WO1999028301A1 - Substituted pyrimidine and pyridine herbicides - Google Patents

Substituted pyrimidine and pyridine herbicides Download PDF

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Publication number
WO1999028301A1
WO1999028301A1 PCT/US1998/022088 US9822088W WO9928301A1 WO 1999028301 A1 WO1999028301 A1 WO 1999028301A1 US 9822088 W US9822088 W US 9822088W WO 9928301 A1 WO9928301 A1 WO 9928301A1
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Prior art keywords
ocf
uaj
haloalkyl
alkyl
methyl
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PCT/US1998/022088
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French (fr)
Inventor
Gerard Michael Koether
Thomas Paul Selby
Thomas Martin Stevenson
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E.I. Du Pont De Nemours And Company
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Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to CA2309260A priority Critical patent/CA2309260C/en
Priority to EP98952379A priority patent/EP1036066B1/en
Priority to AU98096/98A priority patent/AU9809698A/en
Priority to DE69837621T priority patent/DE69837621T2/en
Priority to US09/555,746 priority patent/US6525001B1/en
Publication of WO1999028301A1 publication Critical patent/WO1999028301A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

Definitions

  • This invention relates to certain pyrimidines and pyridines, their N-oxides, agriculturally suitable salts, compositions thereof, 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.
  • EP 723,960 discloses herbicidal substituted pyrimidines and pyridines of Formula i:
  • A is an optionally substituted aryl or 5- or 6-membered nitrogen containing heteroaromatic group
  • X is oxygen or sulfur
  • Z is nitrogen or CH;
  • R 1 .and R 2 are independently hydrogen, halogen, alkyl, haloalkyl, nitro or cyano; n is 0, 1 or 2; and m is 0 to 5.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation:
  • W is N or CR 11 ;
  • X, Y and Z are independently N or CR 12 ;
  • R 1 and R 2 are independently H, halogen, cyano, C1-C4 alkoxy, C j -C haloalkoxy, C 2 -C 4 alkoxyalkyl, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, S(O) n R 13 , C 2 -C 4 alkylthioalkyl, C 2 -C4 alkylsulfonylalkyl, C ] -C 4 alkylamino or C 2 -C dialkylamino; R 3 is H, F, Cl, Br, cyano, C r C 4 alkyl, C r C 4 haloalkyl or CO 2 R 14 ; R 4 is H, F, C r
  • R 5 is halogen, cyano, SF 5 , C1-C4 alkyl, Cj-C 4 haloalkyl, C 1 -C4 alkoxy, C1-C 4 haloalkoxy or S(O) n R 13 ;
  • R 6 and R 10 are independently H, halogen, cyano, Cj-C 4 alkyl, CJ-C4 haloalkyl, C1-C4 alkoxy, C ] -C 4 haloalkoxy or S(O) n R 13 ;
  • R 7 is halogen, cyano, SF 5 , C j -C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C r C 4 haloalkoxy or S(O) n R 13 ;
  • R 8 is C r C 4 alkyl or C r C 4 haloalkyl;
  • R 9 is H, halogen, cyano, SF 5 , C2-C4 alkoxy, C1-C 4 haloalkoxy, C1-C 4 alkyl, C j -C 4 haloalkyl, C -C alkenyl, C 2 -C4 alkynyl, C3-C4 alkenyloxy, C3-C 4 alkynyloxy or S(O) n Rl 3 ;
  • R 1 1 is H, halogen, cyano, C j -C 4 alkyl, C1-C 4 haloalkyl, C C4 alkoxy, C1-C 4 haloalkoxy or S(O) n R 13 ;
  • R 12 is H, halogen, cyano, C 1 -C4 alkyl, C 1 -C4 haloalkyl, C C 4 alkoxy, C 1 -C4 haloalkoxy or S(O) n R 13 ; each R
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, «-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 .
  • Alkenyloxy includes straight-chain or branched alkenyloxy moieties.
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 G ⁇ CCH 2 O and CH 3 G ⁇ CCH CH 2 O.
  • 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 .
  • Alkylsulfinyl includes both enantiomers of an alkylsulfmyl group.
  • alkylsulfmyl examples include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples 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.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • 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.
  • alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • C j -C The total number of carbon atoms in a substituent group is indicated by the "C j -C.” prefix where i and j are numbers from 1 to 4.
  • C j -C 3 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
  • C4 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 .
  • the compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof.
  • the compound 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). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • 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, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • R 1 and R 2 are independently H, C1-C4 alkyl or C 1 -C4 alkoxy;
  • R 5 and R 7 are independently halogen, C 1 -C 4 haloalkyl, C1-C4 haloalkoxy or
  • R 6 is H or F
  • R 8 is C r C 4 alkyl
  • R 9 is halogen, cyano, C ] -C 4 alkoxy, C1-C 4 haloalkoxy, C1-C4 alkyl, C ! -C haloalkyl or S(O) n R 13
  • R 10 is H, halogen, cyano or Cj-C haloalkyl
  • R 1 1 is H, halogen, cyano or C 1 -C4 haloalkyl
  • R 12 is H, halogen, cyano or C1-C4 haloalkyl
  • n is 0.
  • R 5 and R 7 are independently C 1 -C 4 haloalkyl or C1-C 4 haloalkoxy; and R 9 is halogen, C r C 4 haloalkoxy, C r C 4 haloalkyl or S(O) n R 13 .
  • Preferred 3 Compounds of Preferred 2 wherein
  • R 1 is CJ-C4 alkyl or C 1 -C4 alkoxy;
  • R 2 is H;
  • R3 and R4 are independently H, F or methyl
  • R 5 and R 7 are independently Cj-C 2 haloalkyl or C ] -C 2 haloalkoxy; and R 9 is C r C 2 haloalkoxy, C r C 2 haloalkyl or S(O) n R 13 .
  • R 5 and R 7 are independently C ⁇ -C 2 haloalkyl or C j -C 2 haloalkoxy; and R 9 is C r C 2 haloalkoxy, C r C 2 haloalkyl or S(O) n R 13 .
  • Preferred 7 Compounds of Preferred 5 wherein J is J-1 or J-5. Most preferred is the compound of Formula I selected from the group consisting of: (a) 5-ethyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[3-(trifluoromethyl)- lH-pyrazol-l-yl]pyrimidine;
  • 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 1-12.
  • the definitions of J, A, W, X, Y, Z, R 1 , R 2 , R 3 , R 4 , R 9 , R 10 , and R 14 in the compounds of Formulae 1-16 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae la-Ic are various subsets of the compounds of Formula I, and all substituents for Formulae la-Ic are as defined above for Formula I.
  • Scheme 1 illustrates the preparation of compounds of Formula la (Formula I wherein A is A-l).
  • Substituted heterocycles of Formula 1 (where L 1 is halogen) can be coupled with metalated aryls or heteroaryls of Formula 2 (where Met is Sn(alkyl) 3 , B(OH) 2 or Zn(L*) 2 ) in the presence of a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0) or in the presence of a palladium(II) catalyst such as dichlorobis(triphenylphosphine)- palladium(II) to provide compounds of Formula la.
  • a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0)
  • a palladium(II) catalyst such as dichlorobis(triphenylphosphine)- palladium(II)
  • Palladium(II) catalysts are generally used with a suitable base such as aqueous sodium bicarbonate or sodium carbonate.
  • suitable solvents for this coupling include NN-dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 20 °C to 130 °C.
  • Scheme 2 illustrates the preparation of compounds of Formula lb (Formula I wherein A is A-2).
  • Substituted heterocycles of Formula 1 are allowed to react with substituted azoles of Formula 3 in the presence of a suitable base such as an alkali carbonate, alkali hydroxide, or alkali hydride in a solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 °C to 130 °C to provide compounds of Formula lb.
  • a suitable base such as an alkali carbonate, alkali hydroxide, or alkali hydride
  • a solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran
  • Scheme 3 illustrates a method for preparing compounds of Formula Ic wherein J is an azole heterocycle of Formula J-7 and A is A-l or A-2.
  • Compounds of Formula 4 are allowed to react with an azole heterocycle of Formula 3 in a pro tic or aprotic solvent at temperatures ranging from 0 °C to 100 °C in the presence of a suitable base such an alkali carbonate, alkali hydroxide, or alkali hydride to provide compounds of Formula Ic.
  • a suitable base such an alkali carbonate, alkali hydroxide, or alkali hydride to provide compounds of Formula Ic.
  • Particularly suitable are potassium carbonate as base and acetonitrile or NN-dimethylformamide as solvent at a reaction temperature range of 20 °C to 80 °C.
  • Substituted pyrimidine intermediates of Formula 1 can be prepared by the method shown in Scheme 4.
  • a dihalopyrimidine of Formula 5 (where L 1 and L 2 are halogen) is coupled with a substituted alkyl zinc reagent of Formula 6 (where L 3 is halogen) in the presence of a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0) or in the presence of a palladium(II) catalyst such as dichloro-bis(triphenylphosphine)palladium(II).
  • a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0)
  • a palladium(II) catalyst such as dichloro-bis(triphenylphosphine)palladium(II).
  • Palladium(II) catalysts are generally used with a suitable base such as sodium bicarbonate or sodium carbonate.
  • suitable solvents for this coupling include NN-dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 0 °C to 130 °C.
  • Metalated aryls and heteroaryls of Formula 2 can be obtained commercially or can be prepared by methods known in the art: Sandosham, j. and Undheim, K. Tetrahedron (1994), 50, pp 275-284; Undheim, K. and Benneche, T. Acta Chemica Scandinavica (1993), 47, pp 102-121; Advances in Heterocyclic Chemistry; Katritzky, A.R., Ed.; Academic Press: New York, 1995; volume 62, pp 305-418.
  • Azoles of Formula 3 can be obtained commercially or can be prepared by methods known in the art Elguero, J. et al., Organic Preparations and Procedures Int. (1995), 27, pp 33-74; Comprehensive Heterocyclic Chemistry; Potts, K., Ed.; Pergamon Press: New York, 1984; volume 5, chapters 4.04 - 4J3; Heterocyclic Compounds; Elderfield, R., Ed.; John Wiley: New York, 1957; volume 5, chapters 2 and 4; Robinson, J. et al. J. Med. Chem., (1975), 18, pp 895-900; Evans, J.J. et al. U.S. Patent 4,038,405.
  • Dihaloheterocycles of Formula 5 can be obtained commercially or can be readily prepared by known methods in the art; for example, see Advances in Heterocyclic Chemistry; Katritzky, A.R., Ed.; Academic Press: New York, 1993; volume 58, pp 301-305; Heterocyclic Compounds; Elderfield, R.C., Ed.; John Wiley: New York, 1957; volume 6, chapter 7, pp 265-270.
  • Zinc reagents of Formula 6 can be made by the method shown in Scheme 5.
  • a substituted alkyl halide of Formula 7 (where L 3 is halogen) is allowed to react with activated zinc (see Jubert, C. and Knochel, P. J. Org. Chem. (1992), 57, p 5425; Knochel, P. and Singer, R. D. Chem. Rev. (1993), 93, p 2117) in a suitable solvent such as NN- dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 0 °C to 130 °C.
  • heterocyclic benzylic bromides of Formula 4 can be made by bromination of heterocycles of Formula 8 with bromine in an acidic solvent such as acetic acid at temperatures ranging from 20 °C to 100 °C (see, for example, Strekowski et al. /. Org. Chem. (1992), 56, p 5610).
  • Heterocycles of Formula 8 can be made from precursor heterocycles of Formula 9 as shown in Scheme 7.
  • the addition of lithium or Grignard reagents of formula R 3 R 4 CHLi or R 3 R 4 CHMgL 1 to heterocycles of Formula 9 is carried out in ethereal solvents such as ether or tetrahydrofuran at temperatures ranging from -70 °C to 30 °C.
  • the reaction mixture is worked up by the addition of water and an oxidizing agent.
  • a particularly suitable oxidizing agent is dichlorodicyanoquinone (DDQ). See Strekowski et al. J. Org. Chem. (1992), 56, p 5610 for examples of this synthetic method.
  • Heterocycles of Formula 9 can be prepared according to methods taught by Strekowski et al. J. Org. Chem. (1992), 56, p 5610; Bredereck et. al., Chem. Ber. (1960), 93, p 1208; Burdeska et al. Helv. Chim. Ada (1981), 64, p 113; Undheim, K. and Benneche, T. Advances in Heterocyclic Chemistry; Katritzky, A. R., Ed.; Academic Press: New York, 1995, volume 62, pp 305-418; and Comprehensive Heterocyclic Chemistry; Boulton, A.
  • Lithium and Grignard reagents of formulae R 3 R 4 CHLi or R 3 R 4 CHMgL 1 are commercially available or can be prepared by methods well known in the art.
  • This reaction is carried out in the presence of a strong base such as an alkali hydride, preferably sodium hydride, in solvents such as dichloromethane, dioxane, tetrahydrofuran, benzene, toluene or other aprotic solvent.
  • a strong base such as an alkali hydride, preferably sodium hydride
  • solvents such as dichloromethane, dioxane, tetrahydrofuran, benzene, toluene or other aprotic solvent.
  • the reaction may be carried out at temperatures between 0 and 120 °C.
  • a wide variety of azolium salts are known to catalyze this transformation; see, for example, Miyashita Heterocycles, (1996), 43, 509-512 and references cited therein.
  • a preferred catalyst is 1,3-dimethylimidazolium iodide.
  • L is halogen or alkylsulfonyl
  • a wide variety of reduction conditions can be utilized, but for reasons of ease of use and selectivity, alkali borohydrides are preferred reductants.
  • the reduction can be carried out at 0 to 100 °C in a variety of solvents which are inert to the action of borohydrides.
  • Especially preferred conditions are the use of sodium borohydride in ethanol at 0 to 25 °C.
  • compounds of Formula 1 wherein J is J-7 can also be made via the bromination of compounds of Formula 14 with molecular bromine in an acidic solvent such as acetic acid at temperatures ranging from 20 to 100 °C in the same way as previously described in Scheme 6.
  • the brominated products of Formula 15 can be displaced by heterocycles of Formula 3 in the presence of a base such as potassium carbonate as previously described for Scheme 2.
  • Compounds of Formula 14 are known in the literature or are commercially available. See Benneche (Acta Chemica Scandanavia, 1997, 51, 302) for preparation of these compounds from compounds of Formula 5.
  • Compounds of Formula I substituted with the group S(O) n R 13 wherein n is 1 or 2 can be prepared from compounds of Formula I substituted with said S(O) n R 13 group wherein n is 0 by treatment with an oxidizing reagent such as /w-chloroperoxybenzoic acid or Oxone ® (potassium peroxymonosulfate).
  • an oxidizing reagent such as /w-chloroperoxybenzoic acid or Oxone ® (potassium peroxymonosulfate).
  • the cooled reaction solution was decanted into a solution of 2,4-dichloro-5-methylpyrimidine (3.3 g, 20 mmol) and dichlorobis(triphenylphosphine)- palladium(II) (0.44 g, 0.63 mmol) stirring in 15 mL of tetrahydrofuran. Upon heating, the reaction mixture exothermed strongly again at 55 °C and was then heated to reflux. The reaction mixture was allowed to cool and partitioned between diethyl ether and water. The organic layer was separated, washed with 1 N aqueous hydrochloric acid and brine, dried over magnesium chloride and concentrated under reduced pressure to give a crude oil.
  • Step A Preparation of 5-methyl-4-[[3-(trifluoromethyl)phenyl]methylJ-2-[3-
  • Step A The title compound of Step A (9.0 g, 38 mmol) was dissolved in 50 mL of tetrahydrofuran and treated with methyl lithium (1.4 M in ether, 34 mL, 47 mmol) at a temperature of -70 °C. The reaction mixture exothermed to -35 °C. The mixture was stirred at -30 °C for 1.5 h and then treated with 1 mL of water and dichlorodicyanoquinone (9.44 g, 42 mmol). The mixture was stirred at 25 °C for 30 minutes and then partitioned twice between 100 mL of water and 100 mL of dichloromethane. The combined organics were washed with brine and dried over magnesium sulfate.
  • Step C Preparation of 4-bromomethyl-5-methyl-2-(4- trifluoromethylphenyl)pyrimidine
  • the title compound of Step B (2.0 g, 8 mmol) was dissolved in 10 mL of acetic acid and treated with bromine (0.4 mL, 8 mmol). The mixture was heated at 80 °C until the orange color was discharged (1 h). The mixture was evaporated under reduced pressure, diluted with 50 mL of ether and washed twice with 50 mL of sodium bicarbonate and then 50 mL of brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield 2.54 g of the title compound of Step C as a tan solid which was used immediately in the next step without further purification.
  • Step D Preparation of 5-methyl-2-(4-trifluoromethylphenyl)-4-[3-(trifluoromethyl)- lH-pyrazol- 1 -yljmethylpyrimidine
  • the title compound of Step C (0.7 g, 2 mmol), 3-trifluoromethylpyrazole (0.27 g, 2 mmol) and potassium carbonate (0.83 g, 6 mmol) were suspended in 10 mL of acetonitrile and heated to reflux for 1 h. The salts were filtered and the acetonitrile was removed under reduced pressure.
  • Step B Preparation of [5-methyl-2-[3-(trifluoromethyl)- lH-pyrazol- 1 -yl]-4- pyrimidinyl] [3 -(trifluoromethyl)phenyljmethanone
  • the title compound of Step A (0.6 g, 2 mmol), 3-trifluoromethylpyrazole (0.25 g), and potassium carbonate (0.8 g, 6 mmol) were suspended in acetonitrile (15 mL) and heated at reflux for 3 h. The cooled reaction mixture was filtered and the cake washed with acetonitrile.
  • Tj Tj Tj Tj ] Tj Tj j j Tj Tj Tj Tj Tl Tl ⁇ T, Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj
  • X and Y are N; Z is CH
  • Y is CH; X and Z are N
  • X, Y and Z are CH
  • X and Y are CH; Z is N
  • X is N; Y and Z are CH
  • X and Y are ; CH; Z is N
  • X, Y and Z are CH
  • X is N; Y and Z are CT I
  • X and Z are CH; Y is > J
  • X and Y are CH; Z is > I
  • X, Y and Z are CH
  • X is CH; Y and Z are N
  • X and Z are CH; Y is N
  • X and Y are CH; Z is N
  • X is CH; Y and Z are N
  • X and Z are : CH; Y is N
  • X and Y are ; CH; Z is N
  • X and Y are N; Z i s CH
  • X, Y and Z are CH
  • X, Y and Z are CH
  • X is N; Y and Z are CH
  • X and Y are CH; Z is N
  • X and Y are CH; Z is N
  • X and Y are N; Z is CH
  • X is CH; Y and Z are N
  • Y is CH; X and Z are N
  • X, Y and Z are CH
  • X is N; Y and Z are CH
  • X and Z are CH; Y is N
  • X and Y are CH; Z is N
  • X and Y are N; Z is CH
  • Y is CH; X and Z are N
  • X, Y and Z are CH
  • X is N; Y and Z are CH
  • X and Y are N; Z is CH
  • X is CH; Y and Z are N
  • Y is CH; X and Z are N
  • X, Y and Z are CH
  • X is N; Y and Z are ; CH
  • X and Z are CH; Y is N
  • X and Y are CH; Z is N
  • X and Y are N; Z is CH
  • X is CH; Y and Z are N
  • Y is CL [; X and Z are N
  • X, Y and Z are CH
  • X is N; Y and Z are ( H

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Abstract

Compounds of formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation, wherein J is (J-1), (J-2), (J-3), (J-4), (J-5), (J-6) or (J-7); and J, W, X, Y, Z, A, R1-R8 are as defined in the disclosure. Also disclosed are compositions containing the compounds of formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of formula (I).

Description

TITLE SUBSTITUTED PYRIMIDLNE AND PYRIDINE HERBICIDES BACKGROUND OF THE INVENTION This invention relates to certain pyrimidines and pyridines, their N-oxides, agriculturally suitable salts, compositions thereof, 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.
EP 723,960 discloses herbicidal substituted pyrimidines and pyridines of Formula i:
Figure imgf000003_0001
wherein, inter alia,
A is an optionally substituted aryl or 5- or 6-membered nitrogen containing heteroaromatic group;
X is oxygen or sulfur;
Z is nitrogen or CH; R1 .and R2 are independently hydrogen, halogen, alkyl, haloalkyl, nitro or cyano; n is 0, 1 or 2; and m is 0 to 5.
