EP0901485A1 - 1,2-benzoxathin- und thiepin 2,2-dioxid-herbizide - Google Patents

1,2-benzoxathin- und thiepin 2,2-dioxid-herbizide

Info

Publication number
EP0901485A1
EP0901485A1 EP97922598A EP97922598A EP0901485A1 EP 0901485 A1 EP0901485 A1 EP 0901485A1 EP 97922598 A EP97922598 A EP 97922598A EP 97922598 A EP97922598 A EP 97922598A EP 0901485 A1 EP0901485 A1 EP 0901485A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
formula
independently
scheme
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.)
Withdrawn
Application number
EP97922598A
Other languages
English (en)
French (fr)
Inventor
Morris Padgett Rorer
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0901485A1 publication Critical patent/EP0901485A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
    • C07D291/08—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
    • C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D419/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/10—Spiro-condensed systems

Definitions

  • This invention relates to certain 1 ,2-benzoxathiin and 1 ,2-benzothiepin 2,2-dioxides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation.
  • the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • Rj, R la , R , R 2a , 3, and R 4 are independently hydrogen or Ci-Cg alkyl
  • R 5 is C r C 8 alkyl, halogen, cyano, nitro, -(O) n S(O) rn R 12 or - ⁇ R 15 SO 2 R 12 ;
  • R 6 and R 7 are independently hydrogen, C ⁇ -C 8 alkyl, halogen, cyano, nitro, -(0)n S (°)m R 12 or " NR 15S0 2 R 12 ; provided that at least one of R 5 , R 6 or R 7 is a group -OS(O) 2 R 12 or -NR ]5 SO 2 R 12 ;
  • Rg is hydrogen or a salt forming moiety
  • R J2 is C r C 8 alkyl optionally substituted with one to six halogens
  • R15 is hydrogen or C j -Cg alkyl; n is 0 or 1 ; and m is 0, 1 or 2.
  • the 1 ,2-benzoxathiin and 1 ,2-benzothiepin 2,2-dioxides of the present invention are not disclosed in this patent.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
  • R 1 is OR 8 , SH, C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C Cg alkylsulfonyl, C j -Cg haloalkylsulfonyl, halogen or ⁇ R21a 2lb ; or Rl j s phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro; each R 2 is independently H, C j -C 3 alkyl, CyC 6 alkenyl, C 3 -C 6 alkynyl, C j -C 3 alkoxy, formyl, C 2 -Cg alkoxycarbonyl, -CH(C ] -C 3 al
  • R 3 is H, Ct-Cg alkyl, C j -Cg haloalkyl, halogen, cyano or nitro;
  • R 4 is H, C C 6 alkyl, C C 6 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R * * is phenyl or benzyl, each optionally substituted on the phenyl ring with C J -C3 alkyl, halogen, cyano or nitro;
  • R 5 is H, C,-C 6 alkyl, -Cg haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C j -C 6 alkylsulfonyl or C j -Cg haloalkylsulfonyl; or R 5 is benzoyl or phenylsulfonyl, each optionally substituted with C ⁇ .-Cj alkyl, halogen, cyano or nitro;
  • R 6 is H, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl, CO 2 H or cyano;
  • R 7 is H, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl;
  • R 8 is H, C,-C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C(O)NR 21a R 21b , C,-C 6 alkylsulfonyl or C r C 6 haloalkylsulfonyl; or R 8 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C j -C 3 alkyl, halogen, cyano or nitro;
  • R 9 and R 10 are independently H, C,-C 6 alkyl, C,-C 6 haloalkyl, C j -C 6 alkoxy, C j -Cg haloalkoxy, C ⁇ -C 6 alkylthio, Cj-Cg haloalkylthio, C ⁇ -C 6 alkyl sulfinyl, C l -C 6 haloalkylsulfmyl, C ⁇ C 6 alkylsulfonyl, C ] -C 6 haloalkylsulfonyl, aminosulfonyl, C ⁇ C 2 alkylaminosulfonyl, C 2 -C4 dialkylaminosulfonyl, halogen, cyano or nitro;
  • R 1 1 , R 12 , R 13 , R 17 and R 18 are independently H, halogen, cyano, C j - alkyl, C,-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Cj-C 6 alkoxy, Cj-C 6 haloalkoxy, C j -C 6 alkylthio or C j - haloalkylthio;
  • R 14 is H, halogen, C,-C 6 alkyl or C,-C 6 haloalkyl
  • R 15 is H, halogen, cyano, Cj-C 6 alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, - alkoxy, C ] -C 6 haloalkoxy, C ⁇ Cg alkylthio or C ⁇ -C 6 haloalkylthio;
  • R 16 is H, C ! -C 6 alkoxy, C 2 -C 6 haloalkoxy, C,-C 6 alkylthio, C 2 -C 6 haloalkylthio; or R 15 and R i 6 are taken together to form -X 1 -(CH 2 ) r -X 2 -, -(CH 2 ) S -X 3 -,
  • X 1 and X 2 are each independently O, S or N(C j -C 3 alkyl); X 3 is O or S;
  • G is O or CH 2 ;
  • R 19 is H, C j -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl;
  • R 20 is Cj-C alkyl; or R 20 is phenyl optionally substituted with C ⁇ C 3 alkyl, halogen, cyano or nitro; R 21 is H, C ] -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl;
  • R 21 s H or C r C 6 alkyl
  • R 21b is C,-C 6 alkyl or C r C 6 alkoxy
  • R 1a and R l t> can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
  • Y and Z together with the carbons to which they are attached form a fused lH-4,5- dihydropyrazole or pyridine ring optionally substituted with up to three groups independently selected from the group halogen and Cj-C alkyl, provided that when the nitrogen atom of the fused lH-4,5-dihydropyrazole ring is substituted, then the nitrogen substituent is C j -Cg alkyl; or Y and Z together with the carbons to which they are attached form a fused pyrazole, pyrimidine or thiophene ring, each optionally substituted with up to two groups independently selected from the group halogen and C j -Cg alkyl, provided that when the nitrogen atom of the fused pyrazole ring is substituted, then the nitrogen substituent is C j -Cg al
  • Ci-Cg alkyl is O or 1; m is 0 or 1 ; n is 1 or 2; q is 0, 1, 2, 3 or 4; r is 2, 3 or 4; s is 2, 3, 4 or 5; t is 1, 2, 3 or 4; v is 2 or 3; and w is 2, 3, 4, 5 or 6; provided that:
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl which are independently selected.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, * ?-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfmyl group. Examples of
  • alkylsulfinyl include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkylamino dialkylamino
  • alkenylthio alkenylsulfinyl
  • alkenylsulfonyl alkynylthio
