH3
19.015 CH3 OC2H5 SO2CH3 Cl SCH3
19.016 CH3 OC2H5 SO2CH3 Br SCH3
19.017 CH3 CH2OCH3 SO2CH3 Cl SCH3
19.018 CH3 CH2OCH3 SO2CH3 Br SCH3
19.019 Cl CO2CH3 SO2CH3 Cl SCH3
19.020 Cl CO2CH3 SO2CH3 Br SCH3
19.021 Cl H Cl Cl Cl
19.022 Cl H Cl Br Br 88-90 CO CD CO CD CO CD CO CO CO CO CO CO CO O CO CO CO CO eo eo CO CD CO CO co eo CD b b O b o O O o o O o b b o o b b b b b b b
4- 4- b 4- 4- 4- o 4- 4- 4- 4 CO CO co co b CO c bo co ω CO e bo ro ro ro ro ro ro ro CD 00 ■ l cn en 4k ω ro ->■ o CD 00 •>j en en co I o co oo en en co
Figure imgf000086_0001
o o o o o o o X X o O O O o o r oo r oo ro r oo o o r oo r oo o o o o o o o o ro o r Oo ro o to o X X o o X X X X o o X X X o X X
X X X X o o X X X X X X o
X X X X
co co co co co co co co co co co co co co co co CO CO CO CO o o to o o o o o o o t oo o o to o o o o o o o o o o o o o o o o o o o o o O O l o o r oo r oo r oo r Oo o ^ * o ^* x x x x x x x x x x x x x O O O O J1 J1
X X X X X X X
ro ro o ro o ro o ro o ro o ro o ro o x x x x x x ro o ro o ro o
CO CO CO CO
00 O O 00 o ro o
■- x x - — - — ro o o o ro o ro o ro o ro o o ro ro o ro o ro o e Xo
Figure imgf000086_0002
Figure imgf000087_0001
ø)
oo o I 3 σ
00 ro cn O
ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro IO o ro ro ro ro o o o o o o o o o o o o o o o o o o o ro r 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 z o
4- 4- 4- 4- 4- 4- 4- 4 4- CO CO CO CO CO CO CO CO CoO eo ro ro to ro to co 00 -sl cn en 4. ω ro o CD 00 en en 4k ω ro o CO 00 -s| en en
Figure imgf000088_0001
Figure imgf000088_0002
CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO
O' roO rOo rOo rOo rOo rOo rOo rOo rO roO rO roO O rO rO rOo O ^ * O ' O C O C roO rOo roO O X ^ Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox J1 ,?1 - — ox ox ox ox
en en I en 3 en 00 σ o
-si o co O
Figure imgf000089_0001
O
ro i io ro ro ro ro ro ro ro ro ro ro ro ro ro to ro ro ro ro ro ro o o O o o O o O o o o o o o o o o o z o o o o
4- 4- 4- 4 4- 4- 4- 4*. 4k 4- co ω CO CO eo eo ω eo eo ω ro ro ιo o co 00 -sl σ> en 4- eo ro -— O CO 00 -M en en 4- ω ro o CD oo -s|
Figure imgf000090_0001
Figure imgf000090_0002
co co co co ω co co ω co ω co ω co ω co co ω ω o i^ roo roo roo roo roo roo Too roo roo roo roo roo roo roo roo roo o ii o ii to O to O l xO xO xO Ox xO Ox Ox xO xO Ox xO Ox Ox xO xO xO j1 ^ - - o X o X
3 TJ σ
O
Formulation Examples for active inqredients of formula I (throughout, percentages are bv weight)
F1. Emulsifiable concentrates a) b) c) d) a compound of Tables 1 -19 5% 10% 25% 50% calcium dodecylbenzene- 6% 8% 6% 8% sulfonate castor oil polyglycol ether 4 % - 4 % 4 %
(36 moles of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 moles of ethylene oxide) cyclohexanone - - 10 % 20 % aromatic hydrocarbon 85% 78% 55% 16% mixture C9-Cι2
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
F2. Solutions a) b) c) d) a compound of Tables 1-19 5% 10% 50% 90%
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% - polyethylene glycol 20% 10% - -
(mol. wt.400)
N-methyl-2-pyrrolidone - - 30% 10% aromatic hydrocarbon 75% 60% - - mixture C9-C12
These solutions are suitable for application in the form of micro -drops.
F3. Wettable powders a) b) c) d) a compound of Tables 1-19 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium laurylsulfate 2% 3% - 4% sodium diisobutylnaphthalene- - 6 % 5 % 6 % sulfonate octylphenol polyglycol ether - 1 % 2 %