The pyrimidines .and pyridines of the present invention are not disclosed in this reference. SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation:
Figure imgf000004_0001
wherein
Figure imgf000004_0002
J-1 J-2 J-3 J-4
Figure imgf000004_0003
J-5 J-6 J-7
A
Figure imgf000004_0004
A-l A-2
W is N or CR11;
X, Y and Z are independently N or CR12;
R1 and R2 are independently H, halogen, cyano, C1-C4 alkoxy, Cj-C haloalkoxy, C2-C4 alkoxyalkyl, CrC4 alkyl, CrC4 haloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy, S(O)nR13, C2-C4 alkylthioalkyl, C2-C4 alkylsulfonylalkyl, C]-C4 alkylamino or C2-C dialkylamino; R3 is H, F, Cl, Br, cyano, CrC4 alkyl, CrC4 haloalkyl or CO2R14; R4 is H, F, CrC4 alkyl, OH or OR14; R3 and R4 can be taken together with the carbon to which they are attached to form
C(=O) or C(=NOR14); R5 is halogen, cyano, SF5, C1-C4 alkyl, Cj-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or S(O)nR13; R6 and R10 are independently H, halogen, cyano, Cj-C4 alkyl, CJ-C4 haloalkyl, C1-C4 alkoxy, C ] -C4 haloalkoxy or S(O)nR 13 ;
R7 is halogen, cyano, SF5, Cj-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, CrC4 haloalkoxy or S(O)nR13; R8 is CrC4 alkyl or CrC4 haloalkyl;
R9 is H, halogen, cyano, SF5, C2-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkyl, Cj-C4 haloalkyl, C -C alkenyl, C2-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy or S(O)nRl3; R1 1 is H, halogen, cyano, Cj-C4 alkyl, C1-C4 haloalkyl, C C4 alkoxy, C1-C4 haloalkoxy or S(O)nR13; R12 is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C C4 alkoxy, C1-C4 haloalkoxy or S(O)nR13; each R13 is independently Cj-C4 alkyl or C1-C4 haloalkyl; each R14 is independently C1-C4 alkyl; and each n is independently 0, 1 or 2.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, «-propyl, -propyl, or the different butyl, pentyl or hexyl isomers. The term "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 CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C-CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH2=CHCH2CH O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3G≡CCH2O and CH3G≡CCH CH2O. "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 CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylsulfinyl" includes both enantiomers of an alkylsulfmyl group. Examples of "alkylsulfmyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3) CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(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. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "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 F3C, C1CH2, CF3CH2 and CF3CC12. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O.
The total number of carbon atoms in a substituent group is indicated by the "Cj-C." prefix where i and j are numbers from 1 to 4. For example, Cj-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a group contains a substituent which can be hydrogen, for example R9, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
The compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof. The compound of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that 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). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
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, tartaric, 4-toluenesulfonic or valeric acids.
Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, geometric or stereoisomers thereof,
N-oxides thereof and agriculturally-suitable salts thereof, wherein R1 and R2 are independently H, C1-C4 alkyl or C1-C4 alkoxy; R5 and R7 are independently halogen, C1-C4 haloalkyl, C1-C4 haloalkoxy or
S(O)nRl3; R6 is H or F; R8 is CrC4 alkyl; R9 is halogen, cyano, C]-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkyl, C!-C haloalkyl or S(O)nR13; R10 is H, halogen, cyano or Cj-C haloalkyl; R1 1 is H, halogen, cyano or C1-C4 haloalkyl; R12 is H, halogen, cyano or C1-C4 haloalkyl; and n is 0.
Preferred 2. Compounds of Preferred 1 wherein W is N;
R5 and R7 are independently C1-C4 haloalkyl or C1-C4 haloalkoxy; and R9 is halogen, CrC4 haloalkoxy, CrC4 haloalkyl or S(O)nR13. Preferred 3. Compounds of Preferred 2 wherein
R1 is CJ-C4 alkyl or C1-C4 alkoxy; R2 is H;
R3 and R4 are independently H, F or methyl;
R5 and R7 are independently Cj-C2 haloalkyl or C]-C2 haloalkoxy; and R9 is CrC2 haloalkoxy, CrC2 haloalkyl or S(O)nR13.
Preferred 4. Compounds of Preferred 3 wherein
J is J-1, J-5 or J-7. Preferred 5. Compounds of Preferred 2 wherein
R3 and R4 can be taken together with the carbon to which they are attached to form C(=O).
Preferred 6. Compounds of Preferred 5 wherein R1 is C C4 alkyl or C1-C4 alkoxy; R2 is H;
R5 and R7 are independently Cι-C2 haloalkyl or Cj-C2 haloalkoxy; and R9 is CrC2 haloalkoxy, CrC2 haloalkyl or S(O)nR13.
Preferred 7. Compounds of Preferred 5 wherein J is J-1 or J-5. Most preferred is the compound of Formula I selected from the group consisting of: (a) 5-ethyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[3-(trifluoromethyl)- lH-pyrazol-l-yl]pyrimidine;
(b) 5-ethyl-4-[[3-(trifluoromethyl)phenyl]methyl]-2-[3-(trifluoromethyl)-lH- pyrazol- 1 -yljpyrimidine; (c) 5-methyl-2-[4-(trifluoromethyl)phenyl]-4-[[3- (trifluoromethyl)phenyl]methyl]pyrimidine; (d) 5-methyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[4- (trifluoromethyl)phenyl]pyrimidine; (e) 5-methyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[3-(trifluoromethyl)- lH-pyrazol- 1 -yljpyrimidine;
(f) [5-methyl-2-[4-(trifIuoromethyl)phenyl]-4-pyrimidinyl] [3-
(trifluoromethyl)phenyl]methanone;
(g) [5-methyl-2-[3-(trifluoromethyl)-lH-pyrazol-l-yl]-4-pyrimidinyl][3- (trifluoromethyl)phenyl]methanone; and
(h) 5-methyl-4-[[3-(trifluoromethyl)phenyl]-2-[3-(trifluoromethyl)-lH- pyrazol- 1 -yljpyrimidine. This invention also relates to herbicidal 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. 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.
DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-12. The definitions of J, A, W, X, Y, Z, R1, R2, R3, R4, R9, R10, and R14 in the compounds of Formulae 1-16 below are as defined above in the Summary of the Invention. Compounds of Formulae la-Ic are various subsets of the compounds of Formula I, and all substituents for Formulae la-Ic are as defined above for Formula I.
Scheme 1 illustrates the preparation of compounds of Formula la (Formula I wherein A is A-l). Substituted heterocycles of Formula 1 (where L1 is halogen) can be coupled with metalated aryls or heteroaryls of Formula 2 (where Met is Sn(alkyl)3, B(OH)2 or Zn(L*)2) in the presence of a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0) or in the presence of a palladium(II) catalyst such as dichlorobis(triphenylphosphine)- palladium(II) to provide compounds of Formula la. Palladium(II) catalysts are generally used with a suitable base such as aqueous sodium bicarbonate or sodium carbonate. Suitable solvents for this coupling include NN-dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 20 °C to 130 °C. Scheme 1
Figure imgf000010_0001
1 A is halogen) la
Scheme 2 illustrates the preparation of compounds of Formula lb (Formula I wherein A is A-2). Substituted heterocycles of Formula 1 are allowed to react with substituted azoles of Formula 3 in the presence of a suitable base such as an alkali carbonate, alkali hydroxide, or alkali hydride in a solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 °C to 130 °C to provide compounds of Formula lb.
Scheme 2
Figure imgf000010_0002
lb
Scheme 3 illustrates a method for preparing compounds of Formula Ic wherein J is an azole heterocycle of Formula J-7 and A is A-l or A-2. Compounds of Formula 4 are allowed to react with an azole heterocycle of Formula 3 in a pro tic or aprotic solvent at temperatures ranging from 0 °C to 100 °C in the presence of a suitable base such an alkali carbonate, alkali hydroxide, or alkali hydride to provide compounds of Formula Ic. Particularly suitable are potassium carbonate as base and acetonitrile or NN-dimethylformamide as solvent at a reaction temperature range of 20 °C to 80 °C. Scheme 3
base, solvent
Figure imgf000011_0002
Figure imgf000011_0001
Substituted pyrimidine intermediates of Formula 1 (wherein J is J-1 to J-6) can be prepared by the method shown in Scheme 4. By the synthetic protocol of Menta, E. and Oliva, A. J. Heterocyclic Chem. (1997), 34, p 27, a dihalopyrimidine of Formula 5 (where L1 and L2 are halogen) is coupled with a substituted alkyl zinc reagent of Formula 6 (where L3 is halogen) in the presence of a palladium(O) catalyst such as tetrakis(triphenylphosphine)palladium(0) or in the presence of a palladium(II) catalyst such as dichloro-bis(triphenylphosphine)palladium(II). Palladium(II) catalysts are generally used with a suitable base such as sodium bicarbonate or sodium carbonate. Suitable solvents for this coupling include NN-dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 0 °C to 130 °C.
Scheme 4
Figure imgf000011_0003
Metalated aryls and heteroaryls of Formula 2 can be obtained commercially or can be prepared by methods known in the art: Sandosham, j. and Undheim, K. Tetrahedron (1994), 50, pp 275-284; Undheim, K. and Benneche, T. Acta Chemica Scandinavica (1993), 47, pp 102-121; Advances in Heterocyclic Chemistry; Katritzky, A.R., Ed.; Academic Press: New York, 1995; volume 62, pp 305-418.
Azoles of Formula 3 can be obtained commercially or can be prepared by methods known in the art Elguero, J. et al., Organic Preparations and Procedures Int. (1995), 27, pp 33-74; Comprehensive Heterocyclic Chemistry; Potts, K., Ed.; Pergamon Press: New York, 1984; volume 5, chapters 4.04 - 4J3; Heterocyclic Compounds; Elderfield, R., Ed.; John Wiley: New York, 1957; volume 5, chapters 2 and 4; Baldwin, J. et al. J. Med. Chem., (1975), 18, pp 895-900; Evans, J.J. et al. U.S. Patent 4,038,405.
Dihaloheterocycles of Formula 5 can be obtained commercially or can be readily prepared by known methods in the art; for example, see Advances in Heterocyclic Chemistry; Katritzky, A.R., Ed.; Academic Press: New York, 1993; volume 58, pp 301-305; Heterocyclic Compounds; Elderfield, R.C., Ed.; John Wiley: New York, 1957; volume 6, chapter 7, pp 265-270.
Zinc reagents of Formula 6 can be made by the method shown in Scheme 5. A substituted alkyl halide of Formula 7 (where L3 is halogen) is allowed to react with activated zinc (see Jubert, C. and Knochel, P. J. Org. Chem. (1992), 57, p 5425; Knochel, P. and Singer, R. D. Chem. Rev. (1993), 93, p 2117) in a suitable solvent such as NN- dimethylformamide, dimethoxyethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 0 °C to 130 °C.
Scheme 5
L activated zinc
R 'X3/ .R4 solvent
As shown in Scheme 6, heterocyclic benzylic bromides of Formula 4 can be made by bromination of heterocycles of Formula 8 with bromine in an acidic solvent such as acetic acid at temperatures ranging from 20 °C to 100 °C (see, for example, Strekowski et al. /. Org. Chem. (1992), 56, p 5610).
Scheme 6
Figure imgf000012_0001
Heterocycles of Formula 8 can be made from precursor heterocycles of Formula 9 as shown in Scheme 7. The addition of lithium or Grignard reagents of formula R3R4CHLi or R3R4CHMgL1 to heterocycles of Formula 9 is carried out in ethereal solvents such as ether or tetrahydrofuran at temperatures ranging from -70 °C to 30 °C. The reaction mixture is worked up by the addition of water and an oxidizing agent. A particularly suitable oxidizing agent is dichlorodicyanoquinone (DDQ). See Strekowski et al. J. Org. Chem. (1992), 56, p 5610 for examples of this synthetic method.
Scheme 7
R3R4CHLi orR3R4CHMgL1 solvent oxidizing agent
Figure imgf000013_0001
9
Heterocycles of Formula 9 can be prepared according to methods taught by Strekowski et al. J. Org. Chem. (1992), 56, p 5610; Bredereck et. al., Chem. Ber. (1960), 93, p 1208; Burdeska et al. Helv. Chim. Ada (1981), 64, p 113; Undheim, K. and Benneche, T. Advances in Heterocyclic Chemistry; Katritzky, A. R., Ed.; Academic Press: New York, 1995, volume 62, pp 305-418; and Comprehensive Heterocyclic Chemistry; Boulton, A. J., and McKillop, A., Eds.; Pergamon Press: New York, 1984; volume 3, chapter 2.13. Lithium and Grignard reagents of formulae R3R4CHLi or R3R4CHMgL1 are commercially available or can be prepared by methods well known in the art. Compounds of Formula 1 (wherein R3 and R4 are taken together as C(=O)) can be prepared by the condensation of pyrimidines and pyridines of Formula 10 with aldehydes of Formula 11 in the presence of an imidazolium catalyst of Formula 12 as shown in Scheme 8. This reaction is carried out in the presence of a strong base such as an alkali hydride, preferably sodium hydride, in solvents such as dichloromethane, dioxane, tetrahydrofuran, benzene, toluene or other aprotic solvent. The reaction may be carried out at temperatures between 0 and 120 °C. A wide variety of azolium salts are known to catalyze this transformation; see, for example, Miyashita Heterocycles, (1996), 43, 509-512 and references cited therein. A preferred catalyst is 1,3-dimethylimidazolium iodide.
Figure imgf000014_0001
10 11 12
L is halogen or alkylsulfonyl
Compounds of Formula I (wherein R3 and R4 are taken together as C(=NOR1 )) can be formed directly from compounds of Formula I (wherein R3 and R4 are taken together as
C(=O)) by the action of hydroxylamine or capped hydroxylamine salts of Formula 13 as shown in Scheme 9. Many hydroxylamines are commercially available as acid salts and are freed by the action of a base in the presence of the ketone of Formula I. Suitable bases include alkali carbonates, acetates, and hydroxides. These reactions are best carried out in protic solvents, such as lower alcohols, at temperatures between 0 and 120 °C. Especially preferred conditions use sodium carbonate or sodium acetate as base in ethanol at 70 to
80 °C.
Scheme 9 base
NH2OR14-HX
(wherein R3and R4 (wherein R3 and R4 are taken together X is halogen are taken together
88 ^"^ as C(=NOR14))
13
Compounds of Formula I (wherein R3 is OH and R4 is H) can be made by the reduction of ketones of Formula I (wherein R3 and R4 are taken together as C(=O)) as shown in Scheme 10. A wide variety of reduction conditions can be utilized, but for reasons of ease of use and selectivity, alkali borohydrides are preferred reductants. The reduction can be carried out at 0 to 100 °C in a variety of solvents which are inert to the action of borohydrides. Especially preferred conditions are the use of sodium borohydride in ethanol at 0 to 25 °C.
Scheme 10
I + Z+(BH )" *• I
(wherein R3 and R (wherein R3 is OH are taken together z is an alkali metal and R4 is H) as C(=0)) As shown in Scheme 11, compounds of Formula 1 wherein J is J-7 can also be made via the bromination of compounds of Formula 14 with molecular bromine in an acidic solvent such as acetic acid at temperatures ranging from 20 to 100 °C in the same way as previously described in Scheme 6. The brominated products of Formula 15 can be displaced by heterocycles of Formula 3 in the presence of a base such as potassium carbonate as previously described for Scheme 2. Compounds of Formula 14 are known in the literature or are commercially available. See Benneche (Acta Chemica Scandanavia, 1997, 51, 302) for preparation of these compounds from compounds of Formula 5.
Scheme 11
en
Figure imgf000015_0001
14 15
Compounds of Formula 1 in which R- is cyano can be made as shown in Scheme 12. The reaction of acetonitrile derivatives of formula 16 with compounds of Formula 5 in the presence of a base gives compounds of formula 1 with a cyano group. The reaction can be carried out in a variety of solvents such as dimethylformamide, tetrahydrofuran, or other solvents inert to strong bases. A wide variety of bases which can deprotonate substituted acetonitriles can be used. Sodium hydride and potassium t-butoxide are preferred due to their ease of use and availability. The reaction can be carried out at temperatures ranging from 0 to 100 °C. Compounds of formula 16 are well known in the literature and many are commercially available
Scheme 12
l)
Figure imgf000015_0002
(wherein W is TJ) 16
Compounds of Formula I substituted with the group S(O)nR13 wherein n is 1 or 2 can be prepared from compounds of Formula I substituted with said S(O)nR13 group wherein n is 0 by treatment with an oxidizing reagent such as /w-chloroperoxybenzoic acid or Oxone® (potassium peroxymonosulfate). This type of oxidation reaction is well known in the art; for example, see March, J. Advanced Organic Chemistry; John Wiley: New York, 1992; 4th edition, pp 1201-1203.
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. !H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet.
EXAMPLE 1 Step A: Preparation of 2-chloro-5-methyl-4-[[3- (trifluoromethyl)phenyl]methyl]pyrimidine
To a suspension of zinc dust (2.5 g, 38 mmol) stirred in 25 mL of tetrahydrofuran were added 2 drops of 1,2-dibromoethane and the mixture was heated to reflux. The suspension was then cooled and 2 drops of trimethylsilyl chloride were added followed by portionwise addition of 3-(trifluoromethyl)benzyl bromide (6.0 g, 25 mmol) with heating. When the reaction temperature reached 55 °C, a strong exotherm occurred and the reaction mixture was allowed to heat at reflux. The cooled reaction solution was decanted into a solution of 2,4-dichloro-5-methylpyrimidine (3.3 g, 20 mmol) and dichlorobis(triphenylphosphine)- palladium(II) (0.44 g, 0.63 mmol) stirring in 15 mL of tetrahydrofuran. Upon heating, the reaction mixture exothermed strongly again at 55 °C and was then heated to reflux. The reaction mixture was allowed to cool and partitioned between diethyl ether and water. The organic layer was separated, washed with 1 N aqueous hydrochloric acid and brine, dried over magnesium chloride and concentrated under reduced pressure to give a crude oil. Purification by flash chromatography on silica gel (15 to 25% ethyl acetate in hexane) yielded 2.4 g of the title compound of Step A as an oil. lH NMR (CDC13): δ 8.35 (s, 1H), 7.60-7.35 (m, 4H), 4J5 (s, 2H), 2.25 (s, 3H).
Step B: Preparation of 5-methyl-2-[4-(trifluoromethyl)phenyl]-4-[[3-
(trifluoromethyl)phenyl]methyl]pyrimidine A stirred mixture of 4-(trifluoromethyl)benzene boronic acid (430 mg, 2.3 mmol), the title compound of Step A (500 mg, 1.7 mmol), dichlorobis(triphenylphosphine)palladium(II) (120 mg, 0J7 mmol) and sodium carbonate (550 mg, 5.2 mmol) in a mixture of 6 mL of water and 2 mL of tetrahydrofuran was heated at reflux for 1.5 h. The reaction mixture was then partitioned between diethyl ether and water. The organic layer was separated, washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. Flash chromatography on silica gel (20 to 25% ethyl acetate in hexane) followed by trituration with 10% diethyl ether in hexane afforded 350 mg of the title compound of Step B, a compound of this invention, as a yellow-tinted solid melting at 112-113 °C. *H NMR (CDC13): δ 8.55 (m, 3H), 7J0 (d, 2H), 7.60 (s, 1H), 7.55-7.40 (m, 3H), 4.25 (s, 2H), 2.30 (s, 3H). EXAMPLE 2
Step A: Preparation of 5-methyl-4-[[3-(trifluoromethyl)phenyl]methylJ-2-[3-
(trifluoromethyl)- lH-pyrazol- 1 -yljpyrimidine A stirred mixture of 3-(trifluoromethyl)pyrazole (390 mg, 2.9 mmol), the title compound of Step A in Example 1 (750 mg, 2.6 mmol), and powdered potassium carbonate (1.1 g, 7.9 mmol) in 10 mL of NN-dimethylformamide was heated at 60 °C for 3 h followed by heating at 80 °C for 1 h. The reaction mixture was then partitioned between diethyl ether and water. The organic layer was separated, washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. Column chromatography on silica gel (5% diethyl ether in 1-chlorobutane) afforded 210 mg of the title compound of Step A as an oil which solidified to a white solid melting at 90-92 °C. !Η ΝMR (CDC13): δ 8.55 (t,2H), 7.55-7.50 (m, 2H), 7.45-7.40 (m, 2H), 6.72 (d, 1H), 4.26 (s, 2H), 2.32 (s, 3H).