  • alkynylsulfinyl “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • N-oxides One skilled in the art will also recognize that tertiary amines can form N-oxides.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O),
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R) j _ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • Some compounds of this invention can exist as one or more tautomers.
  • compounds of Formula Ia (Formula I where Q is Q- 1, R 1 is OR 8 , and R 8 is H) can also exist as the tautomers of Formulae lb and Ic as shown below.
  • said tautomers often exist in equilibrium with each other.
  • the present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartarie,
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein
  • A is selected from A-l, A-2 and A-6;
  • R 9 and R 10 are independently H, halogen, nitro, C j -C 3 alkyl or Cj-C 3 alkoxy;
  • R 11 and R 12 are independently H, halogen or C j -C 3 alkyl;
  • R 13 and R 14 are independently H or C j -C 3 alkyl;
  • R 15 and R 16 are independently H, C ] -C 3 alkyl , C j -C 3 alkoxy, C 2 -C 3 haloalkoxy, C j -C 3 alkylthio or C 2 -C 3 haloalkylthio; or
  • A-6 is selected from A-6a, A-6b, A-6c, A-6d, A-6e and A-6f:
  • R 22 , R 24 and R 30 are independently C]-C 6 alkyl
  • R 23 , R 2 5, R 2 6, R 27 , R 28 and R 29 are independently H or C j -C 4 alkyl;
  • R 31 and R 32 are independently H or C j -C 2 alkyl.
  • Preferred 2 Compounds of Preferred 1 wherein k is O; m is O;
  • R 9 and R 10 are independently C ⁇ -C 3 alkyl or halogen
  • R 11 and R 12 are independently H or C j -C 3 alkyl; R 15 and R ] 6 are taken together as -OCH 2 CH 2 O- or -SCH 2 CH 2 S- ; or R 15 and
  • R 21 is C!-C 2 alkyl
  • R 22 , R 24 and R 30 are independently C j -C 3 alkyl; and R 23 , R 25 , R 26 , R 27 , R 28 and R 29 are independently H or C,-C 2 alkyl; and
  • R 31 and R 32 are independently H or C ] -C 2 alkyl.
  • Preferred 3 Compounds of Preferred 2 wherein
  • Q is Q-2.
  • Preferred 5 Compounds of Preferred 2 wherein Q is Q-3. Most preferred is the compound of Preferred 3 which is selected from the group:
  • compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • a surfactant a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-63. Unless otherwise specified, the definitions of Q, A, R'—R 32 , X -X 3 , G, Y, Z, k, m, n, q, r, s, t, v and w in the compounds of Formulae Id- If and Formulae 1-49 below are as described in the Summary of the Invention.
  • Compounds of Formulae Id— are various subsets of the compounds of Formula I. For example, compounds of Formula Id below are compounds of Formula I wherein Q is Q-1.
  • Scheme 2 illustrates the preparation of compounds of Formula Id (A is as defined in Scheme 1; R 1 is S(O) x R 34 wherein x is 1 or 2, and R 34 is C j -C 6 alkyl or C C 6 haloalkyl) whereby a compound of Formula Id (A is as defined in Scheme 1; R 1 is SR 34 ) is reacted with an oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®) or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate).
  • an oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®) or hydrogen peroxide
  • the oxidation is carried out by methods known in the art (or by slight modification of these methods); for example, see B. M. Trost et al., J. Org. Chem. (1988), 53, 532; B. M. Trost et al., Tetrahedron Lett. (1981), 21, 1287;
  • Id (Rl is OH)
  • R is halogen
  • halogenating reagent e.g., oxalyl bromide or oxalyl chloride
  • aqueous hydrochloric or hydrobromic acid 0.1 to 12N
  • This conversion is carried out by methods known in the art (or slight modification of these methods); see for example, P. A. Grieco et al., J. Am. Chem. Soc. (1977), 99, 5773; P. A. Grieco et al, J. Org. Chem. (1978), 43, 4178.
  • Scheme 6 illustrates the preparation of compounds of Formula Id (A is as defined in
  • Enol esters of Formula 3 (A is as defined in Scheme 1) can be prepared by reacting a dione of Formula 4 with an acid chloride of Formula 5 (A is as defined in Scheme 1 ) in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 and 110 °C
  • a base such as triethylamine
  • an inert organic solvent such as acetonitrile, dichloromethane or toluene
  • Acid chlorides of Formula 5 can be prepared by reacting an acid of Formula 6 (A is as defined in Scheme 1) with oxalyl chloride (or thionyl chloride) and a catalytic amount of N,N-dimethylformamide (DMF) (Scheme 8). This chlorination is well known in the art; see for example, W. J. Michaely, EP 369,803.
  • acids of Formula 6 can also be utilized to directly react with dione 4 in a direct ester formation reaction to provide esters of Formula 3.
  • a promoter such as 1,3-dicyclohexyl carbodiimide, 1,1-carbonyl diimidazole, or 2-chloro-N-methylpyridinium iodide and other reagents known to couple acids and alcohols or phenols can be utilized together with an acid acceptor.
  • the acid acceptor is usually an amine base such as triethylamine or pyridine; see for example, Larock, Comprehensive Organic
  • This conversion is carried out by general methods known in the art (or slight modification of these methods); for example, see V. K. Lusis et al., Khim. Geterotsiklt. (1986), 5, 709;
  • the acids of Formula 6 can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 11-55 and 63 (or by slight modification of these methods). For example, the preparation of acids of Formula 6a are described in Schemes 11-23 and 63.
  • acids of Formula 6a (m is 0; k is 0 or 1) can be prepared whereby an acid of Formula 7 (k is 0 or 1) is reacted with chlorosulfonic acid (Scheme 11).
  • the chlorosulfonic acid is used in excess (at least 2 to 10 mole excess) and serves as both reactant and solvent.
  • the reaction is carried out at a temperature between about 25 and 80 °C for a period of time ranging from 1 hour to about 72 hours. After quenching the reaction into excess ice, the mixture is filtered (if a solid is present) or extracted with a solvent such as dichloromethane and concentrated.
  • Rl ' is C 2 -C 6 alkyl, C ⁇ -C ⁇ haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl or C 2 -C 6 haloalkynyl; and R l2 is R 1 as just defined and also H.