(7-8 moles of ethylene oxide) highly dispersed silicic acid 1 % 3 % 5 % 10 % kaolin 88 % 62 % 35 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c) a compound of Tables 1 -19 0.1 % 5 % 15 % highly dispersed silicic acid 0.9 % 2 % 2 % inorganic carrier 99.0 % 93 % 83 %
( E 0.1 - 1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c) a compound of Tables 1-19 0.1 % 5 % 15 % polyethylene glycol 1.0 % 2 % 3 %
(mol. wt. 200) highly dispersed silicic acid 0.9 % 1 % 2 % inorganic carrier 98.0 % 92 % 80 %
( E 0.1 - 1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d) a compound of Tables 1 -19 0.1 % 3 % 5 % 15 % sodium lignosulfonate 1.5 % 2 % 3 % 4 % carboxymethylcellulose 1.4 % 2 % 2 % 2 % Ό kaolin 97.0 % 93 % 90 % 79 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) a compound of Tables 1-19 0.1 % 1 % 5 % talcum 39.9 % 49 % 35 % kaolin 60.0 % 50 % 60 %
Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) a compound of Tables 1-19 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
(15 moles of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Biological Examples
Example B1 : Pre-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots.
Immediately after sowing, the test compounds are applied by spraying in the form of an aqueous suspension (prepared from a 25 % wettable powder formulation (Example F3, b)) or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate
(Example F1 , c)) at the rate of 2 kg a.i./ha (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a 3-week test period, the test is evaluated using a scale of nine ratings (1 = plant completely destroyed, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
In this test, compounds of Tables 1 to 19 exhibit good herbicidal action.
The same results are obtained when the compounds of Tables 1 to 19 are formulated according to Examples F2 and F4 to F8.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are grown in a greenhouse in plastics pots containing standard soil and are sprayed, at the 4- to 6-leaf stage, with an aqueous suspension of the test compounds of formula I prepared from a 25 % wettable powder formulation (Example F3, b)) or with an emulsion of the test compounds of formula I prepared from a 25 % emulsifiable concentrate (Example F1 , c)), at the rate of 2 kg a.i./ha (500 litres of water/ha). The test plants are then grown on in the greenhouse under optimum conditions. After a test period of about 18 days, the test is evaluated using a scale of nine ratings (1 = plant completely destroyed, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action. In this test, the compounds of formula I of Tables 1 to 19 exhibit good herbicidal action.
The same results are obtained when the compounds of Tables 1 to 19 are formulated according to Examples F2 and F4 to F8.
Examples of the biological action of the compounds of Tables 1 to 19 are given in Tables B1 and B2 below: Table B1 : Pre-emeroence action
Test plant Sinapsis Solanum Stellaria Rate (g a.i./ha)
Compound No.
19.024 2 1 2 2000
10.023 2 3 3 2000
1.023 1 2 2 2000
1.068 2 2 3 2000
1.264 2 2 3 2000
5.014 3 2 3 2000
1.263 2 3 4 2000
1.042 3 2 2000
1.115 2 2 2000
1.260 3 1 2000
10.260 4 2 2000
1.261 3 4 2000
1.262 4 4 2000
Table B2: Post-emeroence action
Test plant Sinapsis Solanum Setaria Rate (g a.i./ha)
Compound No.
19.024 1 1 2 2000
10.023 3 3 6 2000
14.014 3 4 6 2000
1.023 1 2 5 2000
1.068 3 4 3 2000
1.264 3 3 5 2000
5.014 2 3 4 2000
1.263 3 3 4 2000
1.042 2 2 3 2000
1.115 1 2 4 2000
1.083 2 3 6 2000
1.260 1 2 2 2000
10.260 2 5 2 2000
1.261 1 2 2 2000
1.106 2 2 2 2000