EXAMPLE 3 Step A: Preparation of 5-methyl-2-(4-trifluoromethylphenyl)pyrimidine
A sample of 4-trifluoromethylbenzamidine hydrochloride dihydrate (Maybridge, 15.2 g, 58 mmol) was dissolved in 100 mL of methanol and 3-ethoxy-2-methylacrolein (Janssen, 7.8 g, 64 mmol) was added. Sodium methoxide (25% solution in methanol, 14.7 mL) was added and the mixture was heated at 50 °C for 3 h. The cooled reaction mixture was then added to 500 ml of ice water and stirred for 30 minutes. The white solid was filtered, air dried, dissolved in 300 mL of dichloromethane and dried over magnesium sulfate. The solvent was removed under reduced pressure to yield, after trituration with hexanes, 12.5 g of the product as a white solid melting at 143-146 °C. lH NMR (CDCI3): δ 2.37 (s, 3H), 7.73 (d, 2H), 8.53 (d, 2H), 8.66 (s, 2H). Step B: Preparation of 4,5-dimethyl-2-(4-trifluoromethylphenyl)pyrimidine
The title compound of Step A (9.0 g, 38 mmol) was dissolved in 50 mL of tetrahydrofuran and treated with methyl lithium (1.4 M in ether, 34 mL, 47 mmol) at a temperature of -70 °C. The reaction mixture exothermed to -35 °C. The mixture was stirred at -30 °C for 1.5 h and then treated with 1 mL of water and dichlorodicyanoquinone (9.44 g, 42 mmol). The mixture was stirred at 25 °C for 30 minutes and then partitioned twice between 100 mL of water and 100 mL of dichloromethane. The combined organics were washed with brine and dried over magnesium sulfate. The residue after evaporation was subjected to silica gel chromatography using hexanes/ethyl acetate (95:5) as eluent to give 9.02 g of the title compound of Step B as a white solid melting at 128-131 °C. *H NMR (CDCI3): δ 2.31 (s, 3H), 2.56 (s, 3H), 7.71 (d, 2H), 8.49 (d, 2H), 8.53 (s, 1H). Step C: Preparation of 4-bromomethyl-5-methyl-2-(4- trifluoromethylphenyl)pyrimidine The title compound of Step B (2.0 g, 8 mmol) was dissolved in 10 mL of acetic acid and treated with bromine (0.4 mL, 8 mmol). The mixture was heated at 80 °C until the orange color was discharged (1 h). The mixture was evaporated under reduced pressure, diluted with 50 mL of ether and washed twice with 50 mL of sodium bicarbonate and then 50 mL of brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield 2.54 g of the title compound of Step C as a tan solid which was used immediately in the next step without further purification. ^H NMR (CDCI3): δ 2.44 (s, 3H), 4.54 (s, 2H), 7.74 (d, 2H), 8.56 (d, 2H), 8.62 (s, 1H).
Step D: Preparation of 5-methyl-2-(4-trifluoromethylphenyl)-4-[3-(trifluoromethyl)- lH-pyrazol- 1 -yljmethylpyrimidine The title compound of Step C (0.7 g, 2 mmol), 3-trifluoromethylpyrazole (0.27 g, 2 mmol) and potassium carbonate (0.83 g, 6 mmol) were suspended in 10 mL of acetonitrile and heated to reflux for 1 h. The salts were filtered and the acetonitrile was removed under reduced pressure. The residue was purified by chromatography on silica gel eluting with hexanes/ethyl acetate (85:15) to afford 0.52 g of the title compound of Step D, a compound of this invention, as a white solid melting at 112-114 °C. *H NMR (CDCI3): δ 2.39 (s, 3Η), 5.53 (s, 2H), 6.62 (d, 1H), 7.6-7.8 (m, 3H), 8.44 (d, 2H), 8.6 (s, 1H). EXAMPLE 4 Step A: Preparation of (2-chloro-5-methyl-4-pyrirnidinyl)[3-
(trifluoromethyl)phenyljmethanone 2,4-Dichloro-5-methylpyrimidine (3.6 g, 18.4 mmol) was dissolved in dichloromethane (50 mL) and treated sequentially with 3-trifluoromethylbenzaldehyde (3.3 g, 18.4 mmol), and 1,3-dimethylimidazolium iodide (1.37 g, 6.2 mmol). Sodium hydride (0J4 g, 18.4 mmol) was added and an exotherm was noted. After being heated at reflux for 3h, the reaction was quenched with water and the layers were separated. The dried (magnesium sulfate) organic layer was purified by chromatography on silica gel using hexanes/ethyl acetate 85:15 as eluent. The title compound of Step A (1.8 g) was isolated as a white solid melting at 113-116 °C. Η NMR (CDCl3/200 MHz) 2.39 (s, 3H), 7.66 (m, 1H), 7.90 (d, 1H), 8.07 (sJH), 8.69 (s, 1H).
Step B: Preparation of [5-methyl-2-[3-(trifluoromethyl)- lH-pyrazol- 1 -yl]-4- pyrimidinyl] [3 -(trifluoromethyl)phenyljmethanone The title compound of Step A (0.6 g, 2 mmol), 3-trifluoromethylpyrazole (0.25 g), and potassium carbonate (0.8 g, 6 mmol) were suspended in acetonitrile (15 mL) and heated at reflux for 3 h. The cooled reaction mixture was filtered and the cake washed with acetonitrile. After evaporation of the solvent under reduced pressure, the residue was subjected to silica gel chromatography using hexanes/ethyl acetate (85:15) to give 0J2 g of the title compound of Step B, a compound of the invention, as a white solid. !Η NMR
(CDCl3/200 MHz) 2.45 (s, 3H), 6J5 (d, 1H), 7.67 (d, 1H), 7.92 (d, 1H), 8J0 (s, 1H), 8.27 (s, 1H), 8.54 (d, 1H), 8.9 (s, 1H).
EXAMPLE 5 Step A: Preparation of [5-methyl-2-[4-(trifluoromethyl)phenyl]-4-pyrimidinyl] [3- (trifluoromethyl)phenyljmethanone
The title compound of Example 1, Step A (0.6 g, 2 mmol), 4-trifluoromethyl- benzeneboronic acid (1J g, 6 mmol), and bis(triphenylphosphine)palladium dichloride were dissolved in dimethoxyethane (15 mL) and aqueous sodium carbonate (2 M, 4 mmol). The resulting mixture was heated at 80 °C for 3 h. The mixture was diluted with dichloromethane (50 mL) and water (50 mL). The dichloromethane layer was dried over magnesium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel chromatography using hexanes/ethyl acetate (85: 15). The title compound of Step A, a compound of the invention, was isolated as a white solid (0.56 g) melting at 159-161 °C. !H NMR (CDCl3/200 MHz) 2.47 (s, 3H), 1.62-1.18 (m, 3H), 7.94 (d, 1H), 8J7 (d, 1H), 8.34 (s, 1H), 8.5 (d, 2H), 8.9 (s, 1H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 34 can be prepared. Table 1
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Figure imgf000026_0001
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Tj Tj Tj r Tj Tj j Tj Tj Tj Tj Tj Tj j Tj Tj Tj Tj Tj Tj Tj I* O O O O O O O O O O O O
00 CΛ CΛ CΛ CΛ CΛ CΛ O O O O CΛ 00 CΛ 00 00 CΛ n CΛ CΛ 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 J τι τι o O O O aτι a Tl aτi 3, a Tl T al a TJ a T| a TJ a T| a TJ a T| a Tl aJ q UJ ■ - 12 a TJ a TJ a Tl a TJ a Tl a T a aJ a TJ a TJ a TJ a TJ to τι o to t to to to to to to to to to to to to to to to to to o to to IO to to
Figure imgf000030_0001
O o O O O O O O O to a to a to a N to a t a to a to a 0
^H W W W S S M W W S W M ^ W M W HH W K W M M W */ . to a to a IO a to a to a 4
O O O O O O O O O O O O
U aJ aJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ aJ U aJ
TI Tj 4--| -rJ Tl Tl T| I* O O O O O O O O O O O
CΛ oo 00 00 CΛ 00 CΛ CΛ O O O O O O O O .. . CΛ CΛ CΛ CΛ O O O Tl o ol o Tl T| TI O O O O O O O O O 2
Tl T Tl o o o o o o o o o o o o
UJ UJ UJ ω UJ UJ UJ
Figure imgf000030_0002
Figure imgf000031_0001
j Tj j Tj Tj τj j Tj Tj Tj Tj Tj Tj τι τι τι τι τι T] T] Hj| H| J
Figure imgf000031_0002
Oo oo Oo Oo O O O
U aJ U aJ U aJ U aJ U aJ U aJ
Figure imgf000031_0003
Tj Tj ] Tj Tj j j j Tj Tj Tj Tj Tl Tl τι T, Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj Tj
Figure imgf000031_0004
Figure imgf000032_0001
to to a ιo a to a IOa toa toa o a to a to a to a to a ta t a to a o to a to a to a to a
Figure imgf000032_0002
J Tj *τl Tj Tj Tj Tj TJ TJ TJ TJ TJ Tl 4τj TJ Tj Tj Tj j Tj Tj Tj j Tj Tj Tj
CΛ CΛ CΛ CΛ CΛ 00 o o o o o o o o o CΛ CΛ O O O O O O O O
Tl o T| o Tl τι Tl τι Q O O O O O O O O O O O O O O O O O o TI o TJ o Tl
UJ UJ UJ UJ UJ UJ
Figure imgf000032_0003
Table 2
Figure imgf000033_0001
Figure imgf000034_0001
CF3 CF3
CF3 OCF3
OCF3 CF3
Figure imgf000034_0002
OCF3 OCF3
Table 3
Figure imgf000034_0003
X and Y are N; Z is CH
Figure imgf000034_0004
CH2CH3 CF3 CF3 CH3 CF3 CF3 CH2CH3 CF3 OCF3 CH3 CF3 OCF3 CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000035_0001
X and Y are CH; Z is N
Rl R5 R9 Ri R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000036_0001
Rl R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
Rl R5 R9 R-- R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000036_0002
Table 5
Figure imgf000037_0001
Figure imgf000038_0001
Table 6
Figure imgf000038_0002
Figure imgf000039_0001
Table 7
Figure imgf000039_0002
X, Y and Z are CH
Figure imgf000039_0003
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N X is N; Y and Z are CH
Figure imgf000040_0001
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X and Y are CH; Z is N
Figure imgf000040_0002
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N ' CH
CH2CH3 OCF3 OCF3 N N
Figure imgf000041_0001
o o
(J Tj t Tj
Figure imgf000041_0002
Figure imgf000041_0003
oa Z Z oa oa z z oa oa z z oa oa z z Ω Ω z I
CH3 CF3 CF3 N CH CH
CH3 CF3 CF3 CH N N
CH3 CF3 OCF3 CH CH N
CH3 CF3 OCF3 CH N CH
CH3 CF3 OCF3 N CH CH
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH CH N
CH3 OCF3 CF3 CH N CH
CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
CH3 OCF3 OCF3 CH N CH
CH3 OCF3 OCF3 N CH CH
CH3 OCF3 OCF3 CH N N
X is N; Y and Z are CH
Rl R7 R9 X γi Zl
CH2CH3 CF3 CF3 CH CH N
CH2CH3 CF3 CF3 CH N CH
CH2CH3 CF3 CF3 N CH CH
CH2CH3 CF3 CF3 CH N N
CH2CH3 CF3 OCF3 CH CH N
CH2CH3 CF3 OCF3 CH N CH
CH2CH3 CF3 OCF3 N CH CH
CH2CH3 CF3 OCF3 CH N N
CH2CH3 OCF3 CF3 CH CH N
CH2CH3 OCF3 CF3 CH N CH
CH2CH3 OCF3 CF3 N CH CH
CH2CH3 OCF3 CF3 CH N N
CH2CH3 OCF3 OCF3 CH CH N
CH2CH3 OCF3 OCF3 CH N CH
CH2CH3 OCF3 OCF3 N CH CH
CH2CH3 OCF3 OCF3 CH N N
CH3 CF3 CF3 CH CH N
CH3 CF3 CF3 CH N CH
CH3 CF3 CF3 N CH CH
CH3 CF3 CF3 CH N N
CH3 CF3 OCF3 CH CH N CH3 CF3 OCF3 CH N CH
CH3 CF3 OCF3 N CH CH
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH CH N
CH3 OCF3 CF3 CH N CH
CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
CH3 OCF3 OCF3 CH N CH
CH3 OCF3 OCF3 N CH CH
CH3 OCF3 OCF3 CH N N
X and Y are ; CH; Z is N
Rl R7 R9 Xl γi Zl
CH2CH3 CF3 CF3 CH CH N
CH2CH3 CF3 CF3 CH N CH
CH2CH3 CF3 CF3 N CH CH
CH2CH3 CF3 CF3 CH N N
CH2CH3 CF3 OCF3 CH CH N
CH2CH3 CF3 OCF3 CH N CH
CH2CH3 CF3 OCF3 N CH CH
CH2CH3 CF3 OCF3 CH N N
CH2CH3 OCF3 CF3 CH CH N
CH2CH3 OCF3 CF3 CH N CH
CH2CH3 OCF3 CF3 N CH CH
CH2CH3 OCF3 CF3 CH N N
CH2CH3 OCF3 OCF3 CH CH N
CH2CH3 OCF3 OCF3 CH N CH
CH2CH3 OCF3 OCF3 N CH CH
CH2CH3 OCF3 OCF3 CH N N
CH3 CF3 CF3 CH CH N
CH3 CF3 CF3 CH N CH
CH3 CF3 CF3 N CH CH
CH3 CF3 CF3 CH N N
CH3 CF3 OCF3 CH CH N
CH3 CF3 OCF3 CH N CH
CH3 CF3 OCF3 N CH CH
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH CH N CH3 OCF3 CF3 CH N CH
CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
CH3 OCF3 OCF3 CH N CH
CH3 OCF3 OCF3 N CH CH
CH3 OCF3 OCF3 CH N N Table 9
Figure imgf000044_0001
X, Y and Z are CH
Rl R5 R Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is N; Y and Z are CT I
Ri R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Z are CH; Y is > J
CH2CH3 R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
H OCF3 OCF3 CH3 OCF3 OCF3
X and Y are CH; Z is > I
Rl R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCP 3 OCF3 CH3 OCF3 OCF3
Figure imgf000045_0001
Table 10
Figure imgf000045_0002
X, Y and Z are CH
Rl R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000046_0001
CF3
OCF3
CF3
Figure imgf000046_0002
OCF3
Figure imgf000046_0003
X is CH; Y and Z are N
Rl R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000046_0004
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000047_0001
Table 11
Figure imgf000047_0002
CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000048_0001
Table 12
Figure imgf000048_0002
CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000049_0001
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000050_0001
Table 13
Figure imgf000050_0002
UΛ
Figure imgf000051_0001
o z z o z z o z z o Z 2 o z z o Z |N
Figure imgf000051_0002
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X and Z are CH; Y is N
Figure imgf000052_0001
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X and Y are CH; Z is N
Figure imgf000052_0002
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X is CH; Y and Z are N
Figure imgf000053_0001
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
Figure imgf000054_0001
Z tj; z z o a o a o a 4 z→ O a O a o o a a z z o a o a z z o a o a * S S * |
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH CH N
CH3 OCF3 CF3 CH N CH
CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
CH3 OCF3 OCF3 CH N CH
CH3 OCF3 OCF3 N CH CH
CH3 OCF3 OCF3 CH N N
X and Z are : CH; Y is N
Figure imgf000055_0001
CH2CH3 CF3 CF3 CH CH N
CH2CH3 CF3 CF3 CH N CH
CH2CH3 CF3 CF3 N CH CH
CH2CH3 CF3 CF3 CH N N
CH2CH3 CF3 OCF3 CH CH N
CH2CH3 CF3 OCF3 CH N CH
CH2CH3 CF3 OCF3 N CH CH
CH2CH3 CF3 OCF3 CH N N
CH2CH3 OCF3 CF3 CH CH N
CH2CH3 OCF3 CF3 CH N CH
CH2CH3 OCF3 CF3 N CH CH
CH2CH3 OCF3 CF3 CH N N
CH2CH3 OCF3 OCF3 CH CH N
CH2CH3 OCF3 OCF3 CH N CH
CH2CH3 OCF3 OCF3 N CH CH
CH2CH3 OCF3 OCF3 CH N N
CH3 CF3 CF3 CH CH N
CH3 CF3 CF3 CH N CH
CH3 CF3 CF3 N CH CH
CH3 CF3 CF3 CH N N
CH3 CF3 OCF3 CH CH N
CH3 CF3 OCF3 CH N CH
CH3 CF3 OCF3 N CH CH
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH CH N
CH3 OCF3 CF3 CH N CH CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
CH3 OCF3 OCF3 CH N CH
CH3 OCF3 OCF3 N CH CH
CH3 OCF3 OCF3 CH N N
X and Y are ; CH; Z is N
Rl R7 R9 χi Yl Zi
CH2CH3 CF3 CF3 CH CH N
CH2CH3 CF3 CF3 CH N CH
CH2CH3 CF3 CF3 N CH CH
CH2CH3 CF3 CF3 CH N N
CH2CH3 CF3 OCF3 CH CH N
CH2CH3 CF3 OCF3 CH N CH
CH2CH3 CF3 OCF3 N CH CH
CH2CH3 CF3 OCF3 CH N N
CH2CH3 OCF3 CF3 CH CH N
CH2CH3 OCF3 CF3 CH N CH
CH2CH3 OCF3 CF3 N CH CH
CH2CH3 OCF3 CF3 CH N N
CH2CH3 OCF3 OCF3 CH CH N
CH2CH3 OCF3 OCF3 CH N CH
CH2CH3 OCF3 OCF3 N CH CH
CH2CH3 OCF3 OCF3 CH N N
CH3 CF3 CF3 CH CH N
CH3 CF3 CF3 CH N CH
CH3 CF3 CF3 N CH CH
CH3 CF3 CF3 CH N N
CH3 CF3 OCF3 CH CH N
CH3 CF3 OCF3 CH N CH
CH3 CF3 OCF3 N CH CH
CH3 CF3 OCF3 CH N N
CH3 OCF3 CF3 CH . CH N
CH3 OCF3 CF3 CH N CH
CH3 OCF3 CF3 N CH CH
CH3 OCF3 CF3 CH N N
CH3 OCF3 OCF3 CH CH N
Figure imgf000057_0001
Figure imgf000057_0002
o O O O O O O O O O o O O o O O O O Q Q O O O O O O O toa toa toa toa toa toa toa ta toa toa toa toa toa toa toa toa toa toa toa ta toa toa toa toa toa toa toa toa toa toa toa toa toa ta toa toa toa toa
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ aJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ
hr] Mr] Mr] Mr] o o o o o o o o o o o n o o o o π o o o n o a a3 a ffi HH HH a pH a a a a E HH HH HH HH a a HH
UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000058_0001
O o O O O O O O O O O O o O O O o O O O O O O O O o o O o O O O o O O o a U toa toa toa toa toa toa toa oa toa toa ta toa toa toa toa toa toa toa toa toa toa IOa toa toa to IOa toa toa toa toa IOa IOa toa toa toa toa toa toa σ
O O O O O O O O o O O O O O O O O O O O O O O O O O O O O O O O O O O o
UaJ UaJ UaJ a UaJ UaJ UaJ UaJ UaJ UaJ UaJ aJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ aJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ
TJ TI TJ T) l Tl Tj TJ Tl J TJ TJ O O O O O O O O O O O O O O O O O O O O O O
TJ Tl Tl Tl T
UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ UaJ
in m CΛ CΛ CΛ ΓΛ CΛ CΛ O O O O O O O O Λ CΛ CΛ CΛ CΛ CΛ CΛ CΛ
O o o o o o o τι τι TJ τι O T| Q TJ OTI Oτ| O4T| O)-r) O>τι Oιτl O4 ) O4Tj OT) O O O O O O O TJ Oτι TJ O T| O T| O T| Tl Q TJ o
UJ UJ UJ UJ TJ oTJ oT o
UJ UτJι J T) oτi oτι UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ J UJ UJ UJ
Figure imgf000058_0002
O O O O O O O O 0 0 0 0 0 0 0 0 o o a to a to a to a to a to a to a t a to a IO a to a to a to a to a t a to a to a to a to a to a to a to a to a to a t a to a t a to a to a to a to a to a to a
U aJ U aJ U aJ U aJ U aJ O O O O O O O O O O 0 0 0 0 0 0 0 0
U aJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ UaJ UaJ UaJ UaJ UaJ UaJ U aJ U aJ UaJ UaJ UaJ UaJ UaJ a UaJ U aJ U aJ U aJ U aJ U aJ U aJ U aJ
a a a a a a Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Tl Tj 4τJ TJ
CΛ CΛ CΛ CΛ CΛ CΛ CΛ m 0 0 0 0 0 0 0 0 CΛ CΛ CΛ CΛ CΛ CΛ CΛ in
0 0 0 0 0 0 0 O 0 (1 O fi O (. 0 0 0 0 0 0 0 0 0 0 O O O O O O O O O O J Tl TJ TJ Tl τi TI T TJ TJ τι τι τι
UJ UJ UJ UJ UJ UJ a TJ a T| a TJ X TJ aτι aτι aτι Xτι a TJ a TJ T aJ aJ aτι aτι a TJ a l TJ
TJ a TJ a Tl aJ a Tj aτι a T| a TJ a TJ to t to to to to to to to to to to to to to to 1 to to to t t to to
Figure imgf000059_0001
a a a a a o o o o o o o o o o o o o o o o o o o o o o o T Tj Ti Ti Ti Hri Hf
Figure imgf000059_0002
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
HH HH HH HH a HH a
o o o o o o o o o o o o o o o o o o o o a a a a a a a a a a a a a ffi pπ a a a a a
Figure imgf000060_0001
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
W HH W K W ffi K HH W K W ffi HH ffi HH ffi ffi W K W HH W K K HH W K W K E K HH ffi HH HH 3H *H ffi
O O O O O O O O O O O O O O O O O O O O a a HH Hπ HH HH HH W HH a H HH HH a a
CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ O O O O O O O O CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ 0 0 0 O Q OJ O TJ O O O Q O O O O O O O O O O O O O O o τι O O O J Q TJ T O
TJ Tl T T| τι Tl Tl T| TJ T 0
TJ TJ
UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000060_0002
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
^ PH X ?H HH S H HH HH W HH HH S 7H HH HH HH S HH S S X HH X X ?H W S X
O O O O O O O O O O TJ O O O
Tl TJ Tl τι τι TJ a a a O a
CΛ CΛ CΛ CΛ o TJ ToJ ToJ o TJ ToJ oτι τoι τoι o o o o
UJ UJ UJ J UJ UJ UJ UJ a Tl a Tl a Tl a Tl
Figure imgf000061_0001
to to to to
Figure imgf000061_0002
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o ffi ffi ffi ffi W K W HH HH HH W W K ffi ffi W K HH K ffi K W HH W W W K W K K W K E E K K h-H HH
O O O O O O O O O O TJ TJ TI TI J TJ TJ Tl T Tl Tl Tl Tl
Figure imgf000061_0003
CΛ CoΛ Oo Oo oO Oo Oo Oo Oo Oo o o o o o o o o CoΛ CoΛ CΛ CΛ CΛ CΛ CΛ
O O O CΛ O O O O O O O O τι Tl Oτι Tl Tl o o o o o o o o o o o o o
UJ UJ UJ UJ UJ
Figure imgf000061_0004
O O O O O O O O O O O O O
Figure imgf000062_0001
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z i s CH
Rl R5 R9 Ri R5 RJ
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000063_0001
Table 18
Figure imgf000063_0002
Figure imgf000064_0001
O O O a a a a a a a a UaJ USJ USJ USJ a a a a a a a a a a a a a a a a a a a a a a a a |2
CΛ CΛ CΛ CΛ O O O O O O O O CΛ O .. .