  • Scheme 12 illustrates a method for preparing many acids of Formula 7 whereby a corresponding bromo compound of Formula 8 is reacted with n-butyllithium (or magnesium) and the lithium salt (or Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid.
  • This conversion is carried out by methods known in the art (or slight modification of these methods); see for example, M. A. Ogliaruso et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives,
  • Scheme 13 illustrates the preparation of many dihydrobenzofurans of Formula 8 (L is H or Br; k is 0) whereby an allyl phenyl ether of Formula 9 (L is H or Br) is heated under Claisen rearrangement conditions (e.g., about 200 °C optionally in the presence of a catalyst such as anhydrous magnesium bromide) by methods known in the art (or slight modification of these methods); see for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), John Wiley & Sons, pp. 1028-1032 and references therein.
  • Claisen rearrangement conditions e.g., about 200 °C optionally in the presence of a catalyst such as anhydrous magnesium bromide
  • the allyl phenyl ethers of Formula 9 can be prepared from corresponding phenols and allyl bromides or allyl chlorides by reaction in the presence of a base such as potassium carbonate by methods known in the art; see for example, M. P. Rorer, United States Patent 4,514,211 (published 1985). Also, bromination of dihydrobenzofurans of Formula 8 (L is H) by methods generally known in the art can also provide bromo compounds of Formula 8 (L is Br).
  • R 1 la is H, Cj-C; alkyl or C ⁇ C ⁇ haloalkyl; Rl 1 is C,-C 6 alkyl or C,-C 6 haloalkyl; and Rl 2 is R ⁇ and also H.
  • Chromanes of Formula 8 (k is 1) can be prepared by one skilled in the art also by methods known in the art; see for example, The Chemistry of Heterocyclic Compounds, G. P. Ellis, Ed. (1981), Volume 36, John Wiley & Sons, New York.
  • acids of Formula 6a can also be readily prepared, as illustrated in Scheme 14, whereby an ester of Formula 10 (L is CO 2 CH 3 ) is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, acid hydrolyzed (e.g., 5N HCl in acetic acid) by methods known in the art (or slight modification of these methods); see for example, M. A. Ogliaruso et al., Synthesis of Carboxylic Acids,
  • Scheme 15 illustrates many acids of Formula 6a can be prepared whereby an iodo compound of Formula 10 (L is I) is reacted with carbon monoxide (CO) in the presence of a palladium catalyst such as palladium acetate (Pd(OAc) 2 ), a phosphine catalyst such as l,3-bis(diphenylphosphino)propane (dppp), an excess of an alcohol such as methanol, and a base such as triethylamine to form the corresponding ester of Formula 10 (L is CO 2 CH 3 ).
  • a palladium catalyst such as palladium acetate (Pd(OAc) 2 )
  • a phosphine catalyst such as l,3-bis(diphenylphosphino)propane (dppp)
  • dppp l,3-bis(diphenylphosphino)propane
  • dppp l,3-bis(diphenylphosphino
  • Scheme 16 illustrates the preparation of many esters of Formula 10 (L is CO 2 CH 3 ) or iodo compounds of Formula 10 (L is I) whereby a corresponding hydroxy compound of
  • Formula 1 1 (L is CO 2 CH 3 or I) is reacted with appropriate reagents known in the art to cause water elimination (e.g., with phosphorus oxychloride (POCl 3 ) in pyridine).
  • This reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, J. Erhrenfreund et al, U.S. 4,589,911 (published 1986) and J. M. Clancy et al., Int.
  • Scheme 17 illustrates the preparation of many hydroxy compounds of Formula 11 whereby a sulfonate of Formula 12 is reacted with a suitable base such as 5 l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to cause cyclization.
  • a suitable base such as 5 l,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
  • DBU 5 l,8-diazabicyclo[5.4.0]undec-7-ene
  • Scheme 18 illustrates the preparation of many sulfonates of Formula 12 whereby a phenol of Formula 13 is reacted with a sulfonyl chloride of Formula 14 in the presence of a suitable base such as triethylamine by methods known in the art (or slight modification of these methods); see for example, the two references cited in Scheme 17 and J. F. King et al., J. Am. Chem. Soc. (1964), 86, 287.
  • a suitable base such as triethylamine
  • Scheme 19 illustrates the preparation of many aldehydes of Formula 13 (k is 0; R i2 is H) whereby a phenol of Formula 15 is reacted with appropriate reagents to introduce an aldehyde group ortho to the phenyl hydroxy group.
  • This reaction can be carried out by a variety of methods well known in the art (or slight modification of these methods); see for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), John Wiley & Sons, pp. 487-491; G. Casiraghi et al., J. Chem. Soc. Perkin I (1980), 1862; R. X. Wang et al., Synthetic Commun. (1994), 24 (12), 1757.
  • a preferred method is hexamethylenetetramine (HMT) in an acid such as polyphosphoric acid; see for example, Y. Suzuki et al., Chem.
  • Scheme 20 illustrates the preparation of many ketones of Formula 13 whereby an ester of Formula 16 is heated under Fries rearrangement conditions (e.g., about 150 to 200 °C in the presence of a suitable Lewis catalyst such as aluminum chloride) by methods known in the art (or slight modification of these methods); see for example, F. Shawcross et al., J. Het. Chem. (1995), 32, 1393; J. March, Advanced Organic Chemistry (1985), 3rd edition, John Wiley & Sons, pp. 499-501.
  • Fries rearrangement conditions e.g., about 150 to 200 °C in the presence of a suitable Lewis catalyst such as aluminum chloride
  • iodo compounds of Formulae 13, 15, and 16 can be prepared by one skilled in the art by reacting corresponding compounds of Formulae 13, 15, and 16 (wherein L is H) with appropriate iodination reagents known in the art (e.g., with iodine monochloride in acetic acid, optionally with a base such as sodium acetate); see for example, K. M. Tramposch et al., J. Am. Chem. Soc. (1983), 26, 121; J. March, Advanced Organic Chemistry, 3rd Edition (1985), John Wiley & Sons, p. 478.
  • appropriate iodination reagents e.g., with iodine monochloride in acetic acid, optionally with a base such as sodium acetate