Claims

What is claimed is:
1. A compound of formula
Figure imgf000097_0001
wherein
Z is S, SO or SO2;
R. is hydrogen, CrCθalkyl or CrC8alkyl substituted by halogen, CrC4alkoxy, Cι-C4alkylthio, Cι-C4alkylsulfonyl, C C4alkylsulfinyl, hydroxy, cyano, nitro, -CHO, -CO2R2, -COR3, -COSR4, -NR5R6, CONR36R37 or by phenyl which in turn may be substituted by C C alkyl, CrC6halo- alkyl, d-C4alkoxy, CrC4haioalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyloxy, halogen, nitro, cyano, -COOH, COOCrC4alkyl, COOphenyl, CrC alkoxy, phenoxy, (CrC4alkoxy)-Cι-C4alkyll (C C4alkylthio)-CrC4alkyl, (Cι-C4alkylsulfinyl)-C C alkyl, (C C4alkylsulfonyl)-Cι-C4alkyl, NHSO2-C1-C4alkyl, NHSO2-phenyl, N(C1-Cβalkyl)SO2-Cι-C4- alkyl, N(Cι-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-C C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-CrC4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-C C4alkyl, N(phenyl)SO2-phenyl, OSO2- CrC4alkyl, CONR25R26, OSO2-C C4haloalkyl, OSO2-phenyl, C C4alkylthio, C C4haloalkyl- thio, phenylthio, CrC4alkylsulfonyl, C1-C haloalkylsulfonyl, phenylsulfonyl, C C alkylsulfinyl, CrC haloalkylsulfinyl, phenylsulfinyl, -(CH2)m-phenyl or by -NR15CO2R27; or R. is C2-C8alkenyl or C2-C8alkenyl substituted by halogen, CrC alkoxy, CrC4alkylthio, C C4alkylsulfonyl, C C4alkylsulfinyl, -CONR32R33, cyano, nitro, -CHO, -CO2R38, -COR39, -COS-C C alkyl, -NR34R35 or by phenyl which in turn may be substituted by Cι-C4alkyl, d-Cehaloalkyl, C C4alkoxy, C C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOCrC4alkyl, COOphenyl, C C4alkoxy, phenoxy, (C C4alkoxy)-Cι-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C C4alkylsulfinyl)-C C4alkyl, (CrC4alkylsulfonyl)-C C4alkyl, NHSO2-C C4alkyl, NHSO2-phenyl, N(Ci-C6alkyl)SO2-C C4- alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-CrC4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C1-C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-C C4alkyl, N(phenyl)SO2-phenyl, OSO2- Cι-C alkyl, CONR40R4ι, OSO2-Cι-C4haloalkyl, OSO2-phenyl, Cι-C4alkylthio, d-C4haloalkyl- thio, phenylthio, d-dalkylsulfonyl, C C4haloalkylsulfonyl, phenylsulfonyl, d-dalkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)p-phenyl or by -NR43CO2R42; or Ri is C3-C6alkynyl or C3-C6alkynyl substituted by halogen, d-C4haloalkyl, cyano, -CO2R_M or by phenyl which in turn may be substituted by Cι-C4alkyl, d-C6haloalkyl, d-C4alkoxy, d-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C4alkyl, COOphenyl, C C4alkoxy, phenoxy, (d-C alkoxy)- d-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (Cι-C4alkylsulfinyl)-d-C4alkyl, (Cι-C4alkylsulfonyl)- d-dalkyl, NHSO2-d-C4alkyl, NHSO2-phenyl, N(d-C6alkyl)SO2-Cι-C4alkyl, N(C C6alkyl)- SO2-phenyl, N(C2-C6alkenyl)SO2-CrC4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)- SO2-d-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-d-C4alkyl, N(C3-C7cyclo- alkyl)SO2-phenyl, N(phenyl)SO2-C C alkyl, N(phenyl)SO2-phenyl, OSO2-C C4alkyl, CONR28R2g, OSO2-d-C4haloalkyl, OSO2-phenyl, d-C4alkylthio, d-C haloalkylthio, phenylthio, Cι-C4alkylsulfonyl, d-C4haloalkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, d-dhalo- alkylsulfinyl, phenylsulfinyl, -(CH2)x-phenyl