Ω TI ΩTJ ΩTJ ΩTJ TjΪ OHrt OHt Oi-rj Oj OHij OHri OHri O-- O-- O _ O_ O_ O-_. O-_ O_ Ol Olτj | 2v_-| UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000064_0003
U
Figure imgf000064_0002
Figure imgf000064_0004
Figure imgf000064_0005
o a
Figure imgf000065_0001
CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ o O O o o o O o O CΛ CΛ oo CΛ 00 CΛ CΛ CΛ O O O O
O O O
Tl τι o O o O o O O o o o O o O O O O O O O o O O O O O o o o O O o UJ UJ i si si si o si to si to si si si si Si aJ a Tl O O si s J J to to to to to toi T to to Si Tl τι Tl Tl Tl J UJ UJ UJ UJ UJ UJ UJ UJ a Tl al a Tl a TJ a TJ a Tl to to to to to t to to si T to to to to to to si to SJ to si to si to si
Figure imgf000065_0002
o o CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ
O Q O o o O O O O o o CΛ CΛ CΛ CΛ o o O O O O O O o O O O O
TJ J TJ TJ Tl ol o Tl o O O O
Tl o J U TJl Tl T o O O O o o o o o o O O τi o
UJ UJ J TJ T) TJ TJ TJ τι
UJ UJ UJ UJ UJ UJ U UJ UτJι Tl TJ Tl
UJ J UJ J UJ UJ UJ UJ UJ J
Figure imgf000065_0003
Figure imgf000066_0001
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000067_0001
Table 2 >0
Figure imgf000067_0002
Figure imgf000068_0001
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000069_0001
Table 21
Figure imgf000069_0002
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000070_0001
Table 22
Figure imgf000070_0002
X, Y and Z are CH
Ri R5 R9 Rl R£ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3 CH2CH3 CF3 OCF3 CH3 CF3 OCF3 CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000070_0003
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000071_0001
Figure imgf000071_0002
CF3
OCF3
CF3
Figure imgf000071_0003
OCF3
Figure imgf000071_0004
Table 23
Figure imgf000072_0001
X andZ are CH
El ^ El R9 El R9 El R9
CH2CH3 CF3 CH3 CF3 CH2CH3 OCF3 CH3 OCF3
Figure imgf000072_0002
X,YandZareN
El ^_ El R9 E R9 El R9
CH2CH3 CF3 CH3 CF3 CH2CH3 OCF3 CH3 OCF3
Figure imgf000073_0001
X, Y and Z are CH
El R^ ^. XI zi
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X is N; Y and Z are CH
El EZ R9 γi zj_
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH
CH3 CF3 CF3 N N
CH3 CF3 OCF3 CH N
CH3 CF3 OCF3 N CH
CH3 CF3 OCF3 N N
CH3 OCF3 CF3 CH N
CH3 OCF3 CF3 N CH
CH3 OCF3 CF3 N N
CH3 OCF3 OCF3 CH N
CH3 OCF3 OCF3 N CH
CH3 OCF3 OCF3 N N
X and Y are CH; Z is N
El R^ R9 Xi zi
CH2CH3 CF3 CF3 CH N
CH2CH3 CF3 CF3 N CH
CH2CH3 CF3 CF3 N N
CH2CH3 CF3 OCF3 CH N
CH2CH3 CF3 OCF3 N CH
CH2CH3 CF3 OCF3 N N
CH2CH3 OCF3 CF3 CH N
CH2CH3 OCF3 CF3 N CH
CH2CH3 OCF3 CF3 N N
CH2CH3 OCF3 OCF3 CH N
CH2CH3 OCF3 OCF3 N CH
CH2CH3 OCF3 OCF3 N N
CH3 CF3 CF3 CH N
CH3 CF3 CF3 N CH t
Figure imgf000075_0001
R o 2 o o o 0 o
Ω τι G J 1 I2 vo o o o
Ω uT ω u7 w u? w Tl τι | I2o G Q o TJ | I2 vo
Figure imgf000075_0002
X and Y are CH; Z is N
El ? R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z is CH
El R5 R9 El ^_ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is CH; Y and Z are N
El ^L R9 El R£ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
El ^L R9 El ? R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El _ R9 El ^. R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 Table 26
Figure imgf000077_0001
X, Y and Z are CH
El R£ R_ El R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is N; Y and Z are CH
Rl R^ R9 El ^L R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Z are CH; Y is N
El R5 R9 El R_ E?
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are CH; Z is N
El R5 R9 El _£ E?
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z is CH
Rl R5 R9 Rl ^L R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 X is CH; Y and Z are N
El R£ R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
El _£ R9 El _£ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El R5 R_ El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 Table 2' 7
Figure imgf000078_0001
X, Y and Z are CH
El R R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is N; Y and Z are CH
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3 CH2CH3 CF3 OCF3 CH3 CF3 OCF3 CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 X and Z are CH; Y is N
El Ei R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000079_0001
X and Y are N; Z is CH
El R_ R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is CH; Y and Z are N
El R5 R9 El R5 ^ .
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
El ^. R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 Table 28
Figure imgf000080_0001
X, Y and Z are CH
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is N; Y and Z are ; CH
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Z are CH; Y is N
El R5 Ei El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are CH; Z is N
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z is CH
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 19
X is CH; Y and Z are N
El _£ R9 El R5 ^
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CL [; X and Z are N
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Table 29
Figure imgf000081_0001
X, Y and Z are CH
El El. El R9 El ^L El ^L
CH2CH3 CF3 CH3 CF3 CH2CH3 OCF3 CH3 OCF3
Figure imgf000081_0002
Figure imgf000082_0001
X, Y and Z are N
El R9 El R9 El R9 El R_
CH2CH3 CF3 CH3 CF3 CH2CH3 OCF3 CH3 OCF3
Figure imgf000082_0002
X is N; Y and Z are ( H
El Ei R9 γl z 1
CH2CH3 CF3 CF CH j> I
CH2CH3 CF3 CF3 N Cl H
CH2CH3 CF3 CF3 N j> I
CH2CH3 CF3 OCF3 CH is r
CH2CH3 CF3 OCF3 N Cl i
CH2CH3 CF3 OCF3 N JN l
CH2CH3 OCF3 CF3 CH J\
CH2CH3 OCF3 CF3 N Cl ϊ
CH: CH3 OCF3 C F3 N N 0
Figure imgf000083_0001
oa z z oa Z Z oa z z oa z z oa z z 9 z z 8ΪS z z a z z a z z oa z z a o z z a o
a z z a z z a z z τ aj z< z aι z z: S a: a S Z |N o a z z o a Z Z o HjH Z o a z z o a
0
Figure imgf000084_0001
£ * * 9 II a s z z o z g z z o a * * 9 z z o a z z o z z S IM z z o a
z z s IN O a z z o z z o a z z o a z z H- z z o a z z o a z z o IN o z z
Figure imgf000084_0002
Figure imgf000085_0001
Figure imgf000085_0002
CH2CH3 OCHF2 OCF3 CH2CH3 SCF3 OCF3
CH2CH3 OCHF2 SCF3 CH2CH3 SCF3 SCF3
CH2CH3 OCHF2 OCHF2 CH2CH3 SCF3 OCHF2
CH2CH3 OCHF2 SCHF2 CH2CH3 SCF3 SCHF2
CH2CH3 OCHF2 C F5 CH2CH3 SCF3 C F5
CH2CH3 OCHF2 Cl CH2CH3 SCF3 Cl
CH2CH3 OCHF2 SCH2CH3 CH2CH3 SCF3 SCH2CH3
CH2CH3 SCHF2 CF3 CH2CH3 Cl CF3
CH2CH3 SCHF2 OCF3 CH CH3 Cl OCF3
CH2CH3 SCHF2 SCF3 CH2CH3 Cl SCF3
CH2CH3 SCHF2 OCHF2 CH2CH3 Cl OCHF2
CH2CH3 SCHF2 SCHF2 CH2CH3 Cl SCHF2
CH2CH3 SCHF2 C2F5 CH2CH3 Cl C2F5
CH2CH3 SCHF2 Cl CH2CH3 Cl Cl
CH2CH3 SCHF2 SCH2CH3 CH2CH3 Cl SCH2CH3
CH3 CF3 CF3 CH3 OCF3 CF3
CH3 CF3 OCF3 CH3 OCF3 OCF3
CH3 CF3 SCF3 CH3 OCF3 SCF3
CH3 CF3 OCHF2 CH3 OCF3 OCHF2
CH3 CF3 SCHF2 CH3 OCF3 SCHF2
CH3 CF3 C F5 CH3 OCF3 C2F5
CH3 CF3 Cl CH3 OCF3 Cl
CH3 CF3 SCH2CH3 CH3 OCF3 SCH2CH3
CH3 OCHF2 CF3 CH3 SCF3 CF3
CH3 OCHF2 OCF3 CH3 SCF3 OCF3
CH3 OCHF2 SCF3 CH3 SCF3 SCF3
CH3 OCHF2 OCHF2 CH3 SCF3 OCHF2
CH3 OCHF SCHF2 CH3 SCF3 SCHF2
CH3 OCHF2 C F5 CH3 SCF3 C F5
CH3 OCHF2 Cl CH3 SCF3 Cl
CH3 OCHF2 SCH2CH3 CH3 SCF3 SCH2CH3
CH3 SCHF2 CF3 CH3 Cl CF3
CH3 SCHF2 OCF3 CH3 Cl OCF3
CH3 SCHF2 SCF3 CH3 Cl SCF3
CH3 SCHF2 OCHF2 CH3 Cl OCHF2
CH3 SCHF2 SCHF2 CH3 Cl SCHF2
CH3 SCHF2 C F5 CH3 Cl C F5
CH3 SCHF2 Cl CH3 Cl Cl
CH3 SCHF2 SCH2CH3 CH3 Cl SCH2CH3
Figure imgf000087_0001
X is N; Y and Z are CH
?1 R5 R9 Rl R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000087_0002
X and Y are CH; Z is N
Rl R5 R9 El ^. ^
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z is CH
^ R5 R9 Rl Ei R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is CH; Y and Z are N
El R9 Ei R9
CH2CH3 CF3 CF3 CH3 CF3 CF3 CH2CH3 CF3 OCF3 CH3 CF3 OCF3 CH2CH3 OCF3 CF3 CH3 OCF3 CF3 CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Figure imgf000088_0001
X, Y and Z are N
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Table 33
Figure imgf000088_0002
X , Y and Z are CH
El ^ R9 El ? R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is N; Y and Z are CH
El ^. R9 El Ei R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are CH; Z is N
El ^L R9 El ^ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCI 3 OCF3 CH3 OC *3 OCF3 X and Y are N; Z is CH
El ? R9 El ^. R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is CH; Y and Z are N
El ? R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
El ? R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El ? R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 C 3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Table 3 1
Figure imgf000089_0001
X, Y and Z are CH
El E£ R9 El H R9 CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3 X is N; Y and Z are CH
El R5 R9 El R5 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are CH; Z is N
El R5 R9 El ^. R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X and Y are N; Z is CH
El R5 Ei El R R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X is CH; Y and Z are N
El R5 y[ El ^ R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Y is CH; X and Z are N
El R5 R9 El ^1 R9
CH2CH3 CF3 CF3 CH3 CF3 CF3
CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
X, Y and Z are N
El R5 ^. El ^i R9
CH2CH3 CF3 CF3 CH3 CF3 CF3 CH2CH3 CF3 OCF3 CH3 CF3 OCF3
CH2CH3 OCF3 CF3 CH3 OCF3 CF3
CH2CH3 OCF3 OCF3 CH3 OCF3 OCF3
Formulation/Utility
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 emulsifϊable 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.
Weight Percent
Active Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifϊable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2
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 Emulsifwrs 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, NN-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, NN-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, including emulsifiable concentrates, 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. 4,112,114.
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. For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A. Example A
High Strength Concentrate
Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
Example B
Wettable Powder
Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example C
Granule Compound 1 10.0% attapulgite granules (low volatile matter,
0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example D Extruded Pellet Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. 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. 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, chlomethoxyfen, chlor-amben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlomitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-methyl-3-pyridine- carboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, fla-zasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, im.az.amox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyι)phenoxy]-2- nitrophenyl]-2-methoxyethylidene] amino] oxy] acetate (AKH-7088), methyl 5-[[[[(4,6- dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]- 1 -(2-pyridinyl)- lH-pyrazole-4- carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate.
In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds.
The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A-D for compound descriptions. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A
Figure imgf000096_0001
Cmpd Rl R3 R4 mp (°C)
Figure imgf000096_0002
Figure imgf000096_0003
Figure imgf000096_0004
Figure imgf000097_0001
CH3 COOCH3 H 127-129
Figure imgf000097_0002
Figure imgf000097_0003
Figure imgf000097_0004
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
♦See Index Table B for JH NMR data.
INDEX TABLE B
Cmpd No. *H NMR Data (CDC13 solution unless indicated otherwise)a 2 δ 8.55 (t, 2H), 7.55-7.50 (m, 2H), 7.45-7.40 (m, 2H), 6.72 (d, IH), 4.26 (s,
2H), 2.32 (s, 3H). δ 8.70 (d, IH), 8.65 (d, IH), 7.60-7.55 (m, 2H), 7.50-7.45 (m, 2H), 7.05
(d, IH), 6.75 (d, IH), 4.28 (s, 2H). δ 8.62 (s, IH), 8.27 (m, 2H), 7.7 (s, IH), 7.47 (m, 3H), 7.4 (s, IH), 5.28 (s,
2H), 2.36 (s, 3H).
47 δ 8.59 (m, 2H), 7.40-7.10 (m, 4H), 6.71 (d, IH), 4.24 (s, 2H), 2.70 (q,
2H), 1.20 (t, 3H).
48 δ 8.56 (s, 2H), 7.34 (t, IH), 7.15 (m, 3H), 6.72 ( , IH), 4.24 (s, 2H), 2.65
(t, 2H), 1.57 (m, 2H), 0.98 (t, 3H).
49 δ 8.65 (s, IH), 8.47 (s, IH), 8.17 (s, IH), 7.40-7.15 (m, 4H), 4.20 (s, 2H),
2J0 (q, 2H), 1.25 (t, 3H).
50 δ 9.20 (s, IH), 8.60 (s, IH), 7.41 (t, IH), 7.15 (m, 3H), 4.25 (s, 2H), 2.80
(q, 2H), 1.24 (t, 3H.).
58 δ 8.57 (s, IH), 8.54 (m, IH), 7.53 (m, 2H), 7.43 (m, 2H), 6.71 (d, IH),
4.28 (s, 2H), 2.65 (t, 2H), 1.61 (m, 2H), 0.98 (t, 3H).
INDEX TABLE C
Figure imgf000102_0001
Cmpd Rl mp(°C)
Figure imgf000102_0002
Figure imgf000103_0001
Figure imgf000104_0001
♦See Index Table D for lH NMR data.
INDEX TABLE D Cmpd No. IH NMR Data (CDC13 solution unless indicated otherwise)a 63 δ 8.77 (s, IH), 8.57 (s, IH), 8.17 (s, IH), 7.77-7.85 (m, 2H), 7.50-7.60 (m,
2H), 2.42 (s, 3H). 67 δ (s, IH), 8.93 (s, IH), 8.25 (s, IH), 8.07 (d, IH), 7.97 (d, IH), 7.68 (m,
IH), 2.48 (s, 3H).
70 δ 9.13 (d, IH), 8.60 (m, 2H), 8.42 (d, IH), 7.91 (m, 2H), 7.72 (t, IH), 6.70 (d, IH).