  • aldo phenols of Formula 13 containing an ester group can be prepared by one skilled in the art by a sequence of reactions illustrated in Scheme 21. These reactions can be carried out by methods known in the art whereby (a) a phenyl ether of Formula 17 is reacted with phosphorus oxychloride and DMF to form an aldehyde of Formula 17a (see for example, F. Balkau et al., Aust. J. Chem. (1969), 22, 2489; Buu-Hoi et al., Seanc. Acad.
  • Rl ' and R i2 are as originally defined.
  • Rl l is Cl; R 12 is H, C ⁇ -C 6 alkyl or C ⁇ -Cf, haloalkyl; and L is CO 2 CH 3 or I
  • Formula 10 (Rl * is Br; Rl 2 is H, CJ-CG alkyl or Cj-C 6 haloalkyl; and L is CO 2 CH or I)
  • R 1 1 is H
  • R i2 is H, C j -C 6 alkyl or Cj-C 6 haloalkyl; and L is CO 2 CH 3 or I) is halogenated by reaction with chlorine or bromine followed by dehydrohalogenation by reaction with a suitable base such as pyridine.
  • These reactions can be carried out by methods known in the art (or slight modification of these methods); see for example, J. M. Clancy et al., Int. J. S
  • Acids of Formula 6b can be prepared by methods illustrated in Schemes 24-36 by one skilled in the art.
  • Scheme 24 illustrates the preparation of many acids of Formula 6b whereby corresponding acids of Formula 6a are catalytically hydrogenated by methods known in the art (or slight modification of these methods); see for example, W. Werner, United States
  • Patent 4,560,771 (published 1985).
  • H 2 e.g., Pd/C
  • Scheme 27 illustrates the preparation of many halogenated compounds of Formula 19
  • L and Rl 5 is Cl, Br or F) wherein k is 0 or 1; m is 0; R 12 , R ⁇ 4 and Rl° are H; and R 3 is R 1 other than halogen.
  • Scheme 28 illustrates the preparation of compounds of Formula 19 (L is I or CO 2 CH 3 ; Rl 5 is C ⁇ -C 6 alkoxy, C j -C 6 haloalkoxy, C j -C 6 alkylthio, C j -Cg haloalkylthio or cyano; R 6 is H) whereby a halogenated compound of Formula 19 (L is I or CO 2 CH 3 ; R 15 is Cl or Br; R 16 is H) is reacted with a nucleophilic reagent of Formula 20 (R 37 is Cj-C 6 alkoxy, Cj- Cs haloalkoxy, C ⁇ C 6 alkylthio, C ⁇ -C 6 haloalkylthio or cyano; M is Na, K or Li).
  • the reaction is carried out in a suitable solvent such as methanol, DMF or tetrahydrofuran (preferably, methanol) at a temperature range between about 0 and 80 °C and for a time period of about 1 to 8 hours.
  • a suitable solvent such as methanol, DMF or tetrahydrofuran (preferably, methanol)
  • concentration the immediate residue can be further purified by flash column chromatography procedures on silica gel with mixed eluants such as ethyl acetate and hexanes by one skilled in the art.
  • Rl 5 is Cl orBr
  • R M R15 is C -C 6 alkoxy, C!-C 6
  • R ] 5 and Rl 6 are independently C j -Cg alkoxy, C 2 -C 6 haloalkoxy, Cj-C 6 alkylthio or C 2 -C 6 haloalkylthio; or R 15 and R i6 are taken together to form -Xl-(CH 2 ) r -X 2 - optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one C!-C 3 alkoxy; and X J and X 2 are as defined in the Summary of the Invention) whereby a ketone of
  • Formula 21 is reacted with an alcohol, an alkylthiol, or HXl-(CH 2 ) r -X 2 H (optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one Cj-C 3 alkoxy; X 1 , X 2 and r are as defined in the Summary of the Invention) in the presence of a protic acid catalyst such as ?-toluenesulfonic acid (or a Lewis acid such as BF 3 ) in an inert organic solvent such as toluene or in an alcohol (if the alcohol is the reagent).
  • a protic acid catalyst such as ?-toluenesulfonic acid (or a Lewis acid such as BF 3 )
  • an inert organic solvent such as toluene or in an alcohol (if the alcohol is the reagent).
  • Rl are independently C j -Cg alkoxy, C 2 -Cg haloalkoxy, C l -C 6 alkylthio or C 2 -C 6
  • R15 and Rl° are taken together to form -(CH 2 ) s -O-, -(CH 2 ) t -X 3 -CH 2 , -(CH 2 ) V -X 3 -CH 2 CH 2 - or -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one Cj-C 3 alkoxy) where a ketone of Formula 21 is reacted with a Grignard reagent, a sulfonium cycloalkylide, a lithium lithioalkoxide, an organopalladium reagent, a sulfonium ylide or other equivalent reagent in an inert organic solvent.
  • Some of the immediate products from the reactions of Scheme 30 may be further modified to give the desired compounds of Formula 19.
  • the above-mentioned reactions are carried out by methods known in the art (or by slight modification of these methods); for example, see S. Umio et al., J. Med. Chem. (1972), 15, 855; B. Mudryk et al., J. Org. Chem. (1989), 54 (24), 5657; Z. Paryzek et al., Can. J. Chem. (1987), 65 (1), 229; B. M. Trost et al., J. Am.
  • Grignard reagent, sulfonium R 1 are taken together to form cycloalkylide, lithium lithioalkoxide, organopalladium -(CH 2 ) x -0-, -(CH 2 ) t -X 3 -CH 2 -, reagent, sulfonium ylide or -(CH 2 ) V -X 3 -CH 2 CH 2 - or other equivalent reagent -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and C1-C3 alkoxy)
  • Scheme 31 illustrates the preparation of compounds of Formula 19 (L is I or CO CH 3 ;
  • Rl 5 and Rl 6 are taken together to form -(CH 2 ) S -S- optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH and one C ] -C alkoxy) whereby a thioketone of Formula 22 is reacted with a dibromo alkane of Formula 23 in the presence of an equimolar amount or more of ytterbium (Yb) metal in an inert organic solvent such as a mixture of benzene and hexamethylphosphoric triamide.
  • Yb ytterbium
  • Some of the immediate products from the reactions of Scheme 32 may be further modified to give the desired compounds of Formula 19.
  • the above mentioned reactions are carried out by methods known in the art (or by slight modification of these methods); for example, see M. Chini et al., J. Org. Chem. (1989), 54, 3930; B. Chenera et al., Tetrahedron (1986), 42 (13), 3443; R. Mechoulam et al., J. Am. Chem. Soc. (1958), 80, 4386; A. Hosomi et al.,
  • R 9 are independently H, > 15 personallynH p !6 halogen or CH 3 ) one C1-C3 alko ⁇ y or R and R are taken together to form