or by -NR31CO2R 0; or Ri is C3-C7cycloalkyl or C3-C7cycloalkyl substituted by d-C4alkyl, d-C alkoxy, Cι-C4alkyl- thio, d-C alkylsulfinyl, d-C alkylsulfonyl or by phenyl which in turn may be substituted by halogen, nitro, cyano, d-C4alkoxy, C C4haloalkoxy, d-C4alkylthio, d-C4haloalkylthio, d-C4alkyl or by d-C4haloalkyl; or Ri is -(CH2)q-C3-C7cycloalkyl, phenyl or phenyl substituted by d-C alkyl, d-C6haloalkyl, d-dalkoxy, Cι-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C4alkyl, COOphenyl, d-C alkoxy, phenoxy, (d-C4- alkoxy)-C1-C4alkyl, (d-C4alkylthio)-Cι-C4alkyl, (C C4alkylsulfinyl)-CrC4alkyl, (d-C4alkyl- sulfonyl)-d-C4alkyl_ NHSO2-d-C4alkyl, NHSO2-phenyl, N(C C6alkyl)SO2-C1-C4alkyl, N(Cι-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-CrC4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-Cι-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-d-C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-C C4alkyl, N(phenyl)SO2-phenyl, OSO2- d-dalkyl, CONR45R46, OSO2-C C4haloalkyl, OSO2-phenyl, Cι-C4alkylthio, d-dhaloalkyl- thio, phenylthio, d-dalkylsulfonyl, Cι-C4haloalkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, Cι-C4haloalkylsulfinyl, phenylsulfinyl or by -NR48CO2R47; or Ri is -(CH2)s-phenyl, COR7 or 4- to 6-membered heterocyclyl;
R2, R38, R44 and R66 are each independently of the others hydrogen, C C4alkyl, phenyl or phenyl substituted by d-dalkyl, d-C6haloalkyl, Cι-C4alkoxy, CrC4haloalkoxy, C2-C6- alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOCι-C alkyl, COOphenyl, d-C4alkoxy, phenoxy, (Cι-C4alkoxy)-Cι-C4alkyl, (Cι-C4alkyl- thio)-C C4alkyl, (Cι-C alkylsulfinyl)-Cι-C4alkyl, (C C4alkylsulfonyl)-Cι-C4alkyl, NHSO2-d-C4- alkyl, NHSO2-phenyl, N(d-C6alkyl)SO2-CrC4alkyl. N(d-C6alkyl)SO2-phenyl, N(C2-C6- alkenyl)SO2-C C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-CrC4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-Cι-C4alkyl, N(C3-C7cycloalkyl)SO2- phenyl, N(phenyl)SO2-d-C4alkyl, N(phenyl)SO2-phenyl, OSOa-d-dalkyl, CONR49R50, OSO2-CrC4haloalkyl, OSO2-phenyl, C C4alkylthio, C C4haloalkylthio, phenylthio, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, d-C4haloalkyl- sulfinyl, phenylsulfinyl, -(CH2) -phenyl or by -NR52CO2R5i;
R3, R39 and R67 are each independently of the others d-dalkyl, phenyl or phenyl substituted by d-dalkyl, d-C6haloalkyl, C C4alkoxy, C C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C4alkyl, COOphenyl, Cι-C4alkoxy, phenoxy, (Cι-C4alkoxy)-d-C4alkyl, (C C4alkylthio)-Cι-C4alkyl, (Cι-C4alkylsulfinyl)-C C4alkyl, (d-dalkylsulfony -d-dalkyl, NHSO2-d-C4alkyl, NHSO2- phenyl, N(Cι-C6alkyl)SO2-C C4alkyl, N(d-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-d-C4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2-d-C4alkyl, N(C3-C6alkynyl)SO2- phenyl, N(C3-C7cycloalkyl)SO2-C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO - Cι-C4alkyl, N(phenyl)SO2-phenyl, OSO2-C C4alkyl, CONR53RM, OSO2-Cι-C4haloalkyl, OSO2-phenyl, d-dalkylthio, d-C haloalkylthio, phenylthio, d-C4alkylsulfonyl, d-C halo- alkylsulfonyl, phenylsulfonyl, Cι-C4alkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)t- phenyl or by -NR56CO2R55; R4 is C C4alkyl;