71 δ 8.81 (s, IH), 8.58 (s, IH), 8J8 (s, IH), 7.81 (s, IH), 7.77 (m, IH), 7.57 (m, 2H), 2.77 (q, 2H), 1.28 (t, 3H). a lH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
Seeds of barnyardgrass (Echinochloa crus-gallϊ), crabgrass (Digitaria spp.), momingglory (Jpomoea spp.), and velvetleaf (Abutilon theophrasti) were planted into a sandy loam soil and treated preemergence by soil drench with test chemicals formulated in a non-phytotoxic solvent mixture which includes a surfactant. At the same time, these crop and weed species were also treated postemergence sprayed to runoff, with test chemicals formulated in the same manner. Plants ranged in height from two to eighteen cm and were in the one to two leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in
Table A, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results. TABLE A COMPOUND
Rate 2000 g/ha 1 6 8 12 13 59 65 73 74
PRE SOIL DRENCH
Barnyardgrass 10 8 7 7 9 10 5 9 1 Crabgrass 10 9 10 9 10 10 8 10 7 Momingglory 8 5 8 3 3 9 4 9 1 Velvetleaf 9 8 3 5 9 10 4 9 4
TABLE A COMPOUND TABLE A COMPOUND
Rate 1000 g/ha 8 Rate 1000 g/ha 1 6 8 12 13 59 65 73 74
PRE SOIL DRENCH SPRAYED TO RUNOFF
Barnyardgrass 4 Barnyardgrass 9 8 3 5 6 9 4 8 5 Crabgrass 9 Crabgrass 9 9 5 8 9 9 5 9 8 Momingglory 9 Momingglory 9 6 7 2 2 8 10 9 10 Velvetleaf 2 Velvetleaf 9 9 2 6 8 9 5 9 5
TABLE A COMPOUND
Rate 500 g/ha 8
SPRAYED TO RUNOFF
Barnyardgrass 3 Crabgrass 8 Momingglory 3 Velvetleaf 1
TEST B
Seeds of bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), cocklebur (Xanthium strumarium), com (Zea mays), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberiϊ), lambsquarters (Chenopodium album), momingglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flood test consisted of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-gallϊ) grown to the 2-leaf stage for testing. 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 B, 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. TABLE B COMIPOUND
Rate 500 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 16 32 52 53 54 59 61 62 63 64 65 66 67 68 73 74
Postemergence
B. signalgrass 9 - 3 3 5 - 1 9 3 7 7 8 4 1 - 9 2 5 3 5 3 5 8 1 5 9 5 8 2
Barnyardgrass - 6 6 8 3 3 2 8 4 - 3 3 6 4 4 8 2 4 8 4 4 3 5 0 4 6 4 4 0
Beds raw 10 9 9 9 9 8 3 10 10 10 10 10 10 5 - 10 10 9 9 9 4 8 9 7 8 10 10 9 6
Blackgrass 9 9 3 7 5 2 1 9 3 5 4 5 3 3 - 9 6 3 6 8 4 6 9 0 6 10 5 9 1
Cocklebur 10 9 6 - 8 7 - 9 9 9 8 9 7 6 - 9 6 9 8 8 7 8 9 2 5 9 7 8 5
Corn 7 7 3 4 4 3 2 5 3 3 3 4 3 1 - 7 1 3 4 4 2 2 5 1 3 7 2 3 1
Crabgrass 9 10 3 9 8 9 2 10 6 7 3 9 4 7 - 9 4 5 9 9 8 6 9 1 10 10 8 9 3
Ducksalad - 2 6 5 2 6 2 6 5 - 2 3 3 2 6 9 7 3 7 5 2 6 9 0 7 8 3 3 0
Giant foxtail 9 10 5 8 6 6 1 9 5 9 4 5 3 3 - 9 2 4 9 9 3 3 5 1 4 9 3 9 1
Momingglory 10 9 8 9 4 8 5 10 9 - 9 9 8 1 - 10 3 10 10 9 10 10 8 10 10 10 10 10 7
Nutsedge 2 2 0 0 0 3 0 3 3 - 0 0 0 1 - 7 - 0 0 - - - 2 - 1 - - - -
Rape 9 10 7 10 10 8 7 10 9 10 9 9 7 5 - 10 9 9 7 9 3 8 4 2 7 9 7 10 3
Redroot pigweed 10 9 9 10 9 9 7 10 9 10 9 10 9 9 - 10 7 7 9 9 10 9 10 7 10 10 10 10 8
Rice - 6 6 7 3 3 0 8 3 - 3 1 5 4 2 7 2 4 6 2 0 1 3 0 2 4 3 3 0
S. Flatsedge - 9 9 8 5 7 4 9 9 - 8 5 9 3 7 9 9 9 9 9 8 9 9 0 9 9 7 3 0
Soybean 9 8 8 8 6 6 5 9 8 9 5 5 5 4 - 9 7 4 9 6 2 2 6 2 7 8 7 6 3
Sugarbeets 10 9 9 10 10 9 8 9 9 10 9 10 9 9 - 10 10 9 9 10 9 9 10 8 10 9 10 9 7
Velvetleaf 9 9 4 9 9 8 2 9 9 9 8 8 4 2 - 9 7 3 8 8 3 8 9 2 8 8 8 10 2
Wheat 5 5 3 2 4 3 0 6 3 3 4 4 3 1 - 8 2 2 3 4 3 2 5 2 3 6 4 6 2
Wild oats 9 7 3 3 5 3 0 8 3 5 5 4 3 1 - 9 2 3 6 5 3 2 7 1 3 8 3 9 1
TABLE B COMPOUND
Rate 500 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 16 52 53 54 59 61 62 63 64 65 66 67 68 73 74 75
Preemergence
B. signalgrass 9 - 5 - 9 9 0 10 4 8 9 9 5 7 10 6 6 9 9 9 9 10 2 10 10 10 10 0 9
Bedstraw 9 10 5 8 7 5 0 9 10 9 8 6 2 1 10 8 4 8 9 6 8 9 0 8 10 6 10 0 8
Blackgrass 10 10 10 10 7 4 0 10 3 5 6 9 3 4 10 2 4 9 8 5 9 9 0 10 9 7 10 0 10
Cocklebur 10 3 0 1 - 0 0 9 3 - 3 7 - 0 10 1 0 2 10 0 1 7 0 3 5 8 - 0 9
Corn 2 2 1 2 1 0 0 4 1 0 2 2 3 0 8 0 1 3 2 2 2 4 0 3 7 1 2 0 2
Crabgrass 10 10 5 10 9 10 2 10 9 10 10 10 8 8 10 8 8 10 10 10 9 10 0 9 10 10 10 1 10
Giant foxtail 10 10 10 10 10 10 5 10 9 10 9 10 8 10 6 10 10 10 0 4 10 10 10 0
Momingglory 10 10 10 8 9 2 0 10 10 10 10 10 8 1 10 5 2 10 10 7 10 10 5 9 10 9 10 0 10
Nutsedge 1 0 5 0 1 0 0 0 0 1 0 0 0 0 1 0 0 0 - 0 0 2 0 0 0 0 0 0 0
Rape 10 10 7 9 10 7 0 10 7 10 6 9 8 1 10 7 3 10 9 3 8 10 0 8 10 8 10 0 4
Redroot pigweed 10 10 10 10 10 6 2 10 7 10 9 9 4 8 10 8 9 10 10 10 10 10 0 10 10 10 10 0 10
Soybean 5 5 2 3 3 0 0 4 1 2 3 3 1 0 9 0 0 4 2 1 0 1 0 1 8 2 2 0 1
Sugarbeets 10 10 10 10 10 10 1 10 10 10 10 10 9 9 10 9 9 10 10 10 10 10 0 10 10 10 10 0 10
Velvetleaf 10 10 6 7 9 3 0 9 8 10 4 10 7 1 10 8 1 10 10 7 10 10 1 8 10 8 8 0 10
Wheat 9 3 0 5 3 0 0 6 1 3 0 1 0 0 6 1 1 5 4 0 4 2 0 3 4 4 9 0 5
Wild oats 10 10 9 9 8 3 0 9 4 6 4 9 2 3 10 1 4 9 8 4 8 9 0 5 9 8 10 0 9
TABLE B COMPOUND
Rate 250 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Postemergence
B. signalgrass 8 - 3 2 4 - 1 9 3 4 7 7 3 8 1 7 3 2 3 7 7 9 3 3 2 5 9 5 2
Barnyardgrass - 5 6 8 3 2 1 7 3 - 3 3 5 9 4 6 2 3 0 4 6 6 4 5 2 3 5 4 4
Bedstraw 9 9 8 9 9 7 3 10 10 10 10 10 8 9 4 9 9 3 4 9 8 9 10 10 6 9 8 9 6
Blackgrass 9 7 3 6 5 2 - 8 3 7 4 5 3 9 2 7 2 1 3 6 9 9 4 8 1 5 8 5 1
Cocklebur 9 8 5 7 8 7 - 10 9 9 8 9 7 10 5 8 8 3 7 8 8 10 10 9 3 9 8 8 8
Corn 4 6 3 3 2 3 2 5 3 3 3 3 3 5 1 3 2 3 3 4 4 3 1 3 1 3 4 3 2
Crabgrass 9 9 3 9 4 8 2 10 4 6 3 7 2 9 2 4 3 2 3 8 9 9 8 10 1 6 10 9 7
Ducksalad - 2 3 2 1 0 0 7 3 - 1 2 2 7 1 5 2 7 0 5 6 6 3 6 0 2 6 4 5
Giant foxtail 9 9 3 7 4 5 1 9 4 5 3 4 1 8 1 5 1 1 3 9 8 9 3 8 1 4 9 4 2
Mo ingglory 10 9 7 8 3 8 2 10 7 10 9 9 6 9 1 8 8 6 4 9 10 9 10 10 3 8 3 10 9
Nutsedge 1 - 0 0 0 2 0 3 0 1 0 0 0 2 0 0 0 0 0 3 - - - 2 - - - - 2
Rape 9 9 6 10 10 8 6 10 9 10 9 9 6 9 2 8 9 3 5 10 10 10 10 10 6 9 10 9 10
Redroot pigweed 10 9 9 10 9 9 7 10 9 10 9 10 9 9 8 10 9 7 8 10 10 10 10 10 8 10 10 10 9
Rice - 5 4 6 2 2 0 7 2 - 3 0 5 7 3 6 0 2 0 5 5 5 2 5 0 1 3 3 2
S. Flatsedge - 8 9 7 5 7 2 9 9 - 8 4 8 9 2 5 2 6 0 9 9 9 3 7 2 5 8 8 8
Soybean 9 8 7 8 5 6 3 10 8 8 5 5 5 9 4 8 6 4 6 6 8 8 6 7 5 7 7 7 6
Sugarbeets 10 9 9 9 10 8 8 10 9 10 8 10 8 10 9 10 9 6 7 10 10 10 10 10 8 10 10 10 10
Velvetleaf 9 9 3 8 7 8 1 10 8 8 8 8 4 8 2 7 7 2 7 9 9 9 7 9 2 7 8 4 8
Wheat 3 3 2 2 3 2 0 4 3 3 3 3 2 6 0 4 3 0 3 5 6 5 3 4 0 4 5 4 2
Wild oats 7 6 2 3 4 3 0 6 2 3 4 4 3 9 1 5 5 2 3 6 8 9 4 4 0 5 6 4 2
TABLE B COM[POUΓND
Rate 250 g/ha 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64
Postemergence
B. signalgrass 5 2 2 1 1 1 0 1 1 1 6 7 6 5 0 5 8 4 2 9 9 2 4 2 3 4 2 4 6
Barnyardgrass 5 3 3 1 2 0 0 0 0 2 5 5 5 4 0 4 6 6 4 7 7 2 3 5 2 3 3 3 4
Bedstraw 6 10 9 7 8 7 - - 4 6 10 - 10 9 0 10 - - - 10 10 10 7 8 3 9 3 5 7
Blackgrass 4 5 2 1 1 2 0 0 1 2 8 7 8 7 0 6 6 6 8 9 9 1 2 5 2 6 2 3 7
Cocklebur 7 9 6 8 2 3 3 8 5 5 9 9 9 9 0 9 8 9 7 9 9 6 7 7 4 8 7 - 7
Corn 2 1 1 1 1 1 1 1 1 1 3 8 5 3 0 3 4 4 2 9 6 1 3 3 3 3 2 2 4
Crabgrass 9 2 1 1 2 1 1 1 1 3 10 8 10 7 0 8 10 9 6 10 9 4 5 8 4 7 5 4 9
Ducksalad 6 4 2 0 1 1 0 0 0 7 5 8 9 9 0 4 7 4 8 9 9 5 1 6 2 3 0 2 6
Giant foxtail 3 2 1 1 1 1 1 0 1 2 9 9 9 9 0 7 7 5 2 10 9 1 4 8 2 5 2 3 4
Momingglory 4 10 5 2 1 2 1 1 1 5 8 9 10 10 0 10 8 9 3 10 10 - 3 10 9 - 9 10 8
Nutsedge - 1 0 0 0 0 0 0 0 - 0 2 3 3 - - - - 2 - - 0 0 0 0 0 - 0 0
Rape 9 8 7 3 9 5 4 6 4 8 10 10 10 10 0 9 10 9 10 10 9 8 9 7 4 8 2 8 4
Redroot pigweed 9 9 7 6 5 8 7 5 3 6 10 9 10 10 0 10 9 9 9 10 10 7 6 8 7 9 9 9 10
Rice 3 2 3 1 1 0 0 0 0 2 6 6 7 7 0 4 6 5 4 8 7 1 3 4 1 2 0 1 2
S. Flatsedge 8 6 8 3 2 6 0 4 2 5 9 9 9 9 0 7 9 9 9 9 9 9 9 8 6 8 7 8 8
Soybean 7 6 4 2 2 2 0 1 2 2 7 9 9 6 0 9 7 7 7 10 9 7 4 8 2 5 1 2 5
Sugarbeets 10 10 10 9 10 9 5 9 10 10 10 10 10 10 0 10 9 9 10 10 10 10 9 9 9 10 9 9 10
Velvetleaf 4 9 6 1 1 1 1 2 1 2 8 9 9 9 0 9 8 9 8 9 8 7 3 7 2 8 2 8 8
Wheat 4 2 1 1 1 2 0 1 1 2 3 4 5 3 0 4 6 5 4 9 7 1 2 2 3 3 2 2 3
Wild oats 4 3 3 2 2 2 0 1 1 1 7 6 6 5 0 4 9 7 4 9 8 1 3 3 2 3 1 2 5
TABLE B COMPOUND
Rate 250 g/ha 65 66 67 68 70 71 72 73 74 75 76 77 78
Postemergence
B. signalgrass 1 4 7 3 1 - 6 9 1 3 0 1 1
Barnyardgrass 0 4 5 4 0 3 6 6 0 3 0 0 0
Bedstraw 7 6 10 9 1 - 4 9 2 9 0 4 0
Blackgrass 0 5 9 4 0 - 5 9 0 8 0 2 1
Cocklebur 1 4 8 7 2 - 4 9 5 7 4 3 0
Corn 1 2 6 2 2 - 5 3 1 3 1 1 2
Crabgrass 1 8 10 8 1 - 8 9 1 - 1 2 0
Ducksalad 0 5 6 2 0 2 3 2 0 2 0 0 0
Giant foxtail 1 2 9 2 0 - 7 9 1 4 1 1 0
Momingglory 8 9 10 10 2 - 4 9 7 10 1 4 2
Nutsedge 0 1 4 0 0 - - 2 0 0 - - 0
Rape 2 7 8 - 1 - 7 10 1 9 2 2 0
Redroot pigweed 6 10 10 10 3 - 9 10 8 10 2 3 4
Rice 0 1 2 3 0 2 2 6 0 1 0 0 0
S. Flatsedge 0 8 9 7 0 4 4 6 0 1 0 0 0
Soybean 2 6 8 7 3 - 5 9 2 3 1 1 0
Sugarbeets 8 10 9 10 2 - 9 9 6 10 3 3 0
Velvetleaf 2 6 8 7 1 - 5 9 2 9 1 1 0
Wheat 2 2 5 2 0 - 4 5 1 3 0 0 0
Wild oats 1 2 8 2 0 - 4 9 1 3 0 1 0
TABLE B COMPOUND
Rate 250 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Preemergence
B. signalgrass 9 - 2 - 9 9 0 10 2 8 8 9 0 9 3 9 2 0 4 8 9 9 6 6 1 3 9 4 6
Bedstraw 8 10 5 8 7 0 0 10 7 9 4 5 0 8 0 5 5 0 1 8 7 9 1 2 0 - 8 3 10
Blackgrass 10 10 4 10 7 0 0 10 2 5 6 4 0 10 2 9 1 0 4 5 9 9 3 8 0 4 6 3 2
Cocklebur 3 1 0 0 1 0 0 9 1 3 2 5 0 - 0 0 0 0 - 0 2 3 0 8 0 - - 0 0
Corn 2 1 0 1 0 0 0 3 0 0 0 1 0 2 0 1 0 0 0 1 2 1 0 0 0 0 1 0 0
Crabgrass 10 10 2 8 9 8 1 10 9 9 8 10 7 10 2 9 6 0 2 10 10 10 1 1 1 5 10 7 8
Giant foxtail 10 10 9 10 10 9 1 10 8 9 9 10 7 10 7 10 - 0 1 9 10 10 6 9 1 9 10 9 9
Momingglory 10 10 4 8 8 2 0 10 9 9 10 9 2 9 0 2 6 0 0 6 10 10 4 10 0 2 3 3 3
Nutsedge - 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 - - 0 0 - 0 0 - 0
Rape 10 10 2 7 10 4 0 10 4 10 6 9 2 9 0 3 0 0 0 5 10 7 4 10 0 3 4 1 3
Redroot pigweed 10 10 10 10 8 6 2 10 7 10 9 9 4 10 8 10 7 0 1 9 10 10 10 9 4 7 7 3 10
Soybean 3 2 0 1 2 0 0 2 1 1 3 3 0 1 0 0 0 0 0 0 2 1 0 1 0 0 1 0 0
Sugarbeets 10 10 10 10 10 9 0 10 6 10 10 10 6 10 7 9 6 0 2 10 10 10 9 9 0 8 3 4 10
Velvetleaf 10 8 5 7 9 2 0 9 8 8 4 10 1 7 1 1 0 0 0 10 8 10 2 2 0 1 2 0 6
Wheat 8 3 0 1 2 0 0 5 0 1 0 0 0 7 0 3 0 0 0 2 4 6 0 2 0 1 0 0 0
Wild oats 9 9 7 8 6 2 0 9 2 4 4 7 0 9 2 8 5 0 3 8 9 9 4 5 0 3 4 1 2
TABLE B COMPOUND
Rate 250 g/ha 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64
Preemergence
B. signalgrass 9 7 1 1 0 0 0 1 0 1 7 10 9 8 0 9 9 5 1 9 10 2 3 9 3 8 8 8 10
Bedstraw - 10 2 0 1 0 0 2 0 - 8 8 10 10 0 10 8 8 9 9 9 7 1 6 1 6 2 4 8
Blackgrass 3 4 0 0 0 1 0 0 0 2 10 10 8 9 0 10 10 6 10 10 10 1 3 7 2 5 1 8 6
Cocklebur - 0 0 0 0 0 0 - 0 0 0 8 2 8 0 - 2 2 0 10 7 0 0 - 0 1 - - -
Corn 1 0 0 0 0 0 0 0 0 0 1 2 1 1 0 3 3 1 0 8 7 0 1 1 0 1 1 1 4
Crabgrass 10 3 0 1 1 0 0 0 0 0 9 10 10 9 0 10 10 9 9 10 10 6 3 10 6 8 9 8 10
Giant foxtail 10 5 1 1 1 0 0 1 0 3 10 10 9 9 0 10 10 9 8 10 10 6 8 10 5 10 4 6 5
Momingglory 2 3 0 0 0 0 0 0 0 2 2 10 10 10 0 10 6 4 4 10 10 2 2 10 5 10 4 10 10
Nutsedge 0 0 - 0 0 0 0 0 0 0 - 0 - - 0 0 0 0 0 - 0 0 - -
Rape 1 10 2 0 0 1 0 0 0 2 4 10 10 10 0 10 10 10 10 10 10 7 3 7 1 9 2 4 8
Redroot pigweed 3 10 2 2 5 8 0 0 0 2 10 10 10 10 0 10 10 10 9 10 10 7 7 10 10 9 10 10 10
Soybean 0 1 0 0 0 1 0 0 0 0 1 4 7 2 0 7 2 1 1 9 8 0 0 2 0 1 0 0 1
Sugarbeets 3 10 4 0 1 2 0 0 0 6 8 10 10 10 0 10 9 9 10 10 10 9 7 10 9 10 10 10 10
Velvetleaf 0 10 1 0 1 1 0 0 0 1 10 10 10 10 0 10 10 8 9 10 10 4 1 9 1 10 2 10 6
Wheat 0 0 1 0 0 0 0 0 0 0 2 4 2 3 0 5 5 4 2 5 3 0 0 3 0 4 0 3 1
Wild oats 2 4 1 0 1 0 0 0 0 1 9 9 9 9 0 9 10 7 8 8 9 1 3 9 0 7 4 5 5
TABLE B COMPOUND
Rate 250 g/ha 65 66 67 68 70 72 73 74 75 76 77 78
Preemergence
B. signalgrass 1 9 10 9 0 7 9 0 9 0 0 0
Bedstraw 0 3 9 6 0 5 9 0 6 - - 0
Blackgrass 0 8 8 7 0 4 10 0 9 0 0 0
Cocklebur 0 0 2 2 0 0 7 0 2 0 0 0
Corn 0 1 4 1 0 5 2 0 1 0 0 0
Crabgrass 0 9 10 9 0 9 10 0 9 0 1 0
Giant foxtail 0 2 10 9 0 7 10 0 5 0 1 0
Momingglory 0 3 10 5 0 8 9 0 10 0 1 0
Nutsedge 0 - - 0 - - 0 0 0 - - 0
Rape 0 4 10 4 0 9 6 0 4 0 0 0
Redroot pigweed 0 9 10 10 0 9 10 0 10 0 0 0
Soybean 0 0 3 2 0 3 1 0 0 0 0 0
Sugarbeets 0 10 10 10 0 10 10 0 10 0 0 0
Velvetleaf 0 8 10 7 0 7 7 0 9 0 3 0
Wheat 0 2 3 2 0 3 7 0 4 0 0 0
Wild oats 0 5 6 7 0 3 10 0 7 0 0 0
TABLE B COMPOUND
Rate 125 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Postemergence
B. signalgrass 6 - 3 2 4 - 1 8 3 3 5 5 2 4 1 5 2 2 2 4 7 5 2 3 1 5 5 3 2
Barnyardgrass - 4 4 8 2 1 1 5 2 - 2 2 5 8 3 4 1 2 0 4 5 5 3 4 0 2 4 3 3
Bedstraw 9 9 8 8 9 7 3 10 9 9 9 9 4 9 4 9 8 3 4 9 8 9 10 10 3 9 8 9 6
Blackgrass 7 6 2 4 4 2 0 8 1 3 3 3 2 9 1 6 2 1 2 4 8 7 3 4 1 4 5 3 1
Cocklebur 8 8 3 6 7 6 - 9 8 8 8 9 7 9 4 8 7 3 5 8 8 10 9 9 2 7 8 6 8
Corn 4 4 2 2 2 3 1 4 2 3 2 3 2 4 1 2 2 2 3 3 3 3 1 2 1 3 3 2 2
Crabgrass 9 9 2 7 3 8 0 9 2 4 3 4 2 9 2 4 2 2 3 6 9 9 8 7 1 4 9 6 1
Ducksalad - 0 3 0 0 0 0 6 1 - 1 1 2 6 0 5 2 2 0 4 4 4 2 4 0 1 3 3 4
Giant foxtail 7 9 2 3 2 4 1 5 2 4 3 3 1 7 1 4 1 0 2 8 6 5 2 6 1 4 4 4 1
Momingglory 8 9 7 8 3 8 1 10 7 10 9 7 6 8 1 8 8 3 4 8 10 9 10 10 3 8 3 10 5
Nutsedge - 0 0 0 0 - 0 1 0 1 0 0 0 2 0 0 0 0 0 2 0 0 1 1 0 - 3 0 0 v
Rape 9 9 6 10 9 8 5 10 9 9 9 8 6 9 2 8 7 2 4 10 10 10 10 10 6 8 9 9 8
Redroot pigweed 9 9 9 9 9 7 3 10 9 10 9 9 9 9 6 10 6 5 7 9 10 10 10 10 6 9 9 10 9
Rice - 4 4 2 1 2 0 6 2 - 2 0 4 7 1 4 0 0 0 4 4 4 1 4 0 1 2 2 1