  • ketones of Formula 21 can also be prepared, as illustrated in Scheme 34, whereby a propionyl bromide of Formula 25 is reacted with sodium sulfite followed by phosphorus oxychloride.
  • These reactions can be carried out by methods known in the art (or slight modification of these methods); see for example, J. M. Clancy, Int. J. Sulfur Chem., A
  • Alkene compounds of Formula 24 can be prepared from the ketones of Formula 21 by general methods known in the art; see for example, J. Hibino et al., Tetrahedron Lett. (1985), 26 (45), 5579; A. S. Rao, Synthetic Commun. (1989), 19 (5-6), 931-942; R. G. Gentles et al., J. Chem. Soc. Perkin Trans. 1 (1991), (6), 1423; F. A. Davis, Tetrahedron Lett. (1991), 32 (52), 7671.
  • the thioketones of Formula 22 can be prepared from the ketones of Formula 21 by general methods known in the art (Scheme 35); see for example, V. K. Lusis et al., Khim.
  • an oxime of Formula 19 (R i is H) can be further O-alkylated by reaction with an alkylating reagent of Formula 27 (R 21 is Cj-C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C alkynyl; and X 5 is Br, I or trifluorosulfonyloxy) in the presence of a suitable base such as sodium hydride or potassium carbonate and in a suitable solvent such as tetrahydrofuran or DMF.
  • a suitable base such as sodium hydride or potassium carbonate
  • a suitable solvent such as tetrahydrofuran or DMF.
  • Acids of Formula 6c can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 37-40 (or by slight modification of these methods) by one skilled in the art.
  • acids of Formula 6c can be prepared from corresponding iodo compounds of Formula 28 (L is I) by methods analogous to those described in Scheme 15 by one skilled in the art.
  • Scheme 39 illustrates the preparation of epoxides of Formula 28 (L is I or CO 2 CH 3 ; G is O) whereby a corresponding alkene compound of Formula 10 (L is I or CO CH 3 ) is reacted with a suitable oxidizing reagent such as aqueous hydrogen peroxide (preferably), or peroxytrifluoroacetic acid.
  • a suitable oxidizing reagent such as aqueous hydrogen peroxide (preferably), or peroxytrifluoroacetic acid.
  • This reaction is carried out by methods known in the art (or by slight modification of these methods); see for example, B. Z. Zwanenburg et al., Tetrahedron Lett. (1970), 935; G. B. Payne et al., J. Org. Chem. (1959), 24, 54; W. D. Emmons et al., J. Am. Chem. Soc.
  • acids of Formula 6a (Schemes 11, 14 and 15) can also be reacted to form corresponding epoxides of Formula 6c (L is CO 2 H). This reaction can be carried out by methods described above (or by slight modification of these methods) by one skilled in the art.
  • Scheme 40 illustrates the preparation of cyclopropyl compounds of Formula 28 (L is I or CO 2 CH 3 , G is CH 2 ) whereby a corresponding alkene compound of Formula 10 (L is I or CO 2 CH 3 ) is reacted with a suitable sulfur ylide such as dimethylsulfonium methylide.
  • a suitable sulfur ylide such as dimethylsulfonium methylide.
  • Acids of Formula 6d can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 41—43 (or slight modification of these methods) by one skilled in the art.
  • a compound of Formula 29 (wherein R 19 is H) may be N-alkylated by reaction with an alkylating reagent of Formula 31 (Rl9 is C j -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; ⁇ 6 is Br or I) and a suitable base such as potassium carbonate to form a corresponding compound of Formula 29 (wherein R 19 is Cj-C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl).
  • the reaction is carried out in a suitable solvent such as acetonitrile and a temperature range of about -10 to 80 °C for a time range of about 1 to 8 hours.
  • a suitable solvent such as acetonitrile and a temperature range of about -10 to 80 °C for a time range of about 1 to 8 hours.
  • the immediate residue may be further purified by flash column chromatography on silica gel with mixed eluants such as ethyl acetate and hexanes by one skilled in the art.
  • Compounds of Formula 30 can be prepared by one skilled in the art by methods known in the art.
  • Acids of Formula 6e can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 44—47 (or slight modification of these methods) by one skilled in the art.
  • Scheme 46 illustrates the preparation of many compounds of Formula 32 (L is I or
  • Acids of Formula 6f can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 48-55 and 63 (or slight modification of these methods).
  • H + Scheme 50 illustrates the preparation of compounds of Formula 35a (L is I or CO CH 3 ) and Formula 35b (L is I or CO 2 CH 3 ) whereby a ketone of Formula 36 (L is I or CO 2 CH 3 ) is reacted with hydrazine of Formula 37 in an inert organic acidic solvent such as glacial acetic acid at a temperature between about 15 and 120 °C for a period of time ranging from about 1 to 24 hours. The reaction is quenched with excess water and filtered if a solid is formed.
  • an inert organic acidic solvent such as glacial acetic acid
  • the suspension can be extracted with a suitable inert organic solvent such as dichloromethane, dried (e.g., over magnesium sulfate) and concentrated.
  • a suitable inert organic solvent such as dichloromethane
  • dried e.g., over magnesium sulfate
  • the solid from the filtration or the residue from the concentration can be further purified if needed by recrystallization from an inert organic solvent such as acetonitrile or
  • 35a (L is C0 2 CH 3 or I) 35b (L is C0 2 CH 3 or I) wherein R 40 is H or alkyl; R i is H or C ⁇ -C 3 alkyl.
  • compounds of Formula 35c (L is CO 2 CH 3 or I) and Formula 35d (L is CO CH 3 or I) can be prepared by reacting a ketone of Formula 36 with hydroxylamine or hydroxylamine hydrochloride in an inert organic solvent such as ethanol or glacial acetic acid.
  • the reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Volume 6 (1984), Pergamon Press, pp. 61-64 and p 118; H. Boshagen, Chem. Ber. (1967), 100, 3326.