R5 is hydrogen, d-dalkyl, C2-Cealkenyl, C3-C6alkynyl, C3-C cycloalkyl, phenyl or phenyl substituted by d-C4alkyl, d-C6haloalkyl, d-C4alkoxy, Cι-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, d-C4alkoxy, phenoxy, (CrC alkoxy)-d-C4alkyl, (C C4alkylthio)-Cι-C4alkyl, (Cι-C4alkylsulfinyl)-C C4alkyl, (d-C4alkylsulfonyl)-CrC4alkyl, NHSO2-d-C4alkyl, NHSO2- phenyl, N(C1-C6alkyl)SO2-C1-C4alkyl, N(d-C6alkyl)SO2-phenyl. N(C2-C6alkenyl)SO2-C C4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2H, N(C3-C6alkynyl)SO2-C C alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2H, N(C3-C7cycloalkyl)SO2-d-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-CrC4alkyl, N(phenyl)SO2-phenyl, OSO2-CrC4- alkyl, CONR57R58, OSO2-C C4haloalkyl, OSO2-phenyl, C C4alkylthio, Cι-C4haloalkylthio, phenylthio, C C4alkylsulfonyl, CrCthaloalkylsulfonyl, phenylsulfonyl, C C alkylsulfinyl, C C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)u-phenyl or by -NR60CO2R59; R6 is hydrogen, Cι-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, Qrdcycloalkyl, phenyl or phenyl substituted by Cι-C4alkyl, d-C6haloalkyl, C C4alkoxy, d-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, -COOH, COOC C4alkyl, COOphenyl, d-C4alkoxy, phenoxy, (Cι-C4alkoxy)-d-C4alkyl, (C1-C4alkylthio)-Cι-C4alkyl, (d-C4alkylsulfinyl)-d-C4alkyl, (Cι-C4alkylsulfonyl)-d-C4alkyl, NHSO2-C1-C4alkyl, NHSO2- phenyl, N(Cι-C6alkyl)SO2-Cι-C4alkyl, N(Ci-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-Cι-C4- alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)Sθ2-CrC4alkyl, N(C3-C6alkynyl)SO2- phenyl, N(C3-C7cycloalkyl)SO2-C C alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO - d-C4alkyl, N(phenyl)SO2-phenyl, OSO2-d-C4alkyl, CONR61R62, OSO2-d-C4haloalkyl, OSO2-phenyl, d-C4alkylthio, d-C haloalkylthio, phenylthio, d-C alkylsulfonyl, d-dhalo- alkylsulfonyl, phenylsulfonyl, d-C4alkylsulfinyl, d-C haloalkylsulfinyl, phenylsulfinyl, -(CH2)v-phenyl or by
Figure imgf000100_0001
R7 is phenyl, substituted phenyl, Cι-C4alkyl, Cι-C4alkoxy or -NR8R9; R8 and R9 are each independently of the other d-C4alkyl, phenyl or phenyl substituted by halogen, nitro, cyano, d-dalkyl, Cι-C alkoxy, d-C thioalkyl, -CO2R66> -COR6 , d-C alkyl- sulfonyl, d-dalkylsulfinyl or by Cι-C4haloalkyl; or R8 and R9 together form a 5- or 6- membered ring which may be interrupted by oxygen, NR65 or by S; Q is C=O or CHOH;
R is Cι-C6alkyl, Cι-C6alkoxy, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C2-C6alkoxyalkynyl, C2-C6alkoxyalkenyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by d-C alkyl, d-C4haloalkyl or by C C4alkoxy; 3- to 6-membered, saturated heterocyclyl; or phenyl which may be substituted by halogen, C1-C4alkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, C C4alkylthio, nitro, cyano, d-C4alkylthio, Cι-C alkylsulfonyl, Cι-C4alkylsulfinyl, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio;