S. Flatsedge - 5 9 6 3 5 1 9 9 - 6 4 8 8 2 3 1 2 0 8 8 8 1 5 1 5 8 6 6
Soybean 8 7 7 7 3 6 3 9 6 7 5 5 4 9 3 3 4 3 5 6 7 8 6 7 3 5 7 4 3
Sugarbeets 10 9 9 9 10 8 3 10 8 10 8 10 8 9 8 10 7 4 5 9 10 10 10 10 8 9 9 9 10
Velvetleaf 8 9 2 6 7 7 1 10 7 8 7 4 4 8 2 4 6 2 6 8 8 9 6 9 1 7 4 3 6
Wheat 2 2 2 2 2 2 0 3 3 2 3 3 0 4 0 3 3 0 3 4 4 4 2 4 0 4 4 3 2
Wild oats 7 3 2 2 4 3 0 4 2 3 3 3 1 7 0 4 5 1 3 5 6 6 3 3 0 4 5 2 2
TABLE B COMPOUND
Rate 125 g/ha 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64
Postemergence
B. signalgrass 3 2 1 1 1 1 0 1 1 1 3 7 4 4 0 4 5 3 1 8 9 1 3 2 2 4 2 3 5
Barnyardgrass 3 3 2 0 2 0 0 0 0 2 5 4 4 4 0 3 3 5 4 6 6 2 3 4 1 3 2 3 3
Bedstraw 6 6 9 3 6 7 1 7 3 4 9 9 10 9 0 9 - - 10 10 10 8 4 7 3 8 3 2 4
Blackgrass 2 2 1 1 1 0 0 0 1 2 6 7 6 5 0 5 5 6 5 9 9 1 1 3 1 4 1 3 5
Cocklebur 6 8 6 2 2 2 2 7 2 2 8 9 7 9 0 9 8 7 4 9 8 5 3 7 3 7 5 3 7
Corn 2 1 1 1 1 1 1 1 1 1 2 3 4 3 0 2 3 3 2 8 5 1 2 2 2 3 2 2 3
Crabgrass 8 2 0 1 2 1 0 0 0 1 9 7 8 4 0 6 9 6 2 10 8 2 4 6 3 3 3 3 5
Ducksalad 2 3 1 0 0 0 0 0 0 5 3 8 9 7 0 1 3 4 5 9 9 2 0 4 2 1 0 0 6
Giant foxtail 3 1 0 1 1 1 0 1 1 0 6 7 9 7 0 4 4 5 2 10 8 1 3 6 2 4 2 2 3
Momingglory 3 8 5 1 1 2 1 1 1 2 8 9 9 - 0 10 6 6 3 10 10 3 3 - 4 9 4 4 8
Nutsedge 0 0 0 0 0 0 0 0 0 - 0 0 2 2 0 - - - 2 - 3 0 0 0 0 0 0 - 0
Rape 8 8 7 3 6 5 3 3 1 6 10 10 10 10 0 9 10 9 10 9 9 8 8 7 3 7 2 4 4
Redroot pigweed 9 9 2 3 3 4 1 4 2 3 10 9 10 10 0 9 9 9 8 10 10 6 5 8 7 9 9 9 9
Rice 2 1 1 1 1 0 0 0 0 1 5 6 6 6 0 2 5 4 3 5 5 1 2 3 0 0 0 0 1
S. Flatsedge 7 5 7 2 2 5 0 3 2 4 7 9 9 9 0 5 7 4 8 9 9 8 8 7 5 7 6 7 8
Soybean 4 5 2 2 2 1 0 1 1 2 7 9 9 6 0 8 8 7 7 9 9 5 3 7 2 5 1 2 3
Sugarbeets 10 10 10 8 10 8 5 9 9 10 10 10 10 10 0 10 9 9 8 10 10 10 7 9 8 10 9 9 10
Velvetleaf 2 8 4 1 1 1 0 1 1 2 8 9 9 8 0 9 7 8 7 8 8 6 2 7 2 7 2 8 7
Wheat 3 2 1 1 0 1 0 1 1 1 3 3 4 3 0 3 5 5 3 9 7 1 2 2 3 3 2 2 3
Wild oats 3 3 2 1 1 1 0 1 1 0 5 6 5 4 0 4 8 6 3 9 8 1 2 1 2 3 1 2 4
TABLE B COMPOUND
Rate 125 g/ha 65 66 67 68 69 70 71 72 73 74 75 76 77 l i
Postemergence
B. signalgrass 1 3 7 3 3 0 2 4 9 1 2 0 0 0
Barnyardgrass 0 3 3 3 2 0 2 3 5 0 2 0 0 0
Bedstraw 3 3 9 6 9 1 - - 9 1 9 0 1 0
Blackgrass 0 3 8 3 3 0 3 5 7 0 6 0 0 0
Cocklebur 1 4 7 - 8 2 4 4 9 5 7 3 3 0
Corn 1 2 5 1 2 1 3 3 3 1 3 1 1 0
Crabgrass 1 7 9 8 4 1 3 6 9 0 4 0 2 0
Ducksalad 0 3 4 1 1 0 0 2 1 0 1 0 0 0
Giant foxtail 1 2 6 2 3 0 2 6 8 0 2 0 1 0
Momingglory 1 4 7 8 10 1 6 4 9 1 10 0 4 0
Nutsedge 0 1 2 0 - 0 - - 0 0 0 - - 0
Rape 1 3 8 6 8 1 7 7 10 1 7 2 1 0
Redroot pigweed 3 9 10 10 10 2 8 9 9 2 9 1 2 0
Rice 0 1 2 1 2 0 2 0 5 0 1 0 0 0
S. Flatsedge 0 8 8 7 4 0 2 3 3 0 0 0 0 0
Soybean 2 5 7 5 4 2 4 2 9 2 3 0 1 0
Sugarbeets 7 10 9 10 10 1 8 9 10 2 10 2 1 0
Velvetleaf 1 5 8 7 8 1 6 3 9 1 9 1 1 0
Wheat 1 2 4 2 4 0 4 3 4 1 2 0 0 0
Wild oats 1 2 7 2 3 0 2 2 7 1 3 0 0 0
TABLE B COMPOUND
Rate 125 g/ha 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Preemergence
B. signalgrass 9 - 2 - 8 4 0 9 1 3 8 8 0 9 2 7 1 0 1 3 9 9 3 2 0 1 5 3 4
Bedstraw 8 10 0 3 4 0 0 7 7 8 4 2 0 8 0 3 2 0 0 1 7 8 1 1 0 0 4 1 10
Blackgrass 9 7 3 9 3 0 0 9 2 3 4 4 0 10 0 6 0 0 2 3 9 9 2 5 0 2 5 1 2
Cocklebur 2 1 0 0 0 0 0 2 1 0 0 - - 0 0 1 1 0 0 0 - 0 0 0
Corn 1 1 0 0 0 0 0 1 0 0 0 1 0 1 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0
Crabgrass 10 10 1 6 9 2 0 10 7 7 4 10 1 10 0 8 0 0 1 6 10 10 3 0 0 2 4 4 3
Giant foxtail 10 10 8 10 9 6 0 10 7 9 7 10 4 10 3 10 0 0 0 8 10 10 6 4 1 5 9 4 5
Mo ingglory 10 9 3 7 4 1 0 10 3 8 6 10 0 7 0 1 4 0 0 1 10 8 4 3 0 2 2 2 1
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 1 0 0 0 0 0 0 0 0
Rape 10 10 1 4 10 2 0 9 4 9 5 6 1 9 0 2 0 0 0 3 7 3 2 7 0 2 2 1 2
Redroot pigweed 1 100 1 100 9 8 8 3 0 10 6 9 9 9 2 10 0 9 3 0 0 8 10 9 8 3 0 6 6 3 7
Soybean 1 1 0 0 1 0 0 1 0 1 2 1 0 1 0 0 0 0 0 0 1 1 0 0 0 0 0 0 0
Sugarbeets 10 10 8 8 10 3 0 10 - 10 8 10 5 10 1 8 6 0 0 8 9 8 3 8 0 1 2 3 9
Velvetleaf 10 6 1 6 7 2 0 8 7 6 4 7 0 7 0 1 0 0 0 8 8 3 1 0 0 0 1 0 2
Wheat 5 2 0 0 2 0 0 2 0 1 0 0 0 4 0 1 0 0 0 0 2 3 0 1 0 0 0 0 0
Wild oats 9 9 4 7 5 0 0 8 1 4 2 5 0 9 1 5 3 0 2 5 8 8 1 3 0 1 3 0 1
TABLE B COlIPOϋrND
Rate 125 g/ha 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64
Preemergence
B. signalgrass 9 6 1 0 0 0 0 0 0 0 6 9 9 8 0 9 6 1 1 9 9 1 1 9 3 7 4 7 9
Bedstraw - 8 1 0 0 0 0 1 0 - 2 8 9 5 0 9 8 7 7 10 8 3 0 6 0 4 1 4 8
Blackgrass 2 2 0 0 0 0 0 0 0 1 9 10 5 6 0 8 8 4 5 9 8 0 1 3 1 3 1 3 6
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 3 2 5 0 - 2 0 0 10 - 0 0 2 0 0 0 - 1
Corn 0 0 0 0 0 0 0 0 0 0 1 1 1 1 0 1 2 1 0 8 3 0 0 1 0 1 0 1 3
Crabgrass 4 1 0 0 1 0 0 0 0 0 9 10 10 4 0 9 10 7 9 10 10 4 0 9 2 5 3 6 10
Giant foxtail 5 2 1 0 0 0 0 1 0 1 9 10 9 5 0 9 10 8 7 10 9 5 1 10 2 9 2 3 2
Momingglory 2 2 0 0 0 0 0 0 0 1 1 10 10 9 0 10 6 3 3 10 10 2 1 6 2 3 2 7 10
Nutsedge 0 0 0 0 0 0 0 0 0 - - - 0 - 0 0 - - - 9 - 0 0 0 0 0 0 0 -
Rape 0 10 0 0 0 0 0 0 0 1 3 10 10 8 0 9 9 8 10 10 10 5 0 7 0 8 1 3 4
Redroot pigweed 2 10 0 0 0 0 0 0 0 1 10 10 10 9 0 10 9 8 9 10 10 2 2 10 9 9 9 9 9
Soybean 0 0 0 0 0 0 0 0 0 0 0 4 5 2 0 3 0 1 1 9 7 0 0 2 0 1 0 0 1
Sugarbeets 0 10 1 0 0 0 0 0 0 6 6 10 10 10 0 10 7 6 6 10 10 8 1 10 8 10 10 10 10
Velvetleaf 0 9 0 0 0 0 0 0 0 0 3 7 10 10 0 10 10 8 7 10 10 2 0 7 1 10 2 2 6
Wheat 0 0 0 0 0 0 0 0 0 0 1 2 2 1 0 3 3 4 2 3 2 0 0 2 0 3 0 2 0
Wild oats 1 3 0 0 0 0 0 0 0 0 9 8 9 7 0 8 9 6 4 7 5 0 1 8 0 5 3 3 4
TABLE B COMPOUND
Rate 125 g/ha 65 66 67 68 69 70 71 72 73 74 75 76 77 78
Preemergence
B. signalgrass 0 9 9 8 9 0 2 2 9 0 9 0 0 0
Bedstraw 0 2 9 5 9 0 1 - 8 0 6 - - 0
Blackgrass 0 3 4 5 4 0 2 1 9 0 8 0 0 0
Cocklebur 0 0 - - 2 0 0 0 1 0 0 0 0 0
Corn 0 1 4 1 0 0 1 4 1 0 0 0 0 0
Crabgrass 0 9 9 4 9 0 2 9 10 0 9 0 0 0
Giant foxtail 0 1 9 6 8 0 2 5 10 0 5 0 0 0
Momingglory 0 3 10 3 8 0 4 3 9 0 10 0 0 0
Nutsedge 0 - - 0 0 0 - - 0 0 0 0 - 0
Rape 0 0 9 3 8 0 7 5 6 0 3 0 0 0
Redroot pigweed 0 9 10 9 10 0 8 9 10 0 10 0 0 0
Soybean 0 0 2 1 1 0 0 3 1 0 0 0 0 0
Sugarbeets 0 10 10 10 9 0 3 10 9 0 10 0 0 0
Velvetleaf 0 4 9 7 8 0 6 4 4 0 8 0 0 0
Wheat 0 1 3 1 1 0 3 0 4 0 4 0 0 0
Wild oats 0 4 5 6 7 0 3 2 9 0 7 0 0 0
TABLE B COMPOUND
Rate 62 g/ha 1 2 4 5 6 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
Postemergence
B. signalgrass 3 - 1 3 - 5 2 3 4 5 2 4 1 4 2 1 2 3 5 4 2 2 1 3 4 3 1 3 1
Barnyardgrass - 3 4 2 0 5 1 - 2 2 4 6 2 4 2 0 0 3 4 4 2 3 0 1 3 2 3 2 2
Bedstraw 9 9 6 6 5 10 8 8 7 7 4 9 3 8 7 2 4 5 - 9 4 9 1 8 2 2 1 4 6
Blackgrass 7 3 3 3 0 3 1 2 2 3 1 6 1 3 2 1 2 3 5 6 2 3 0 4 4 2 0 2 1
Cocklebur 7 8 5 5 5 9 6 7 - 6 4 9 4 4 6 2 4 7 8 9 9 9 2 7 7 6 5 6 8
Corn 4 2 2 2 3 3 2 3 2 3 2 3 1 2 2 1 3 3 3 2 1 1 1 2 2 2 1 2 1
Crabgrass 4 8 4 2 5 9 2 2 2 3 2 9 2 4 1 1 2 3 9 7 8 7 1 3 3 4 1 4 1
Ducksalad - 0 0 0 0 4 1 - 0 0 2 6 0 3 1 0 0 3 3 2 0 3 0 0 2 1 3 1 2
Giant foxtail 3 7 2 2 - 4 2 2 2 2 1 7 1 2 1 0 2 1 6 2 2 3 1 3 3 3 1 2 1
Mo ingglory 4 8 8 3 3 10 5 7 9 7 2 8 - 7 3 3 3 8 10 6 8 10 3 5 3 8 2 3 7
Nutsedge - 0 0 0 2 0 0 1 0 0 0 0 0 0 0 0 0 2 0 0 0 1 0 2 0 0 0 0 0
Rape 9 9 9 8 8 9 8 9 7 6 5 9 1 7 4 2 3 9 10 10 8 10 3 8 9 8 4 8 8
Redroot pigweed 9 7 8 9 5 10 9 9 9 9 8 9 5 9 6 2 5 8 10 9 9 10 6 7 8 8 7 8 6
Rice - 3 2 1 1 5 0 - 1 0 4 6 1 4 1 0 0 3 3 3 1 3 0 0 2 1 1 1 1
S. Flatsedge - 3 5 3 3 8 6 - 4 2 8 7 1 2 9 0 0 6 3 4 0 3 0 5 5 1 4 4 2
Soybean 8 6 6 3 6 8 6 5 3 4 4 9 3 3 3 2 4 6 6 8 3 4 3 5 4 3 3 4 4
Sugarbeets 10 9 9 9 7 10 8 9 7 9 7 9 8 9 7 2 3 9 10 10 10 10 3 9 9 9 10 10 9
Velvetleaf 7 8 5 6 7 10 6 8 7 4 3 5 1 2 5 1 4 7 8 9 2 8 1 5 3 3 5 2 4
Wheat 2 2 1 2 1 3 2 2 3 2 0 4 0 3 1 0 2 4 4 3 2 2 0 3 3 2 1 1 1
Wild oats 4 3 2 3 0 3 2 2 3 3 0 6 0 3 3 0 2 4 5 5 2 3 0 3 4 1 1 2 1
Figure imgf000115_0001
TABLE B COM[POUND
Rate 62 g/ha 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64 65 66
Postemergence
B. signalgrass 1 1 1 1 0 1 1 1 2 6 4 3 0 3 4 2 1 2 4 1 3 2 2 3 2 4 4 1 2
Barnyardgrass 1 0 0 0 0 0 0 2 5 4 4 3 0 2 2 5 3 5 5 1 2 3 1 2 1 1 2 0 3
Bedstraw 9 2 6 6 1 7 3 4 9 9 9 8 0 8 9 9 9 9 9 5 3 7 2 8 3 2 3 0 2
Blackgrass 0 0 1 0 0 0 1 2 5 6 5 4 0 4 5 5 2 7 5 1 1 2 1 3 1 2 4 0 2
Cocklebur 3 2 2 1 1 4 2 5 7 9 - 8 0 8 7 7 4 6 8 5 3 4 3 3 2 1 6 1 3
Corn 1 1 1 1 1 1 1 1 2 3 3 3 0 2 3 3 1 7 4 1 2 1 2 2 1 0 1 1 1
Crabgrass 0 0 2 0 0 0 0 1 7 4 7 3 0 6 7 5 1 9 6 1 2 6 2 3 2 3 4 1 2
Ducksalad 0 0 0 0 0 0 0 1 2 1 8 4 0 1 3 4 4 8 9 0 0 3 1 0 0 0 4 0 2
Giant foxtail 0 0 1 0 0 0 0 0 2 6 8 2 0 3 4 2 1 8 7 1 2 6 2 2 1 2 1 1 2
Momingglory 2 1 1 1 1 1 1 2 8 8 9 10 0 9 6 2 3 10 10 - 2 7 2 5 3 2 2 - 2
Nutsedge 0 0 0 0 0 0 0 - 0 0 0 1 0 2 - - 2 7 1 0 0 0 0 0 0 0 0 0 0
Rape 6 2 6 4 1 3 1 6 10 10 9 9 0 9 10 9 9 9 9 8 7 6 3 6 2 3 3 1 3
Redroot pigweed 1 1 3 0 1 2 2 2 9 9 10 9 0 9 9 9 8 10 9 2 4 8 5 8 8 8 8 2 8
Rice 1 1 0 0 0 0 0 1 5 4 4 5 0 1 3 3 2 3 3 1 1 2 0 0 0 0 1 0 0
S. Flatsedge 3 2 1 2 0 0 0 2 5 9 9 9 0 4 7 4 6 9 9 5 6 7 4 3 3 4 8 0 6
Soybean 1 1 1 1 0 1 1 2 5 9 8 5 0 8 8 6 6 9 9 5 0 6 2 4 1 0 2 1 5
Sugarbeets 10 8 9 8 1 9 7 10 10 10 10 10 0 10 9 9 7 10 9 9 6 9 8 9 9 10 9 7 : L0 I
Velvetleaf 1 1 1 1 0 1 0 1 8 8 8 8 0 9 7 8 6 7 8 6 2 6 2 7 2 2 2 1 4
Wheat 0 0 0 0 0 1 0 1 2 2 3 3 0 3 5 4 3 6 4 1 0 1 2 3 1 2 2 1 2
Wild oats 1 0 1 0 0 1 1 0 4 6 4 4 0 3 6 5 2 8 6 1 1 1 2 3 1 3 3 1 2
TABLE B COMPOUND TABLE B COMPOUND
Rate 62 g/ha 67 68 69 70 71 72 73 74 75 76 77 78 Rate 62 g/ha 67 68 69 70 71 72 73 74 75 76 77 78
Postemergence Preemergenci
B. signalgrass 5 2 3 0 2 2 8 1 2 0 0 0 B. signalgrass 8 5 8 0 0 1 9 0 8 0 0 0
Barnyardgrass 3 2 1 0 2 2 4 0 2 0 0 0 Bedstjraw 7 3 7 0 - 0 2 0 3 - - 0
Bedstraw 9 5 9 1 - - 9 1 5 0 1 0 Bliackgrass 3 3 1 0 1 1 8 0 3 0 0 0
Blackgrass 5 2 2 0 2 4 7 0 3 0 0 0 Cocklebur - 0 0 0 - 0 0 0 0 0 0 0
Cocklebur 7 3 8 1 4 3 9 1 7 1 1 0 Corn 4 0 0 0 1 3 1 0 0 0 0 0
Corn 4 1 2 1 2 2 2 1 2 1 1 0 Crabgjrass 6 3 6 0 2 6 10
Figure imgf000116_0001
Crabgrass 7 5 3 0 2 4 7 0 - 0 0 0 Giant foxtail 7 3 4 0 1 5 10
Ducksalad 3 0 0 0 0 2 1 0 0 0 0 0 Momingglory 8 3 8 0 2 2 3 0 6 0 0 0
Giant foxtail 5 1 2 0 2 5 6 0 1 0 0 0 Nutsedge - 0 0 0 - - 0 0 0 0 0 0
Momingglory 7 2 9 1 1 - 9 1 10 0 2 0 Rape 7 2 7 0 2 4 2 0 2 0 0 0
Nutsedge 0 0 2 0 - - 0 0 0 - 0 0 Redroot pigweed 9 8 8 0 6 7 9 0 9 0 0 0
Rape 6 6 6 0 5 3 10 1 5 1 1 0 Soybean 1 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 9 9 10 0 8 8 9 2 9 1 2 0 Sugarbeets 9 9 9 0 2 8 9 0 9 0 0 0
Rice 1 0 0 0 2 0 5 0 1 0 0 0 Velvetleaf 8 2 - 0 - 3 2 0 2 0 0 0
S. Flatsedge 5 5 2 0 0 3 3 0 0 0 0 0 Wheat 3 1 1 0 1 0 2 0 0 0 0 0
Soybean 7 3 4 1 3 2 8 2 3 0 0 0 Wild oats 3 4 4 0 0 1 7 0 5 0 0 0
Sugarbeets 9 10 10 0 8 9 10 1 10 1 1 0
Velvetleaf 8 6 8 0 3 2 9 1 8 0 1 0
Wheat 3 2 3 0 4 3 4 1 2 0 0 0
Wild oats 5 2 3 0 2 2 6 1 3 0 0 0
TABLE B COMPOUND
Rate 62 g/ha 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
Preemergence
B. signalgrass 9 - - 3 1 8 1 2 3 7 0 9 0 3 0 0 0 2 5 9 2 1 0 0 2 1 1 3 2
Bedstraw 8 10 - 2 0 4 3 5 2 1 0 6 0 1 0 0 0 0 6 - 0 1 0 0 2 0 3 - 3
Blackgrass 8 3 6 2 0 4 1 3 1 2 0 9 0 2 0 0 1 1 8 6 0 1 0 0 2 1 0 1 1
Cocklebur 2 0 0 0 0 0 - 0 0 0 0 - 0 0 - 0 0 0 1 1 0 0 0 0 0 0 0 0 0
Corn 1 0 0 0 0 0 0 0 0 1 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 10 9 3 7 1 9 5 7 4 9 0 9 0 3 0 0 0 3 7 9 1 0 0 1 2 2 1 1 1
Giant foxtail 10 10 9 7 2 10 3 6 5 9 0 10 0 5 0 0 0 5 9 10 0 1 0 2 4 1 1 2 1
Momingglory 10 7 1 2 1 8 2 3 4 9 0 4 0 0 1 0 0 1 3 4 2 3 0 1 2 0 1 0 1
Nutsedge 0 0 0 0 0 0 0 - 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0 0 0 0
Rape 10 10 2 5 0 9 3 9 0 5 0 6 0 0 0 0 0 2 5 1 0 2 0 1 1 1 0 0 2
Redroot pigweed 1 100 1 100 3 8 0 9 3 9 7 7 0 6 0 4 0 0 0 7 9 9 0 1 0 2 5 0 2 1 8
Soybean 1 0 0 1 0 1 0 1 0 1 0 0 0 0 0 0 0 0 1 1 0 0 0 0 0 0 0 0 0
Sugarbeets 10 10 1 8 0 9 6 10 6 9 3 10 0 1 3 0 0 7 9 8 2 6 0 0 0 0 6 0 8
Velvetleaf 6 6 - 2 1 7 5 3 3 6 0 4 0 0 0 0 0 4 8 1 0 0 0 0 1 0 1 0 6
Wheat 1 1 0 1 0 1 0 0 0 0 0 2 0 0 0 0 0 0 2 2 0 0 0 0 0 0 0 0 0
Wild oats 8 6 2 3 0 5 0 2 1 3 0 8 0 2 2 0 1 4 7 7 0 1 0 0 3 0 1 0 2
TABLE B COM[POUfND
Rate 62 g/ha 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 49 50 51 52 53 54 59 60 61 62 63 64 65 66
Preemergence
B. signalgrass 0 0 0 0 0 0 0 0 2 9 5 6 0 9 5 0 0 4 8 0 0 7 2 5 4 4 8 0 9
Bedstraw 0 0 0 0 0 0 0 - 2 7 8 4 0 8 7 4 2 8 7 1 0 3 0 3 0 2 3 0 1
Blackgrass 0 0 0 0 0 0 0 0 7 6 2 5 0 8 3 4 3 7 5 0 0 2 1 1 1 2 5 0 3
Cocklebur 0 0 0 0 0 0 0 0 0 1 1 2 0 10 1 0 0 3 1 0 - 0 0 0 0 1 1 0 0
Corn 0 0 0 0 0 0 0 0 0 0 1 0 0 0 1 0 0 4 3 0 0 0 0 1 0 0 3 0 0
Crabgrass 0 0 0 0 0 0 0 0 8 9 8 4 0 9 8 5 6 10 9 - 0 8 0 3 2 3 9 0 6
Giant foxtail 0 0 0 0 0 0 0 0 6 10 7 4 0 9 9 5 2 8 9 1 1 8 2 8 1 2 1 0 0
Mo ingglory 0 0 0 0 0 0 0 0 1 9 9 8 0 10 1 1 1 10 9 1 0 6 1 - 1 2 4 0 2
Nutsedge 0 0 0 0 0 0 0 0 - 0 0 2 0 - - - - 3 0 0 0 0 0 0 0 0 0 0 0
Rape 0 0 0 0 0 0 0 0 3 7 8 4 0 9 7 7 6 10 9 2 0 5 0 4 0 3 3 0 0
Redroot pigweed 0 0 0 0 0 0 0 0 4 9 10 7 0 10 8 8 7 10 10 0 1 8 6 8 8 8 9 0 7
Soybean 0 0 0 0 0 0 0 0 0 2 1 0 0 1 0 0 1 9 4 0 0 1 0 0 0 0 0 0 0
Sugarbeets 0 0 0 0 0 0 0 2 3 10 10 9 0 10 7 6 6 10 10 4 0 10 6 10 8 10 9 0 9
Velvetleaf 0 0 0 0 0 0 0 0 1 10 10 8 0 10 8 3 4 10 10 0 0 7 1 9 1 2 4 0 1
Wheat 0 0 0 0 0 0 0 0 1 1 2 0 0 1 2 1 1 0 2 0 0 1 0 1 0 2 0 0 0
Wild oats 0 0 0 0 0 0 0 0 4 4 6 6 0 6 9 2 3 4 3 0 0 7 0 4 1 3 3 0 2
Figure imgf000118_0001
TEST C