  • Scheme 53 illustrates the preparation of compounds of Formula 35f whereby a ketone of Formula 39 is reacted with a hydrazine of Formula 40. This conversion is carried out by methods known in the art (or by slight modification of these methods); see for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry (1984), Volume 5, pp. 278- 279, Pergamon Press. Scheme 53
  • the ketones of Formula 36 can be prepared by one skilled in the art by reacting a ketone of Formula 21 with an amide dimethyl acetal of Formula 41 (Scheme 54).
  • the reaction can be carried out by methods well known in the art (or slight modification of these methods); see for example, G. Litkei et al., Org. Prep. Proced. Int. (1990), 22, 47-56;
  • the ketones of Formula 39 can be prepared by one skilled in the art by reacting a ketone of Formula 21 with an aldehyde or a ketone of Formula 42 (or its equivalent) in the presence of an acid or a base (Scheme 55). This conversion is well known in the art; see for example, J. L. Gras, Tetrahedron Lett. (1978), 2111; L. Engman et al., Tetrahedron Lett.
  • Scheme 56 illustrates the preparation of compounds of Formula le (R 5 is R 5a , R 5a is the same as R 5 as described in the Summary of the Invention excluding H) whereby a compound of Formula le (R 5 is H) is reacted with a reagent of Formula 43 in the presence of a base wherein X 7 is chlorine, bromine, fluorine, OTf, OAc and R 5a is as previously defined.
  • Scheme 57 illustrates the preparation of compounds of Formula le (R 5 is H) whereby an ester of Formula 44 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide).
  • cyanide source e.g., acetone cyanohydrin or potassium cyanide.
  • Esters of Formula 44 can be prepared by reacting a hydroxypyrazole of Formula 45 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 and 110 °C (Scheme 58). This type of coupling is carried out by methods known in the art (or by slight modification of these methods); see for example, W. J. Michaely, EP 369,803. Scheme 58
  • Scheme 59 illustrates the preparation of compounds of Formula If whereby a compound of Formula 46 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate.
  • a salt of hydroxylamine such as hydroxylamine hydrochloride
  • a base or acid acceptor such as triethylamine or sodium acetate.
  • the substituents of the immediate products may be further modified if appropriate.
  • L 1 is a leaving group such as C j -C alkoxy (e.g., OC 2 H 5 ) or N,N-dialkylamino (e.g., dimethylamino), R°a i s R6 0 r CO ⁇ H 2 .
  • C j -C alkoxy e.g., OC 2 H 5
  • N,N-dialkylamino e.g., dimethylamino
  • Scheme 60 illustrates the preparation of compounds of Formula 46 whereby a compound of Formula 47 is reacted with a reagent of Formula 48 or Formula 49. This conversion is carried out by methods known in the art (or by slight modification of these methods); see for example P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622. Scheme 60
  • R 42 is C j - alkyl.
  • Formula 48 is decarboxylated in the presence of a catalyst, such as p-toluenesulfonic acid, in an inert solvent such as toluene. This conversion is carried out by methods known in the art
  • Esters of Formula 48 can be prepared by reacting the metal salt of a compound of Formula 49 with an acid chloride of Formula 5 (Scheme 62). This type of coupling is known in the art; see for example, P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622.
  • Step B Preparation of 3,6-dimethyl-2-(2-propenyl)phenol A 100-mL two-neck round-bottom flask equipped with a thermometer and magnetic stirring bar and containing the title compound of Step A (31.7 g, 0.195 mol) was lowered into an oil bath preheated to 200 °C.
  • the oil in the flask was stirred and heated under nitrogen at 200 °C for 2 h, then the flask was removed from the oil bath and the oil was allowed to cool to room temperature.
  • the oil residue was dissolved in hexane (about 100 mL) and the solution was extracted with aqueous IN ⁇ aOH (four times with 50 mL each).
  • the aqueous extracts were combined, made acidic to pH 1 by addition of concentrated hydrochloric acid, then extracted with dichloromethane.
  • the organic layer was dried (MgSO ) and concentrated under reduced pressure to yield 24.8 g of the title compound of Step B as an oil.
  • the suspension was stirred 1 hour at about -75 °C, then the cooling was removed and 120 mL of aqueous IN ⁇ aOH was added dropwise as the reaction temperature was allowed to rise. After reaching about 10 °C, the suspension was concentrated under reduced pressure until most of the tetrahydrofuran was removed. The aqueous residue was diluted with 200 mL of water, extracted with diethyl ether (twice with 40 mL each), acidified to pH 1 by addition of concentrated hydrochloric acid, then filtered.
  • Step E Preparation of 3,5,8-trimethyl-l,2-benzoxathiin-6-carboxylic acid 2,2-dioxide To chlorosulfonic acid (60 mL) was added portionwise the title compound of Step E
  • Step G Preparation of 3-oxo-l-cvclohexen-l-yl 3,5.8-trimethyI-L2-benzoxathiin-6- carboxylate 2,2-dioxide
  • Step F To oxalyl chloride (about 15 mL) was added the title compound of Step F (2.0 g, 0.0075 mol). The suspension was heated at reflux under nitrogen for about 2.5 h (giving a solution) then concentrated under reduced pressure. The residue was twice taken up in dichloromethane (30 mL) and concentrated under reduced pressure. Another portion of dichloromethane (25 mL) was added to the residual gum and the solution was cooled to about 5 °C. 1,3-Cyclohexanedione (purchased from Aldrich Chemical Company, 0.84 g, 0.0075 mol) was added, followed by triethylamine (1.52 g, 0.015 mol), and the suspension was stirred overnight while warming to room temperature.
  • 1,3-Cyclohexanedione purchased from Aldrich Chemical Company, 0.84 g, 0.0075 mol
  • the solution was concentrated under reduced pressure and the residue was dissolved in ethyl acetate (30 mL).
  • the ethyl acetate solution was extracted with water (30 mL), dilute aqueous sodium bicarbonate (IN, 30 mL), aqueous sodium hydroxide (IN, 20 mL) and then water again (30 mL).
  • the ethyl acetate solution was dried (MgSO 4 ) and concentrated under reduced pressure to yield 1.4 g of the title compound of Step G as a solid with a melting point of 199-203 °C.