Ar is phenyl or phenyl substituted by up to four identical or different substituents selected from halogen, d-dalkyl, d-C4haloalkyl, d-C4alkoxy, d-C4haloalkoxy, (d-C alkoxy)- d-C4a!kyl, (d-C alkylthio)-d-C alkyl, (C C4alkylsulfonyl)-Cι-C4alkyl, (C C alkylsulfinyl)- Cι-C4alkyl, d-C4alkylthio, d-C4haloalkylthio, phenylthio, d-C alkylsulfonyl, d-C4haloalkyl- sulfonyl, phenylsulfonyl, Cι-C alkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (d-dalkoxy)-Cι-C4alkoxy, -COOH, COOC C4alkyl, COOphenyl, Cι-C4alkoxy, phenoxy, -C(=NOR68), -NR13SO2-C C4alkyl, -NRegSOs-d-dalkyl, -NR7oSO2-phenyl, -NR71R72, C3-C6alkenyloxy, C3-C6alkynyloxy and S(O)n-C C haloalkyl; it being possible for two adjacent substituents on the aromatic ring, together with the two atoms to which they are bonded, to form a 5- to 7-membered ring;
Ri3, Rβ9, R 0 and R7ι are each independently of the others hydrogen, d-C6alkyl, C2-C6- alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by d-dalkyl, d-C6halo- alkyl, d-C4alkoxy, Cι-C haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyloxy, halogen, nitro, cyano, -COOH, COOd-dalkyl, COOphenyl, Cι-C4alkoxy, phenoxy, (d-OialkoxyJ-d-dalkyl, (d-C alkylthio)-CrC4alkyl, (CrC4alkylsulfinyl)-CrC4alkyl,
(Cι-C4alkylsulfonyl)-d-C4alkyl, NHSO2-CrC4alkyl, NHSO2-phenyl, N(C C6alkyl)SO2-C1-C4- alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-d-C4alkyl, N(C2-C6alkenyl)SO2-phenyl,
N(C3-C6alkynyl)SO2-C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-d-C4- alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2-CrC4alkyl, N(phenyl)SO2-phenyl, OSO2- d-C4alkyl, CONR^R^, OSO2-C C4haloalkyl, OSO2-phenyl, C C4alkylthio, d-C4haloalkyl- thio, phenylthio, d-C alkylsulfonyl, CrC haloalkylsulfonyl, phenylsulfonyl, d-dalkylsulfinyl, d-C4haloalkylsulfinyl, phenylsulfinyl, -(CH2)u-phenyl or by -NR8oCO2R 9;
R72 is -COOH, COOC C4alkyl, COOphenyl, d-C4alkoxy or phenoxy, or COOphenyl or phenoxy each substituted by halogen, d-C4alkyl, d-C haloalkyl, C C4alkoxy, d-C4halo- alkoxy, d-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio;
R15. R3i> R 3. R48, R52, R56, Reo. Re4> Res and R80 are each independently of the others hydrogen, d-C4alkyl, C2-C6alkenyl, C3-C6alkynyl or C3-C cycloalkyl; n is O, 1 or 2; m, p, q, s, t, u, v and x are each independently of the others 1 , 2, 3 or 4;
R25. R26, R27. R28. R29. R30. R32. R331 3 » R35. R40, R41. R42. R45> R46. R47, R49t R50. R51. R53.
R54, Rss, R57, Res, R59, Rβi, Rβ2, Res, Res, R77, R?8 and R79 are hydrogen, Cι-C4alkyl, C2-C6- alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by halogen, nitro, cyano,
Cι-C4alkoxy, d-C4haloalkoxy, d-C4alkylthio, d-C4haloalkylthio, d-C alkyl or by d-C4halo- alkyl; or an agronomically acceptable salt of such a compound.
2. A compound of formula I according to claim 1 , wherein Ar is a group
Figure imgf000102_0001
wherein
Rβι. Rs2> Rβ3, Rβ4, Rs5> Rβe, Rβ7 and Rββ are each independently of the others hydrogen, halogen, d-dalkyl, d-C4haloalkyl, d-C alkoxy, Cι-C4haloalkoxy, (C C4alkoxy)-C C4alkyl,
(d-C4alkylthio)-Cι-C4alkyl, (Cι-C4alkylsulfonyl)-Cι-C4alkyl, (d-C alkylsulfinyl)-d-C4alkyl,
Cι-C4alkylthio, d-C haloalkylthio, phenylthio, d-C4alkylsulfonyl, d-C4haloalkylsulfonyl, phenylsulfonyl, d-C alkylsulfinyl, d-C haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (C C - alkoxy)-d-C4alkoxy, -COOH, COOd-dalkyl, COOphenyl, C C4alkoxy, phenoxy,