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application) using a sandy loam soil mixture.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf momingglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb smartweed (Polygonum persicaria), lambsquarters (Chenopodium album), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla).
Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table C, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.
TABLE C COMPOUND TABLE C COMPOUND
Rate 140 g/ha 9 Rate 70 g/ha 9
POSTEMERGENCE POSTEMERGENCE
Arrowleaf sida 90 Arrowleaf sida 90
Barnyardgrass 25 Barnyardgrass 25
Cocklebur 80 Cocklebur 80
Common ragweed 10 Common ragweed 30
Corn 15 Corn 15
Cotton 90 Cotton 80
E . blacknightsh 100 E . blacknightsh -
Fall panicum 30 Fall panicum 20
Field bindweed 80 Field bindweed 70
Giant foxtail 30 Giant foxtail 15
H. beggarticks 80 H. beggarticks 70
I . momingglory 100 I . momingglory 60
Johnsongrass 50 Johnsongrass -
Ladysthumb 30 Ladysthumb 30
Lambscjuarters 100 Lambs-quarters 80
Large crabgrass 50 Large crabgrass 40
Purple nutsedge 5 Purple nutsedge 5
Redroot pigweed - Redroot pigweed 70 Soybean 50 Soybean 50
Surinam grass 20 Surinam grass 5 Velvetleaf 90 Velvetleaf 70 Wild poinsettia 100 Wild poinsettia 90
TABLE C COMPOUND
Rate 140 g/ha 1 2 3 9 15 21 23 42 43 46 52 66
PREEMERGENCE
Arrowleaf sida 100 100 0 95 85 90 100 100 100 100 100 100
Barnyardgrass 100 30 0 50 85 5 10 100 50 50 40 5
Cocklebur 0 10 0 0 5 0 5 60 - 5 20 0
Common ragweed 100 50 0 75 75 20 90 85 50 80 100 30
Corn 10 30 0 10 10 0 5 5 55 5 50 0
Cotton 100 15 0 50 10 20 75 60 10 40 70 0
E . blacknightsh 95 90 0 95 95 85 100 95 100 100 100 30
Fall panicum 95 100 0 100 100 90 100 100 100 100 100 100
Field bindweed 50 100 0 90 100 40 100 100 100 100 100 90
Giant foxtail 100 100 0 100 100 100 100 100 100 100 100 0
H. beggarticks 100 100 0 85 - 40 100 90 100 100 30 0
I . momingglory 20 5 0 50 65 0 40 100 100 50 100 10
Johnsongrass 100 60 0 95 100 5 80 85 30 50 80 10
Ladysthumb 95 - - 90 90 5 80 95 - 50 - 70
La bsquarters 100 100 0 100 60 90 100 100 100 100 100 100
Large crabgrass 100 100 0 100 100 100 100 100 100 100 100 100
Purple nutsedge 0 0 0 0 0 0 0 0 0 - 10 0
Redroot pigweed 100 100 0 100 100 100 100 100 100 100 100 100
Soybean 0 40 0 25 10 5 10 35 55 20 70 0
Surinam grass 95 35 0 90 80 10 60 70 10 25 70 20
Velvetleaf 100 50 0 100 70 50 50 95 100 80 100 0
Wild poinsettia 50 45 0 50 20 5 10 85 60 20 100 0
TABLE C COMPOUND
Rate 70 g/ha 1 2 3 9 15 21 23 42 43 46 52 66
PREEMERGENCE
Arrowleaf sida 95 20 0 95 85 85 100 95 100 90 100 5
Barnyardgrass 75 5 0 50 35 0 5 10 30 10 40 5
Cocklebur 0 - 0 0 0 0 - - - 10 0 0
Common ra-gweed 100 0 0 95 20 0 30 85 40 20 60 0
Corn 10 0 0 5 5 0 0 5 30 0 45 0
Cotton 60 5 0 35 10 5 75 60 0 5 0 0
E . blacknightsh 90 5 0 100 95 80 100 95 100 100 80 10
Fall panicum 90 5 0 90 80 0 100 85 100 100 100 80
Field bindweed 50 30 0 100 100 40 100 100 100 70 100 80
Giant foxtail 100 5 0 100 100 100 100 80 100 100 85 0
H. beggarticks 100 40 0 85 - 0 50 - 5 100 0 0
I . momingglory 15 5 0 50 20 0 - 70 100 50 100 10
Johnsongrass 95 5 0 85 85 0 20 70 30 45 50 5
Ladysthumb 90 30 - 85 20 - 80 85 - 10 - -
Lambsquarters 100 - 0 100 20 5 100 100 100 100 100 0
Large crabgrass 100 5 0 100 100 100 100 100 100 100 100 100
Purple nutsedge 0 0 0 0 0 0 0 0 0 - 5 0
Redroot pigweed 100 5 0 100 85 80 100 100 100 100 100 100
Soybean 0 0 0 20 10 0 5 5 5 0 55 0
Surinam grass 90 10 0 80 50 5 45 55 5 5 40 5
Velvetleaf 75 5 0 95 20 50 - 80 100 80 100 0 Wild poinsettia 10 0 50 30 50 15 40
TABLE C COMPOUND
Rate 35 g/ha 9
POSTEMERGENCE
Arrowleaf sida 80
Barnyardgrass 10
Cocklebur 60
Common ragweed -
Corn 10
Cotton 70
E . blacknightsh 100
Fall panicum 5
Field bindweed 60
Giant foxtail 15
H . beggarticks 65
I . momingglory 50
Johnsongrass 10
Ladysthumb 20
Lambsquarters 75
Large crabgrass 20
Purple nutsedge 5
Redroot pigweed 60
Soybean 40
Surinam grass 5
Velvetleaf 10
Wild poinsettia 90
TABLE C COMPOUND
Rate 35 g/ha 1 2 3 9 15 21 23 42 43 46 52 66
PREEMERGENCE
Arrowleaf sida 85 10 0 90 80 70 80 95 100 100 100 5
Barnyardgrass 20 0 0 10 10 0 0 5 10 5 30 0
Cocklebur 0 0 0 0 0 0 - 0 0 0 - 0
Common ragweed 80 0 0 80 10 0 10 20 0 10 40 0
Corn 5 0 0 0 0 0 0 5 0 0 0 0
Cotton 30 0 0 10 5 0 5 30 0 0 0 0
E . blacknightsh 90 5 0 95 70 40 95 90 100 80 40 0
Fall panicum 90 0 0 85 40 10 55 50 100 60 100 80
Field bindweed 65 0 0 50 65 - 20 95 100 10 100 40
Giant foxtail 100 0 0 90 70 85 85 70 100 100 70 0
H. beggarticks 20 40 0 85 - 0 50 0 0 0 0 0
I . momingglory 15 0 0 20 15 0 5 30 20 45 5 5
Johnsongrass 50 5 0 65 35 0 5 70 10 5 40 0
Ladysthumb 25 - - 35 0 0 5 90 - 25 - 0
Lambs-quarters 100 0 0 95 0 0 60 85 100 60 100 0
Large crabgrass 100 0 0 95 100 80 100 80 100 80 100 80
Purple nutsedge 0 0 0 0 0 0 0 0 0 - 0 0
Redroot pigweed 100 5 0 100 60 - 100 100 100 70 100 100
Soybean 0 0 0 20 0 0 5 0 0 0 0 0
Surinam grass 50 0 0 35 20 0 5 50 0 0 5 5
Velvetleaf 20 0 0 75 5 0 50 40 100 50 70 0
Wild poinsettia 0 0 0 10 0 0 5 25 10 0 - 0 TEST D
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were in the 1- to 4-leaf stage (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include alfalfa (Medicago sativa), 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 2 (Galium aparine), green foxtail (Setaria viridis), Italian ryegrass (Lolium multiflorum), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), lentil (Lens culinaris), littleseed canarygrass (Phalaris minor), pea (Pisum sativum), potato (Solanum tuberosum), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), scentless chamomile (Matricaria inodora), sorghum (Sorghum vulgare), spring barley (Hordeum vulgare), sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell (Veronica hederaefolia), spring wheat (Triticum aestivum), winter wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua), windgrass (Apera spica-venti) and winter barley (Hordeum vulgare).
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 D, 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.
TABLE D COMPOUND TABLE D COMPOUND
Rate 250 g/ha 1 22 Rate 125 g/ha 1 22 52
PREEMERGENCE POSTEMERGENCE
Alfalfa - - Annual bluegras - 70 50
Annual bluegras 85 50 Barley (winter) 10 10 10
Barley (winter) 40 10 Blackgrass 30 20 10
Blackgrass 70 40 Blk nightshade 50 100 65
Blk nightshade 100 50 Chickweed 70 100 80
Chickweed 90 30 Common poppy 100 100 100
Common poppy 100 70 Deadnettle 70 90 98
Deadnettle 90 10 Downy brome 10 20 20
Downy brome 100 10 Field violet 80 100 -
Field violet 85 - Galium 70 90 60
Galium 100 30 Green foxtail 20 35 30
Green foxtail 100 100 I . Ryegrass 10 10 10 I . Ryegrass 100 75 Jointed goatgra 10 15 10
Jointed goatgra 50 10 Kochia 70 70 70
Kochia 85 60 Lambscjuarters 50 60 80
Lambsquarters 70 70 LS canarygrass 20 60 20
Lentil - - Rape 85 90 85
LS canarygrass 70 50 Redroot pigweed 50 70 70
Pea - - Russian thistle 50 80 -
Potato - - Scentless chamo 60 80 70
Rape 100 50 Spring Barley 10 20 10
Redroot pigweed 70 70 Spring Wheat 20 20 10
Russian thistle 100 - Sugar beet 100 100 100
Scentless chamo 85 70 Sunflower 20 20 70
Sorghum - - Wheat (winter) 10 10 10
Spring Barley 40 2 Wild buckwheat 20 20 80
Spring Wheat - 5 Wild mustard 100 100 100
Sugar beet 100 80 Wild oat 30 65 10
Sunflower 30 30 Windgrass 30 - 50
Ivyleaf speedwe 100 -
Wheat (spring) 30 -
Wheat (winter) 40 5
Wild buckwheat 85 30
Wild mustard 98 30
Wild oat 90 30
Windgrass 100 30
TABLE D COMPOUND TABLE D COMPOUND
Rate 125 g/ha 1 22 52 Rate 62 g/ha 1 22 52
PREEMERGENCE POSTEMERGENCE
Alfalfa - - - Annual bluegras 50 30 20
Annual bluegras 100 100 100 Barley (winter) 10 10 10
Barley (winter) 30 20 60 Blackgrass 10 10 10
Blackgrass 60 60 90 Blk nightshade 50 90 65
Blk nightshade 100 60 90 Chickweed 80 60 70
Chickweed 85 70 85 Common poppy 100 100 100
Common poppy 100 70 - Deadnettle 70 50 100
Deadnettle 85 70 90 Downy brome 10 10 20
Downy brome 60 100 50 Field violet 100 100 -
Field violet 85 - - Galium 70 70 65
Galium 100 100 - Green foxtail 20 10 10
Green foxtail 100 100 100 I . Ryegrass 10 10 10
I . Ryegrass 100 65 70 Jointed goatgra 10 10 10
Jointed goatgra 70 20 40 Kochia 80 50 70
Kochia 100 65 100 Lambsquarters 60 60 80
Lambsquarters 70 70 100 LS canarygrass 20 20 10
Lentil - - - Rape 100 90 98
LS canarygrass 85 60 90 Redroot pigweed 70 50 60
Pea - - - Russian thistle 60 80 -
Potato - - - Scentless chamo 60 50 60
Rape 100 100 100 Spring Barley 10 10 10
Redroot pigweed 75 100 100 Spring Wheat 10 10 10
Russian thistle - - 85 Sugar beet 90 100 100
Scentless chamo 75 70 - Sunflower 20 10 50
Sorghum - - - Wheat (winter) 10 10 10
Spring Barley 20 10 80 Wild buckwheat 0 20 70
Spring Wheat 0 10 70 Wild mustard 100 100 98 99/28301
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Sugar beet 85 100 100 Wild oat 20 20 10
Sunflower 50 10 Windgrass 30 20
Ivyleaf speedwe 100 -
Wheat (spring) 50 -
Wheat (winter) 20 1 100 60
Wild buckwheat 85 5555 100
Wild mustard 100 6600 100
Wild oat 60 3300 60
Windgrass 100 7700 100
TABLE D COMPOUND TABLE D COMPOUND
Rate 62 g/ha 22 46 51 52 Rate 31 g/ha 1 52
PREEMERGENCE POSTEMERGENCE
Alfalfa Annual bluegras 50 20
Annual bluegras 60 20 90 100 100 Barley (winter) 10 10
Barley (winter) 20 0 2 90 50 Blackgrass 10 10
Blackgrass 50 30 60 80 80 Blk nightshade 60
Blk nightshade 90 10 50 95 40 Chickweed 50
Chickweed 85 40 70 90 80 Common poppy 100 100
Common poppy 100 60 100 100 - Deadnettle 70 100
Deadnettle 65 0 90 80 70 Downy brome 10 20
Downy brome 50 0 70 80 40 Field violet 100
Field violet 70 - 100 65 - Galium 60 50
Galium 100 20 60 100 - Green foxtail 10 10
Green foxtail 100 10 100 100 80 I . Ryegrass 10 10
I . Ryegrass 40 0 60 90 70 Jointed goatgra 10 10
Jointed goatgra 20 0 60 90 40 Kochia 60 70
Kochia 100 10 60 80 80 Lambsquarters 60 80
Lambsgiiarters 70 60 70 70 90 LS canarygrass 10 10
Lentil Rape 100 65
LS canarygrass 60 20 90 90 60 Redroot pigweed 70 60
Pea - ~ - - - Russian thistle
Potato Scentless chamo 60 50
Rape 75 20 100 100 60 Spring Barley 10 10
Redroot pigweed 70 60 70 70 90 Spring Wheat 10 10
Russian thistle 100 - 30 70 85 Sugar beet 75 100
Scentless chamo 70 60 70 70 - Sunflower 10 20
Sorghum Wheat (winter) 10 10
Spring Barley 20 0 5 80 60 Wild buckwheat 0 50
Spring Wheat 0 0 10 70 70 Wild mustard 100 70
Sugar beet 100 30 100 100 100 Wild oat 20 10
Sunflower 35 20 30 40 0 Windgrass 20 10
Ivyleaf speedwe 100 - 100 100 -
Wheat (spring) 10 - - - -
Wheat (winter) 10 0 2 55 60
Wild buckwheat 80 0 40 90 60
Wild mustard 100 30 100 100 90
Wild oat 60 0 70 95 50
Windgrass 100 20 100 100 100 O 99/28301
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TABLE D COMPOUND TABLE D COMPOUND
Rate 31 g/ha 1 46 51 52 Rate 16 g/ha 1 52
PREEMERGENCE POSTEMERGENCE
Alfalfa - - - - Annual bluegras 20 10
Annual bluegras 75 60 85 50 Barley (winter) 5 10
Barley (winter) 10 50 50 50 Blackgrass 10 10
Blackgrass 30 10 60 50 Blk nightshade 60 55
Blk nightshade 55 50 100 10 Chickweed 80 30
Chickweed 55 70 80 30 Common poppy 50 60
Common poppy 80 100 100 - Deadnettle 85 45
Deadnettle 60 90 80 50 Downy brome 2 10
Downy brome 30 70 80 30 Field violet 20 -
Field violet 20 85 65 - Galium 0 40
Galium 20 60 100 - Green foxtail 5 10
Green foxtail 60 80 100 50 I . Ryegrass 5 5
I . Ryegrass 10 60 60 30 Jointed goatgra 5 10
Jointed goatgra 10 50 60 30 Kochia 0 70
Kochia 40 60 85 50 Lambsquarters 0 70
Lambsquarters 10 65 70 90 LS canarygrass 10 10
Lentil - - - - Rape 65 65
LS canarygrass 20 70 80 30 Redroot pigweed 0 45
Pea - - - - Russian thistle 40 -
Potato - - - - Scentless chamo 30 30
Rape 30 50 100 50 Spring Barley 5 10
Redroot pigweed 75 70 70 90 Spring Wheat 5 10
Russian thistle 10 30 60 30 Sugar beet 45 100
Scentless chamo 30 65 65 - Sunflower 5 40
Sorghum - - - - Wheat (winter) 5 10
Spring Barley 10 30 70 50 Wild buckwheat 0 60
Spring Wheat 0 30 60 60 Wild mustard 85 60
Sugar beet 30 70 100 100 Wild oat 5 10
Sunflower 10 10 40 0 Windgrass 5 10
Ivyleaf speedwe 50 100 100 -
Wheat (spring) 10 - - -
Wheat (winter) 10 40 30 50
Wild buckwheat 40 40 90 40
Wild mustard 60 90 100 90
Wild oat 20 50 80 40
Windgrass 60 40 100 80
TESTE
Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), annual bluegrass (Poa annua), arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus- gallϊ), bermudagrass (Cynodon dactylon), citrus (Citrus sinensis), common chickweed (Stellaria media), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), common groundsel (Senecio vulgaris), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), green foxtail (Setaria viridis), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), Johnson grass (Sorghum halepense), kochia (Kochia scoparia), large crabgrass (Digitaria sanguinalis), leafy spurge (Euphorbia esula), pitted momingglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), quackgrass (Agropyron repens), Russian thistle (Salsola kali), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), Spanishneedles (Bidens bipinnata), sugarcane (Saccharum officinarum), Surinam grass (Brachiaria decumbens) and tall mallow (Malva sylvestris) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm).
Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence to the soil surface, postemergence to the plants or as a post directed spray to plants and soil at the base of the target species. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table E, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.
TABLE E COMPOUND TABLE E COMPOUND
Rate 500 g/ha 2 Rate 500 g/ha 2
PREEMERGENCE POSTEMERGENCE
A. bluegrass - Alexandergrass 95
Alexandergrass 100 Bermudagrass 75
Arrowleaf sida - Com . purslane 70
B. signalgrass - Com . ragweed 75
Barnyardgrass - Com . groundsel 75
Bermudagrass 100 Dallisgrass 95
Com. purs1ane 100 Goosegrass 95
Com. ragweed 100 Guineagrass 90
Com. chickweed - Itchgrass 95
Com. groundse1 100 Johnsongrass 95
Dallisgrass 100 Large crabgrass 90
Goosegrass 100 P . morninglory 90
Green foxtail - Purple nutsedge 0
Guineagrass - Sandbur 80
Itchgrass 100 Sourgrass 80
Johnsongrass 100 Spanishneedles 70
Kochia - Sugarcane 25
Large crabgrass 100 Surinam grass 80
Leafy spurge - Tall Mallow 100
P . morninglory 100
Purple nutsedge 0
Quackgrass -
Russian Thistle -
Sandbur 100
Sourgrass 100
Spanishneedles 100
Sugarcane -
Surinam grass 100
Tall Mallow 100 9/28301
125
TABLE E COMPOUND
Rate 250 g/ha 1 2 9 15 23 44 52
POSTEMERGENCE
Alexandergrass 90 80 10 20 80 10 75
Bermudagrass 30 50 10 20 10 0 35
Com. purslane 40 70 80 80 50 70 75
Com. ragweed 70 75 10 10 40 20 80
Com. groundsel 75 40 30 20 40 10 100
Dallisgrass 90 90 20 50 40 10 75
Goosegrass 70 90 10 30 75 20 75
Guineagrass 70 50 35 40 75 85 85
Itchgrass 85 90 30 85 80 10 40
Johnsongrass 90 80 85 100 65 10 20
Large crabgrass 85 80 10 40 40 10 80
P. morninglory 80 90 50 5 40 40 80
Purple nutsedge 0 0 0 0 0 0 50
Sandbur 10 50 0 0 20 0 60
Sourgrass 30 40 30 25 30 20 50
Spanishneedles 10 - 15 10 10 10 60
Sugarcane - 25 - - - - -
Surinam grass 30 70 10 40 - - 75
Tall Mallow 90 100 90 98 90 90 75
TABLE E COMPOUND
Rate 125 g/ha 2 9 15 44 52
POSTEMERGENCE
Alexandergrass 30 10 10 10 10
Bermudagrass 35 10 20 0 35
Com. purslane 65 80 75 70 50
Com. ragweed 75 10 5 10 50
Com. groundse1 20 25 0 10 100
Dallisgrass 70 10 5 10 5
Goosegrass - 5 20 10 5
Guineagrass 50 35 20 85 80
Itchgrass 75 30 80 5 35
Johnsongrass 60 85 98 5 35
Large crabgrass 75 5 10 10 5
P. morninglory 80 40 5 30 80
Purple nutsedge 0 0 0 0 40
Sandbur 10 0 0 0 5
Sourgrass 20 10 20 10 10
Spanishneedles 40 10 5 10 65
Sugarcane 20 - - - -
Surinam grass 50 10 35 - 75
Tall Mallow 100 90 85 85 90
TABLE E COMPOUND
Rate 250 g/ha 1 2 9 15 23 42 44
PREEMERGENCE
A. bluegrass - 100 - ; 100 - - -
Alexandergrass 100 loo loo : 100 98 90 50 60 95
Arrowleaf sida - 100 100 - - -
B. signalgrass - 100 - 98 - - - Barnyardgrass 100 75
Bermudagrass 100 100 100 98 98 98 100 100 100
Com . purslane 100 100 100 100 100 100 100 100 100
Com . ragweed 100 100 100 100 100 90 100 100 100
Com. chickweed 100 100
Com. groundsel 100 100 100 100 100 100 100 100 100
Dallisgrass 100 100 100 100 100 100 100 100 100
Goosegrass 100 100 100 100 100 100 100 100 100
Green foxtail 100 100
Guineagrass 100 100 100 100 100 100 100 98 100
Itchgrass 95 95 100 80 70 70 40 40 80
Johnsongrass 100 100 90 100 90 95 75 0 80
Kochia 100
Large crabgrass 100 100 100 100 100 100 60 100 100
Leafy spurge 100 98
P . morninglory 100 100 100 90 80 75 50 65 90
Purple nutsedge 50 0 0 0 0 30 0 0 10
Quackgrass 100 95
Russian Thistle 95
Sandbur 100 100 20 100 98 70 80 30 75
Sourgrass 100 100 100 100 100 100 100 100 100
Spanishneedles 100 100 60 100 100 90 98 90 50
Sugarcane 10
Surinam grass 100 100 100 100 - 100 - 55 100
Tall Mallow 100 100 100 98 90 100 98 100 98
TABLE E COMPOUND
Rate 125 g/ha 1 2 9 15 23 42 44 46 52 67
PREEMERGENCE
A. bluegrass 100 100 100
Alexandergrass 90 100 65 100 85 90 40 60 75 70
Arrowleaf sida 100 100 100
B. signalgrass 100 100 95
Barnyardgrass 80 100 40
Bermudagrass 100 100 100 98 98 98 98 100 100 90
Com. purslane 100 100 100 100 100 100 100 100 100 100
Com. ragweed 100 100 98 98 100 90 98 98 100 100
Com. chickweed 100 100 98
Com. groundsel 100 100 100 100 100 100 100 100 100 95
Dallisgrass 100 100 100 100 90 100 90 100 90 80
Goosegrass 100 100 100 98 98 100 98 98 100 100
Green foxtail 100 100 100
Guineagrass 100 100 90 100 98 100 100 100 100 100
Itchgrass 50 75 100 60 70 80 30 40 80 65
Johnsongrass 90 85 85 90 80 90 60 0 75 50
Kochia 100 - 95
Large crabgrass 100 100 100 100 100 100 70 100 100 98
Leafy spurge 100 100
P . morninglory 100 100 75 75 50 65 50 65 100 90
Purple nutsedge 0 0 0 0 0 30 0 0 50 5
Quackgrass 100 100 - 95
Russian Thistle - - - 95
Sandbur 95 90 10 50 80 70 70 10 50 65
Sourgrass 100 100 100 100 100 100 100 100 100 100 301
127
Spanishneedles 90 100 30 98 100 100 70 90 35 50
Sugarcane - - - 10 - - - - - -
Surinam grass 98 100 20 100 - 100 - 40 80 75
Tall Mallow 100 100 100 100 85 98 98 100 100 90
TABLE E COMPOUND TABLE E ( COMPOUND
Rate 64 g/ha 2 Rate 32 g/ha 2
POSTEMERGENCE POSTEMERGENCE
Alexandergrass 30 Alexandergrass 20
Bermudagrass 20 Bermudagrass 10
Com. purslane 65 Com. purslane 65
Com. ragweed - Com. ragweed 50
Com. groundse1 20 Com. groundsel 0
Dallisgrass 40 Dall .isgrass 10
Goosegrass 75 Goosegrass 60
Guineagrass - Guineagrass 5
Itchgrass 40 Itchgrass 40
Johnsongrass 60 Johnsongrass 10
Large crabgrass 35 Large crabgrass 35
P . morninglory 80 P . morninglory 80
Purple nutsedge 0 Purple nutsedge 0
Sandbur 10 Sandbur 0
Sourgrass 20 Sourgrass 10
Spanishneedles 60 Spanishneedles 60
Sugarcane 20 Sugarcane 20
Surinam grass 50 Surinam grass 35
Tall Mallow 95 Tall Mallow 98
TABLE E COMPOUND
Rate 64 g/ha 1 2 9 15 23 42 44 46 52 67
PREEMERGENCE
A. bluegrass 100 100 - 100
Alexandergrass 75 90 65 80 0 40 40 0 75 40
Arrowleaf sida 98 100 - 50
B. signalgrass 90 100 - 60
Barnyardgrass 70 95 - 0
Bermudagrass 100 100 98 98 98 95 80 98 90 90
Com. purslane 100 100 100 100 100 100 100 : 100 100 100
Com. ragweed 100 100 100 100 70 75 85 98 80 95
Com. chickweed 95 100 - 85
Com. groundsel 100 100 100 98 100 100 loo : 100 98 50
Dallisgrass 100 100 100 100 85 95 80 98 80 70
Goosegrass 100 100 100 98 98 100 98 90 100 90
Green foxtail 100 100 - 100
Guineagrass 100 50 85 100 98 95 80 85 80 : 100
Itchgrass 20 75 85 30 60 65 0 0 70 40
Johnsongrass 40 98 75 90 80 90 0 0 50 35
Kochia 100 - - 75 - - - - - -
Large crabgrass 100 100 100 100 98 90 60 98 100 95
Leafy spurge 95 98 - 65
P. morninglory 80 100 60 40 0 30 30 65 100 75
Purple nutsedge 0 0 0 0 0 30 0 0 30 5
Quackgrass 80 90 - 65
Russian Thistle - - - 90 - - - - - - Sandbur 65 65 0 20 80 40 60 10 10 60 Sourgrass 100 100 100 100 98 100 100 100 100 100 Spanishneedles 80 100 20 30 70 20 60 85 20 0 Sugarcane - 0 - 0 Surinam grass 35 90 10 20 50 0 70 75 Tall Mallow 100 100 100 100 85 98 80 100 98 90
TABLE E COMPOUND
Rate 32 g/ha 1 2 9 15 23 42 44 46 52 67
PREEMERGENCE
A. bluegrass 90 80 - 100
Alexandergrass 10 50 30 75 0 20 0 0 20 25
Arrowleaf sida 98 98 - 65
B. signalgrass 20 65 - 35
Barnyardgrass 5 20 - 0
Bermudagrass 100 98 70 98 90 90 30 70 70 70
Com. purslane 98 100 100 100 100 100 80 100 100 80
Com . ragweed 90 100 10 100 50 50 40 0 35 90
Com. chickweed 30 100 - 65
Com. groundsel 98 100 98 100 100 90 98 100 35 0
Dallisgrass 98 90 85 95 80 70 65 65 35 40
Goosegrass 100 95 90 98 98 98 98 85 20 80
Green foxtail 100 90 - 100
Guineagrass 90 50 20 90 80 95 20 60 60 80
Itchgrass 20 70 100 10 30 35 0 0 35 40
Johnsongrass 5 65 55 60 70 10 30 0 - 35
Kochia 95 - - 60
Large crabgrass 100 98 70 98 98 50 0 90 98 90
Leafy spurge 75 60 - 35
P . morninglory 70 100 45 5 0 - 20 65 50 60
Purple nutsedge 0 0 0 0 0 20 0 0 5 0
Quackgrass 65 20 - 65
Russian Thistle - - - 70
Sandbur 20 20 0 10 85 0 0 0 0 60
Sourgrass 100 100 85 100 98 100 80 98 95 98
Spanishneedles 40 80 0 50 60 20 20 65 20 0
Sugarcane - - - 0
Surinam grass 65 50 0 20 - 40 - 0 30 35
Tall Mallow 100 98 100 98 80 98 80 100 60 80

Claims

CLAIMSWhat is claimed is:
1. A compound selected from Formula I, geometric or stereoisomers thereof, N-oxides thereof and agriculturally suitable salts thereof,
Figure imgf000131_0001
wherein
Figure imgf000131_0002
J-1 J-2 J-3 J-4
Figure imgf000131_0003
J-5 J-6 J-7
A is
Figure imgf000131_0004
A-l A-2
W is N or CR11;
X, Y and Z are independently N or CR12; R1 and R2 are independently H, halogen, cyano, C1-C4 alkoxy, Cj-C haloalkoxy, C2-C4 alkoxyalkyl, CrC4 alkyl, CrC4 haloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy, S(O)nR13, C2-C4 alkylthioalkyl, C -C4 alkylsulfonylalkyl, C!-C4 alkylamino or C2-C4 dialkylamino;
R3 is H, F, Cl, Br, cyano, CrC4 alkyl, CrC4 haloalkyl or CO2R14; R4 is H, F, CrC4 alkyl, OH or OR14;
R3 and R4 can be taken together with the carbon to which they are attached to form C(=O) or C(=NOR14); R5 is halogen, cyano, SF5, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, Cj-C4 haloalkoxy or S(O)nR13; R6 and R10 are independently H, halogen, cyano, CrC4 alkyl, C]-C4 haloalkyl, Cj-C4 alkoxy, CrC4 haloalkoxy or S(O)nR13; R7 is halogen, cyano, SF5, C!-C4 alkyl, C!-C haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy or S(O)nR 13 ;
R8 is CrC4 alkyl or CrC4 haloalkyl;
R9 is H, halogen, cyano, SF5, C C4 alkoxy, C1-C4 haloalkoxy, C!-C4 alkyl, C!-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy or S(O)nR13; R ! l is H, halogen, cyano, C 1 -C4 alkyl, C 1 -C4 haloalkyl, C x -C alkoxy, C j -C4 haloalkoxy or S(O)nR13; R12 is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, Cj-C4 alkoxy, CrC4 haloalkoxy or S(O)nR13; each R13 is independently C1-C4 alkyl or C -C4 haloalkyl; each R14 is independently C1-C4 alkyl; and each n is independently 0, 1 or 2.
2. A compound of Claim 1 wherein
R1 and R2 are independently H, C2-C4 alkyl or C1-C4 alkoxy; R5 and R7 are independently halogen, Cj-C4 haloalkyl, CrC4 haloalkoxy or S(O)nRl3;
R6 is H or F; R8 is CrC4 alkyl;
R9 is halogen, cyano, CrC4 alkoxy, Cj-C haloalkoxy, CrC4 alkyl, CrC4 haloalkyl or S(O)nR13; R10 is H, halogen, cyano or C1-C4 haloalkyl;
R1 1 is H, halogen, cyano or C1-C4 haloalkyl; R12 is H, halogen, cyano or C1-C4 haloalkyl; and n is 0.
3. A compound of Claim 2 wherein W is N;
R5 and R7 are independently C1-C4 haloalkyl or C1-C4 haloalkoxy; and R9 is halogen, CrC4 haloalkoxy, C!-C4 haloalkyl or S(O)nR13.
4. A compounds of Claim 3 wherein
R1 is C1-C4 alkyl or Cj-C4 alkoxy; R2 is H;
R3 and R4 are independently H, F or methyl;
R5 and R7 are independently Cj-C2 haloalkyl or Cj-C2 haloalkoxy; and R9 is C j -C2 haloalkoxy, C j -C2 haloalkyl or S(O)nR 13.
5. A compound of Claim 4 wherein
J is J-1, J-5 or J-7.
6. A compound of Claim 3 wherein
R3 and R4 can be taken together with the carbon to which they are attached to form C(=O).
7. A compound of Claim 6 wherein
R1 is C1-C4 alkyl or C1-C4 alkoxy; R2 is H;
R5 and R7 are independently C1-C2 haloalkyl or C C2 haloalkoxy; and R9 is CrC2 haloalkoxy, CrC2 haloalkyl or S(O)nR13.
8. A compound of Claim 7 wherein
J is J-1 or J-5.
9. The compound of Claim 1 selected from the group consisting of:
(a) 5-ethyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[3-(trifluoromethyl)- lH-pyrazol-l-yl]pyrimidine;
(b) 5-ethyl-4-[[3-(trifluoromethyl)phenyl]methyl]-2-[3-(trifluoromethyl)-lH- pyrazol- 1 -yljpyrimidine; (c) 5-methyl-2-[4-(trifluoromethyl)phenyl]-4-[[3- (trifluoromethyl)phenyl]methyl]pyrimidine; (d) 5-methyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[4-
(trifluoromethyl)phenyl]pyrimidine;
(e) 5-methyl-4-[[3-(trifluoromethoxy)phenyl]methyl]-2-[3-(trifluoromethyl)-
1 H-pyrazol- 1 -yljpyrimidine;
(f) [5-methyl-2-[4-(trifluoromethyl)phenyl]-4-pyrimidinyl][3- (trifluoromethyl)phenyl]methanone;
(g) [5-methyl-2-[3-(trifluoromethyl)-lH-pyrazol-l-yl]-4-pyrimidinyl][3-
(trifluoromethyl)phenyl]methanone; and (h) 5-methyl-4-[[3-(trifluoromethyl)phenyl]-2-[3-(trifluoromethyl)-lH- pyrazol- 1 -yljpyrimidine.
10. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
11. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.
PCT/US1998/022088 1997-12-03 1998-10-20 Substituted pyrimidine and pyridine herbicides WO1999028301A1 (en)

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AU98096/98A AU9809698A (en) 1997-12-03 1998-10-20 Substituted pyrimidine and pyridine herbicides
DE69837621T DE69837621T2 (en) 1997-12-03 1998-10-20 SUBSTITUTED PYRIMIDINES AND PYRIDINES AS WEED CONTROLS
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