  • Step E Preparation of 6-bromo-3-r(dimethylamino)methylenel-5.8-dimethyl- 1 ,2- benzoxathiin-4(3H)-one 2.2-dioxide 4.9 g (0.04) of 94% dimethylformamide dimethyl acetal (Aldrich Chemical Company) was added to a suspension containing 10.0 g (0.033 mol) of the title compound of Step D in 38 mL of toluene.
  • Step E Preparation of 8-bromo-2,6,9-trimethyl-2H-f 1 ,21benzoxathiinor4,3-clpyrazole
  • Step G Preparation of 2.6.9-trimethyl-2H-r 1.21benzoxathiinof4.3-clpyrazole-8- carbonitrile 4.4-dioxide
  • a suspension containing 5.6 g (0.016 mol) of the title compound of Step F and 2.1 g (0.023 mol) of copper (I) cyanide in about 70 mL of dimethylformamide was refluxed under nitrogen for 21 h then cooled to 25 °C and poured into excess water.
  • Step H Preparation of 2.6.9-trimethyl-2H-r 1 ,21benzoxathiinor4,3-clpyrazole-8- carboxamide 4.4-dioxide
  • polyphosphoric acid being stirred and heated in an oil bath at 115 °C was added portionwise 1.95 g (0.0068 mol) of the title compound of Step G.
  • the suspension was stirred and heated at about 120 °C for 6.5 h then cooled to 25 °C. Excess ice water was added to the suspension. The resulting mixture was filtered and the isolated solid was washed with water then suction dried to yield 1.5 g of the title compound of Step ⁇ as a solid melting at 240-243 °C (decomp).
  • Step I Preparation of 2,6.9-trimethyl-2H-r 1.21benzoxathiino[4,3-clpyrazole-8- carboxylic acid 4.4-dioxide
  • a suspension containing 1.68 g (0.0055 mol) of the title compound of Step ⁇ in 30 mL of acetonitrile under nitrogen was added portionwise 1.28 g (0.011 mol) of nitrosonium tetrafluoroborate (Aldrich Chemical Company) while maintaining the reaction temperature between 20 to 27 °C with external cooling.
  • the suspension was stirred at 25 °C for 1.5 h, heated at 50 °C in an oil bath for 4 h, then cooled to 25 °C.
  • Step J Preparation of 5.5-dimethyl-3-oxo-l-cvclohexen-l-yl 2.6.9-trimethyl-2H-
  • Step I The suspension was heated at reflux for 3 h (giving a solution) and concentrated under reduced pressure. The residue was twice taken up in dichloromethane (20 mL) and concentrated under reduced pressure to yield 1.59 g of solid. The solid was added to 30 mL of dichloromethane and the solution was cooled to 10 °C. 0.86 g (0.0058 mol) of 5,5- dimethylcyclohexanedione (Aldrich Chemical Company) was added followed by 1.76 g (0.0174 mol) of triethylamine. The suspension was stirred at room temperature overnight and then concentrated under reduced pressure. The residue was diluted with water (30 mL) and the suspension was filtered.
  • Step B Preparation of ( l-ethyl-5-hvdroxy- lH-pyrazol-4-yl)(2.6.9-trimethyl-4.4- dioxido-2H-r 1.21benzoxathiinor4.3-c1pyrazol-8-yl)methanone 1.1 g (0.0027 mol) of the title compound of Step A, 0.55 g (0.0055 mol) of triethylamine and 7 drops of acetone cyanohydrin were added sequentially to 50 mL of acetonitrile and the suspension was stirred under nitrogen overnight (ca. 16 h). A few crystals of potassium cyanide were added and the solution was stirred an additional 3 h and then concentrated under reduced pressure.
  • Rl is OH
  • R 9 is CH 3
  • R 10 is 4-CH 3
  • R 3 is H, R 4 is Et, R 5 is H
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 4 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
  • Compound 5 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example C Granule Compound 6 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
  • Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are not limited to alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.
  • a herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
  • Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • a mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
  • Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
  • the compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and were applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application).
  • preemergence application to water that covered the soil surface
  • postemergence application to plants that were in the one-to-four leaf stage
  • a sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.
  • Plant species in the preemergence and postemergence tests consisted of barley
  • Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass2 (Echinochloa crus-galli) and Late watergrass (Echinochloa oryzicola) grown to the 2 leaf stage for testing.
  • Plastic pots were partially filled with silt loam soil. The soil was then saturated with water.
  • Indica Rice Oryza sativa seed or seedlings at the 2.0 leaf stage; seeds, tubers or plant parts selected from barnyardgrass (Echinochloa crus-galli), at a two leaf stage ducksalad (Heteranthera limosa), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammonia species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloa fasicularis), were planted into this soil.
  • Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the two leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied directly to the paddy water, by pipette, or to the plant foliage, by an air-pressure assisted, calibrated belt-conveyer spray system.
  • PD/TA ducksalad 40 ducksalad 65 50 junglerice 15 junglerice 20 30 late watergrass 0 late watergrass 0 0 redstem 85 redstem 95 45 rice flatsedge 50 rice flatsedge 65 50 smallflower fla 30 smallflower fla 30 0 tighthead spran 60 tighthead spran 80 2 LF barnyard g 10
  • Treated plants and untreated controls were maintained under greenhouse conditions for twenty to thirty days at which time treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table D, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control.
  • Crop and weed species include annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed (Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Galium aparine), green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), ryegrass (L
  • Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table E, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result.