-C(=NOR68), -NRι3SO2-C1-C4alkyl, -NR69SO2-CrC alkyl, -NR70SO2-phenyl, -NR71R72, C3-C6- alkenyloxy, C3-C6alkynyloxy or S(O)n-d-C4haloalkyl;
Xι, X2, X3, X , Yι, Y2, Y3 and Y4 are each independently of the others O, S, SO, SO2, NR89,
C=O, C=N-O-d-C4alkyl, -C=N-O-C C4alkenyl, CRι9-O-d-C4alkyl or CRgoR∞;
R89 is hydrogen, d-dalkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C7cycloalkyl;
R19, R20 and R90 are each independently of the others hydrogen or d-dalkyl.
3. A compound according to claim 1 , wherein R is cyclopropyl, 1 -methylcyclopropyl, tert- butyl or isopropyl.
4. A compound of formula I according to claim 1 , wherein Q is C=O.
5. A compound of formula I according to claim 1 , wherein Z is sulfur or SO.
6. A compound of formula I according to claim 1 , wherein"R1 is hydrogen, d-dalkyl, d-dalkyl substituted by halogen, methoxy, ethoxy, cyano or by COOR2, or C3-C6alkenyl or halo- substituted C3-C6alkenyl, or C3-C6alkynyl.
7. A compound of formula PI
Figure imgf000103_0001
wherein Ar and Ri are as defined for formula I and T is cyano or CON(CH3)-OCH3.
8. A compound of formula PIVa
Figure imgf000103_0002
wherein E and G are halogen or S-Ri and Ri is as defined in claim 1 , but E and G are not simultaneously halogen, with the exception of a compound wherein E and G are methylthio, ethylthio or benzylthio.
9. A herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective amount of a compound of formula I on an inert carrier.
10. A composition according to claim 9 comprising from 0.1 % to 95 % of a compound of formula I.
11. A method of controlling undesired plant growth, which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound.
12. A method according to claim 11 , wherein the compound is applied in an amount of from 0.001 to 4 kg per hectare.
13. A method of inhibiting plant growth, which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound.
14. The use of a composition according to claim 9 in controlling undesired plant growth.
15. A compound of formula PVIa
Figure imgf000104_0001
XP1
wherein Ar and Ri are as defined for formula I, T is CO-R, wherein R is as defined for formula I, and XP1 is halogen.
16. A compound of formula PVIIb
(PVIIb)
Figure imgf000104_0002
XP1
wherein Ar and Ri are as defined for formula I, T is CO-R, wherein R is as defined for formula I, and XP1 is halogen.
17. A compound of formula PXVI
Figure imgf000104_0003
wherein Ar, R and R. are as defined for formula I.
18. A compound of formula PXVIII
(PXVIII)
Figure imgf000105_0001
wherein Ar, R and Rt are as defined for formula I and 'Hal is halogen.
19. A compound of formula KUb
Figure imgf000105_0002
wherein Ar, R and Ri are as defined for formula I, n is 1 or 2 and 'Hal is halogen.
20. A compound of formula KUa
Figure imgf000105_0003
wherein R, Ar and Ri are as defined for formula I and n is 1 or 2.
PCT/EP1998/007177 1997-11-12 1998-11-10 Isoxazole derivatives and their use as herbicides Ceased WO1999024409A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU15615/99A AU1561599A (en) 1997-11-12 1998-11-10 Isoxazole derivatives and their use as herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2603/97 1997-11-12
CH260397 1997-11-12