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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
EP97922598A 1996-05-07 1997-05-01 1,2-benzoxathin- und thiepin 2,2-dioxid-herbizide Withdrawn EP0901485A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1654296P 1996-05-07 1996-05-07
US16542P 1996-05-07
PCT/US1997/007363 WO1997042185A1 (en) 1996-05-07 1997-05-01 1,2-benzoxathiin and thiepin 2,2-dioxide herbicides

Publications (1)

Publication Number Publication Date
EP0901485A1 true EP0901485A1 (de) 1999-03-17

Family

ID=21777656

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97922598A Withdrawn EP0901485A1 (de) 1996-05-07 1997-05-01 1,2-benzoxathin- und thiepin 2,2-dioxid-herbizide

Country Status (4)

Country Link
EP (1) EP0901485A1 (de)
JP (1) JP2000509718A (de)
AU (1) AU2822697A (de)
WO (1) WO1997042185A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4290100A (en) * 1999-04-01 2000-10-23 Basf Aktiengesellschaft Tricyclic pyrazolone derivatives
AU3557800A (en) * 1999-04-01 2000-10-23 Basf Aktiengesellschaft Tricyclic cyclohexanedione derivatives
DE19935218A1 (de) 1999-07-27 2001-02-01 Aventis Cropscience Gmbh Isoxazolyl-substituierte Benzoylcyclohexandione, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Pflanzenwachstumsregulatoren

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634465A (en) * 1982-07-16 1987-01-06 Ciba-Geigy Corporation Fused N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'triazinylureas
US4589911A (en) * 1983-05-11 1986-05-20 Ciba-Geigy Corporation Fused N-phenylsulfonyl-N-triazinylureas
AU579369B2 (en) * 1984-05-07 1988-11-24 E.I. Du Pont De Nemours And Company Herbicidal sulfonamides
US4759791A (en) * 1985-06-18 1988-07-26 Ciba-Geigy Corporation N-heterocyclosulfonyl-N'-pyrimidinylureas
US4927450A (en) * 1986-11-28 1990-05-22 Ciba-Geigy Corporation N-heterocyclosulfonyl-n'-pyrimidinylureas
US5089046A (en) * 1988-04-04 1992-02-18 Sandoz Ltd. Aryl and heteroaryl diones
EP0337947A1 (de) * 1988-04-13 1989-10-18 Ciba-Geigy Ag Triazolylsulfonamide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9742185A1 *

Also Published As

Publication number Publication date
WO1997042185A1 (en) 1997-11-13
AU2822697A (en) 1997-11-26
JP2000509718A (ja) 2000-08-02

Similar Documents

Publication Publication Date Title
WO1997008164A1 (en) Bicyclic herbicides
US6172005B1 (en) Heteroaryl azole herbicides
WO1997046530A1 (en) Herbicidal pyridinyl and pyrazolylphenyl ketones
US5952266A (en) Herbicidal ketals and spirocycles
EP0862571B1 (de) Herbizide sulfonamide
US5985799A (en) Tricyclic herbicidal heterocycles
US6525001B1 (en) Substituted pyrimidine and pyridine herbicides
EP0902028A1 (de) Herbizide Tetrazoline
US5631210A (en) Herbicidal thiophene ketones
US5885936A (en) Heterotricyclic herbicides
US5739326A (en) Heterobicyclic herbicides
EP0901485A1 (de) 1,2-benzoxathin- und thiepin 2,2-dioxid-herbizide
EP0973764A1 (de) Bicyclische hydrazon herbizide
EP0946540A1 (de) Substituierte benzothiopyran salze und ihre verwendung als herbizide
WO1997003045A1 (en) Herbicidal sulfonamides
EP0863142A1 (de) Heterocyclische Herbizide
CA2281904A1 (en) Herbicidal pyrazoles
US20040033896A1 (en) Substituted pyrimidine and pyridine herbicides
EP0977760A1 (de) Herbizides sulfonamiden

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT PT

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19990920