Publications (1)

Publication Number Publication Date
WO1999024409A1 true WO1999024409A1 (en) 1999-05-20

Family

ID=4237477

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/007177 Ceased WO1999024409A1 (en) 1997-11-12 1998-11-10 Isoxazole derivatives and their use as herbicides

Country Status (2)

Country Link
AU (1) AU1561599A (en)
WO (1) WO1999024409A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369276B1 (en) 1998-11-19 2002-04-09 Eagleview Technologies, Inc. Catalyst structure for ketone production and method of making and using the same
US6392099B1 (en) 1998-11-19 2002-05-21 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6545185B1 (en) 2001-03-29 2003-04-08 Eagleview Technologies, Inc. Preparation of ketones from aldehydes
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2018004223A1 (en) * 2016-06-27 2018-01-04 (주)목우연구소 Pyridine-based compound including isoxazoline ring, and use thereof as herbicide
CN113666883A (en) * 2021-07-23 2021-11-19 华南理工大学 Method for synthesizing 4-vinyl isoxazole derivative
WO2023210792A1 (en) * 2022-04-28 2023-11-02 日本農薬株式会社 Nitrogen-containing heterocyclic compound having oxime group, agricultural/horticultural herbicide containing said compound, and use of both of foregoing

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418175A2 (en) * 1989-09-11 1991-03-20 Rhone Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0503410A1 (en) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Isoxazol- and Isothiazol 5-carboxylic acids amids
EP0524018A1 (en) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazole herbicides
JPH05105672A (en) * 1991-10-17 1993-04-27 Sankyo Co Ltd Isoxazoline derivative, its production and agricultural and horticultural germicide
WO1997043270A1 (en) * 1996-05-14 1997-11-20 Novartis Ag Isoxazole derivatives and their use as herbicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418175A2 (en) * 1989-09-11 1991-03-20 Rhone Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0503410A1 (en) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Isoxazol- and Isothiazol 5-carboxylic acids amids
EP0524018A1 (en) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazole herbicides
JPH05105672A (en) * 1991-10-17 1993-04-27 Sankyo Co Ltd Isoxazoline derivative, its production and agricultural and horticultural germicide
WO1997043270A1 (en) * 1996-05-14 1997-11-20 Novartis Ag Isoxazole derivatives and their use as herbicides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 119, no. 19, 8 November 1993, Columbus, Ohio, US; abstract no. 203404h, page 896; XP002094410 *
CHEMICAL ABSTRACTS, vol. 93, no. 21, 24 November 1980, Columbus, Ohio, US; abstract no. 204021n, MANFRED PALLAS ET AL: "Preparation of hydroxyiminodithiocarbonic acid esters" page 631; XP002094411 *
Z.CHEM., vol. 20, no. 6, 1980, pages 207 - 209 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369276B1 (en) 1998-11-19 2002-04-09 Eagleview Technologies, Inc. Catalyst structure for ketone production and method of making and using the same
US6392099B1 (en) 1998-11-19 2002-05-21 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6495696B1 (en) 1998-11-19 2002-12-17 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6545185B1 (en) 2001-03-29 2003-04-08 Eagleview Technologies, Inc. Preparation of ketones from aldehydes
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2018004223A1 (en) * 2016-06-27 2018-01-04 (주)목우연구소 Pyridine-based compound including isoxazoline ring, and use thereof as herbicide
CN113666883A (en) * 2021-07-23 2021-11-19 华南理工大学 Method for synthesizing 4-vinyl isoxazole derivative
CN113666883B (en) * 2021-07-23 2023-06-16 华南理工大学 Method for synthesizing 4-vinyl isoxazole derivative
WO2023210792A1 (en) * 2022-04-28 2023-11-02 日本農薬株式会社 Nitrogen-containing heterocyclic compound having oxime group, agricultural/horticultural herbicide containing said compound, and use of both of foregoing
JPWO2023210792A1 (en) * 2022-04-28 2023-11-02
TWI870837B (en) * 2022-04-28 2025-01-21 日商日本農藥股份有限公司 Nitrogen-containing heterocyclic compound having an oxime group, agricultural or horticultural herbicide comprising the compound, and method for using the compound or the herbicide
JP7733225B2 (en) 2022-04-28 2025-09-02 日本農薬株式会社 Nitrogen-containing heterocyclic compound having an oxime group, agricultural and horticultural herbicide containing said compound, and method of using the same

Also Published As

Publication number Publication date
AU1561599A (en) 1999-05-31

Similar Documents

Publication Publication Date Title
JP4965050B2 (en) Substituted pyridine herbicides
JP4299483B2 (en) Isoxazoline derivatives and herbicides containing the same as active ingredients
AU2005291117B2 (en) Isoxazoline derivatives and their use as herbicides
JP3310039B2 (en) Herbicide
DE69923869T2 (en) SUBSTITUTED PYRIDINES WITH HERBICIDAL EFFECT
US20040242456A1 (en) Herbicidal n-alkysulfonamino derivatives
US20040192910A1 (en) Sulfonylamino derivatives useful as herbicides
EP1031573B1 (en) Novel benzoylpyrazole compounds, intermediates, and herbicides
JP2002524554A (en) Pyridine ketones useful as herbicides
CA2059609A1 (en) Herbicides
AU7514600A (en) Novel herbicides
WO1997035851A1 (en) Heterocycle-substituted benzene derivatives and herbicides
JP3234684B2 (en) New herbicides
HUT72276A (en) 4-benzoyl isoxazole derivatives and their use as herbicides
WO1999024409A1 (en) Isoxazole derivatives and their use as herbicides
EP0560483A1 (en) 4 Benzopyl isoxazole derivatives and their use as herbicides
CA2209493A1 (en) Substituted 2-phenylpyridines
WO2001066522A1 (en) Acylated phenyl or pyridine herbicides
AU732154B2 (en) Benzothiophene derivates as herbicides
AU2003276976A1 (en) Nicotinoyl derivatives as herbicidal compounds
JPH11292849A (en) Benzoylpyrazole compound and herbicide
IE910279A1 (en) Heterocyclic compounds
EP0832070A1 (en) Novel herbicides
KR100300219B1 (en) Benzene derivatives and herbicides substituted by heterocycles
JPH11236376A (en) New benzoylpyrazole compound and herbicide

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

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

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

Ref country code: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA