WO1998056789A1 - Pyrimidinyl azole herbicides - Google Patents

Pyrimidinyl azole herbicides Download PDF

Info

Publication number
WO1998056789A1
WO1998056789A1 PCT/US1998/011954 US9811954W WO9856789A1 WO 1998056789 A1 WO1998056789 A1 WO 1998056789A1 US 9811954 W US9811954 W US 9811954W WO 9856789 A1 WO9856789 A1 WO 9856789A1
Authority
WO
WIPO (PCT)
Prior art keywords
haloalkyl
methyl
compounds
trifluoromethyl
haloalkoxy
Prior art date
Application number
PCT/US1998/011954
Other languages
French (fr)
Inventor
Thomas Paul Selby
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU78313/98A priority Critical patent/AU7831398A/en
Publication of WO1998056789A1 publication Critical patent/WO1998056789A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • This invention relates to certain pyrimidinyl azoles, 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.
  • WO 96/06096 discloses herbicidal substituted pyridines of Formula i:
  • 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:
  • Q is O, S(O) n , NR 10 , CH 2 or CH 2 O, wherein the orientation of the CH 2 O group is such that the oxygen is bonded to the pyrimidine ring and the carbon is bonded to J;
  • W is O, S or NR 10 ;
  • X, Y, and Z are independently N or CR 8 ;
  • R 1 and R 2 are independently H, halogen, cyano, C j -C 4 alkoxy, C1-C4 haloalkoxy, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkoxyalkyl, C 3 -C 5 dialkoxyalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, S(O) n R ] 1, C 2 -C 4 alkylthioalkyl, C 2 -C 4 alkylsulfonylalkyl, C j -C ⁇ alkylamino or C 2 -C 4 dialkylamino;
  • R 3 is halogen, cyano, SF 5 , C 1 -C 4 haloalkyl, C1-C4 alkoxy, C ] -C 4 haloalkoxy or S(O) n RH;
  • R 4 is H, halogen, cyano, SF 5 , C 1 -C 4 haloalkyl, C]-C alkoxy, C 1 -C 4 haloalkoxy r or S(O) n RH;
  • R 5 is H, halogen, cyano, SF 5 , C 1 -C4 haloalkyl, C ] -C 4 alkoxy, haloalkoxy or
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, tt-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,
  • 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 ,
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Alkylsulfmyl includes both enantiomers of an alkylsulfmyl group. Examples of “alkylsulfmyl” include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfmyl and hexylsulfmyl 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 alkenylsulfmyl
  • 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.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • CF 3 CH 2 CH CHCH 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfmyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 ,
  • haloalkoxyalkoxy include CF 3 OCH 2 O, ClCH 2 CH 2 OCH 2 CH 2 O, Cl 3 CCH 2 OCH 2 O as well as branched alkyl derivatives.
  • the total number of carbon atoms in a substituent group is indicated by the "C j-C j " prefix where i and j are numbers from 1 to 5.
  • 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 .
  • 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.
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)__ j. then the number of substituents may be selected from the integers between i and j inclusive.
  • Compounds of this invention thus include compounds Formula I, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof.
  • the compounds of the 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.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • R 3 is halogen, C j -C haloalkyl, Cj-C haloalkoxy or C1-C 4 haloalkylthio;
  • R 4 and R 5 are each independently H or F;
  • R 6 is C ] -C haloalkyl, Cj-C 4 haloalkoxy or C r C4 haloalkylthio; and R 8 is halogen, C1-C4 haloalkyl, C 1 -C4 haloalkoxy, C1-C 4 haloalkylthio or C r C 4 alkylthio.
  • R 3 is C1-C 4 haloalkyl or C1-C 4 haloalkoxy.
  • Preferred 5 Compounds of Preferred 4 wherein J is J-l, J-5 or J-6. Most preferred are compounds of Formula I above selected from the group: (a) 5-methyl-2-[5-(trifluoromethyl)-l ,3,4-oxadiazol-2-yl]-4-[3-
  • 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.
  • 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 1-7.
  • the definitions of J, Q, A, R 1 , and R 2 in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention.
  • Scheme 1 illustrates the preparation of compounds of Formula I wherein a substituted chloropyrimidine of Formula 1 is coupled with a heterocyclic trialkylstannane or a heterocyclic boronic acid in the presence of a palladium(O) catalyst such as tetrakis(triphenylphospine)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, dimethoxy ethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 20 °C to 130 °C.
  • R a is alkyl
  • Scheme 2 illustrates the preparation of chloropyrimidines of Formula 1 wherein a substituted 2,4-dichloropyrimidine of Formula 2 is allowed to react with a compound of Formula 3 (wherein Q is O, S, ⁇ HR 10 or CH 2 O) in the presence of a suitable base such as potassium carbonate, potassium hydroxide or sodium hydride in a solvent such as NN- dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 °C to 130 °C.
  • a suitable base such as potassium carbonate, potassium hydroxide or sodium hydride
  • a solvent such as NN- dimethylformamide, acetonitrile or tetrahydrofuran
  • Dichloropyrimidines of Formula 2 can be obtained commercially or are 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. Heteroaryl stannanes and boronic acids can also be readily prepared by methods known in the art; for example, see Sandosham, J. and Undheim, K. Tetrahedron (1994), 50, pp 275-284; Undheim, K. and Benneche, T.
  • G is halogen
  • pyrimidinylstannanes of Formula 4 can be prepared by reaction of a chloropyrimidine of Formula 1 with a metal starmane of Formula 6 (where M is a metal such as sodium or potassium and R a is alkyl) in a suitable solvent such as tetrahydrofuran at temperatures ranging from -78 °C to room temperature.
  • Compounds of Formula I can also be prepared as shown in Scheme 5 by reaction of a methanesulfonyl-substituted pyrimidine of Formula 7 with a compound of Formula 3 (wherein Q is O, S, NHR 10 or CH 2 O) in the presence of an alkali or alkaline metal base such as potassium carbonate, potassium hydroxide or sodium hydride in a suitable solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 to 130 °C.
  • an alkali or alkaline metal base such as potassium carbonate, potassium hydroxide or sodium hydride
  • a suitable solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 to 130 °C.
  • Compounds of Formula 7 can be prepared from compounds of Formula 8 by treatment with an oxidizing agent such as w-chloroperoxybenzoic acid or Oxone® (potassium peroxymonosulfate) in a suitable solvent such as dichloromethane or ethanol (Scheme 6).
  • an oxidizing agent such as w-chloroperoxybenzoic acid or Oxone® (potassium peroxymonosulfate) in a suitable solvent such as dichloromethane or ethanol (Scheme 6).
  • Compounds of Formula 8 can be readily prepared from 2-cyanopyrimidines of Formula 9 by the methods taught in WO 96/06096 (Scheme 7).
  • Compounds of Formula 9 can be made from 2-chloropyrimidines of Formula 10 by treatment with trimethylamine in a solvent such as diethyl ether or tetrahydrofuran (in some cases under pressure) to give amine salts of Formula 11 which can then be treated with tetrabutylammonium cyanide in dichloromethane or with potassium cyanide in a solvent such as NN-dimethylformamide or acetonitrile.
  • Pyrimidines of Formula 10 can be prepared by reaction of a dichloropyrimidine of Formula 2 with sodium or potassium thiomethoxide in a solvent such as tetrahydrofuran at temperatures ranging from 0 to 100 °C.
  • Step A Preparation of 2-chloro-5-methyl-4-(methylthio pyrimidine Sodium thiomethoxide (5.0 g, 71 mmol) was added to a stirred solution of 2,4- dichloro-5-methylpyrimidine (10.0 g, 61 mmol) in 200 mL of tetrahydrofuran, and the mixture was stirred at room temperature overnight. The reaction mixture was then partitioned between 200 mL of ethyl acetate and 200 mL of water. The separated organic layer was washed twice with water and brine, dried over magnesium sulfate, and evaporated in vacuo to give a white solid which was suspended in a minimal amount of hexanes and filtered.
  • Step B Preparation of N.N.N, 5-tetramethyl-4-(methylthio -2-pyrimidinaminium chloride
  • a solution of the title compound of Step A (10 g, 57 mmol) stirring in a dry mixture of 100 mL of tetrahydrofuran and 100 mL of acetone was added 8 mL of trimethylamine via a gas addition funnel equipped with a cold-finger condenser. After stirring overnight, the reaction mixture was evaporated in vacuo to a wet paste which was triturated with diethyl ether to yield a solid.
  • Tetrabutylammonium cyanide (3.5 g, 13 mmol) was added to a mixture of the title compound of Step B (2.75 g, 12 mmol) stirring in 60 mL of dichloromethane. After stirring overnight at room temperature, the reaction mixture was heated at reflux for 1 h. Most of the dichloromethane was removed in vacuo and the residue was partitioned between ethyl acetate and water. The organic layer was separated, washed with water and brine and dried over magnesium sulfate. The solvent was removed in vacuo and chromatography on silica gel provided 1.05 g of the title compound of Step C as a white solid melting at 103-105 °C.
  • Step D Preparation of 5-methyl-4-(methylthio -2-pyrimidinecarbothioamide To a solution of the title compound of Step C (1.5 g, 9 mmol) stirring in 20 mL of ethanol, approximately 3 mL of hydrogen sulfide were added and the reaction mixture stirred at room temperature overnight. The solvent was allowed to evaporate and the remaining solid residue suspended in 20% diethyl ether in hexane and filtered to give 1.6 g of the title compound of Step D as a yellow solid melting with decomposition at 173-175 °C.
  • Step E Preparation of 5-methyl-4-(methylthio -2-[4-(trifluoromethyl -2- thiazolyllpyrimidine
  • a solution of the title compound of Step D (1.5 g, 7.4 mmol) and 3-bromo- 1,1,1 - trifluoropropanone (1.7 g, 8.9 mmol) in 35 mL of methanol was heated at reflux for several hours. The reaction mixture was partitioned between ethyl acetate and water.
  • Step F Preparation of 5-methyl-4-(methylsulfonylV2- 4-(trifluoromethylV2- thiazolyllpyrimidine
  • w-chloroperoxybenzoic acid (1 g, 57-86%) was added.
  • a solid slowly precipitated and the white slurry was stirred for 3 h at room temperature.
  • the reaction mixture was filtered and the solid washed with dichloromethane. After washing the filtrate twice with aqueous sodium bisulfite, aqueous sodium carbonate and brine, the organic layer was dried over magnesium sulfate.
  • Step G Preparation of 5-methyl-4-r3-(trifluoromethyl ' )phenoxyl-2- 4-(trifluoromethylV2- thiazolyllpyrimidine
  • the reaction mixture was partitioned between diethyl ether and water. The organic layer was separated and washed with 1 ⁇ aqueous sodium hydroxide and brine. After drying over magnesium sulfate, the solvent was removed in vacuo.
  • Step B Preparation of 5-methyl-4-(methylsulfonylV2-r5-(trifluoromethyl l .2.4- oxadiazol-3-yllpyrimidine
  • Step C Preparation of 5-methyl-2-[5-(trifluoromethyl -l ,2,4-oxadiazol-3-yl " l-4-
  • the reaction mixture was partitioned between ethyl acetate and water. The organic layer was separated and washed with water, 1 ⁇ aqueous sodium hydroxide and brine.
  • Step B Preparation of 5-methyl-4-(methylthio)-2-pyrimidinecarboxylic acid hydrazide
  • Step C Preparation of 5-methvI-4-(methylthioV2-[5-(trifluoromethvD-l .4-oxadiazol-2- yllpyrimidine Trifluoroacetic anhydride (1.1 g, 5.2 mmol) was added to the title compound of Step B (0.85 g, 4.3 mmol) stirring in 20 mL of tetrahydrofuran, keeping the temperature below 5 °C by cooling in an ice bath.
  • Step D Preparation of 5-methyl-2-[5-(trifluoromethylVl .3,4-oxadiazol-2-yl1-4-[3- (trifluoromethvDphenoxylpyrimidine
  • a solution of the title compound of Step C (0.35 g, 1.3 mmol) stirring in 10 mL of dichloromethane, /w-chloroperoxybenzoic acid (1.1 g, 57-86%) was added. A solid slowly precipitated and the white slurry was stirred for 1 h at room temperature. The solvent was evaporated in vacuo to give a residue which was dissolved in ethyl acetate.
  • Trifluoroacetic anhydride (0.4 mL, 3 mmol) was added to a suspension of the above solid (0.5 g) stirring in 25 mL of tetrahydrofuran. The reaction mixture was stirred at room temperature overnight followed by heating at reflux for 6 h. The reaction mixture was partitioned between ethyl acetate and water. The separated organic layer was washed with brine, dried over magnesium sulfate and evaporated in vacuo. The residue was passed through a plug of silica gel (25% ethyl acetate in hexane) to provide 300 mg of the title compound of Step A as a tan solid. H NMR (CDCI3): ⁇ 8.35 (s, 1H), 2.7 (s,3H), 2.3 (s, 3H).
  • Step B Preparation of 5-methyl-4- 3-(trifluoromethyl)phenoxyl-2- 5-(trifluoromethyl - 1.3.4-thiadiazol-2-yl "
  • pyrimidine To a solution of the title compound of Step A (0.3 g, 1 mmol) stirring in 10 mL of dichloromethane, / ⁇ .-chloroperoxybenzoic acid (0.9 g, 57-86%) was added. A solid slowly precipitated and the white slurry was stirred for 1 h at room temperature. The solvent was evaporated in vacuo to give a residue which was dissolved in ethyl acetate.
  • W is O.
  • X and Z are ⁇ R l R3 R 8 Rl R3 R 8
  • W is O.
  • X is N. and Z is CH 3
  • W is O.
  • X and Z are CH
  • W is S.
  • X is CH. and Z is N
  • ro rs CN CN CN CN CN CN CN to m to ⁇ r ⁇ to to n to cn to o t sn ot sn o to sn to U ot a to U to to ⁇ to a _ to cn to U to a t 00 1 cn u a U rs u a cn to U to X - a t
  • W is S.
  • X ar id Z are CH
  • W is O.
  • X and Z are N
  • W is S.
  • X and Z are CH
  • W is O.
  • X and Z are N
  • W is O.
  • X is N. and Z is CCN
  • W is S.
  • X is N. and Z is CC1
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible
  • 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.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, 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 can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 3 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
  • Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%,
  • Granule Compound 5 10.0% attapulgite granules (low volatile matter
  • Example D Extruded Pellet Compound 6 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).
  • the subject compounds are useful to modify plant growth.
  • a herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
  • Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • a mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, ami-role, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
  • Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
  • Plant species in the flood test consisted of rice ⁇ Oryza sativa), smallflower fiatsedge ⁇ Cyperus difformis), duck salad
  • Rate 500 g/ha 1 2 3 4 Rate 500 g/ha 1 2 3 4
  • Rate 250 g/ha 1 2 3 4 5 6 7 Rate 250 g/ha 1 2 3 4 5 6 7
  • Soybean 5 1 9 1 7 8 4 Wild oats 3 0 9 0 7 7 0
  • Rate 62 g/ha 1 2 3 4 5 6 7 Rate 62 g/ha 1 2 3 4 5 6 7
  • Soybean 3 1 9 1 7 7 4 Wild oats 2 0 9 0 2 6 0
  • Rate 31 g/ha 5 6 7 Rate 31 g/ha 5 6 7
  • Crop and weed species include arrowleaf sida ⁇ Sida rhombifolia), bamyardgrass ⁇ Echinochloa crus-galli), cocklebur ⁇ Xanthium strumarium), common ragweed ⁇ Ambrosia elatior), com 1 ⁇ Zea mays), cotton ⁇ Gossypium hirsutum), eastern black nightshade ⁇ Solanum ptycanthum), fall panicum ⁇ Panicum dichotomiflorum), field bindweed ⁇ Convolvulus arvensis), giant foxtail ⁇ Setariafaberii), hairy beggarticks ⁇ Bidens pilosa), ivyleaf morningglory ⁇ Ipomoea hederacea), johnsongrass ⁇ Sorghum halepense), ladysthumb smartweed ⁇ Polygonum persicaria), lambsquarters ⁇ Chenopodium album), large crabgrass
  • 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 B, 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.
  • Cocklebur 0 Cocklebur 0
  • Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. 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 C, 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.

Abstract

Compounds of Formula (I), geometric and stereoisomers, N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation, wherein J is formula (J-1), (J-2), (J-3), (J-4), (J-5) or (J-6); and Q, A, R1-R7 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 PYRIMIDI YL AZOLE HERBICIDES
BACKGROUND OF THE INVENTION
This invention relates to certain pyrimidinyl azoles, 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.
WO 96/06096 discloses herbicidal substituted pyridines of Formula i:
Figure imgf000003_0001
The pyrimidinyl azoles of the present invention are not disclosed in this publication.
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 imgf000003_0002
wherein J is
Figure imgf000004_0001
J-l J-2 J-3
Figure imgf000004_0002
J-4 J-5 J-6
A is
Figure imgf000004_0003
A-l A-2
Q is O, S(O)n, NR10, CH2 or CH2O, wherein the orientation of the CH2O group is such that the oxygen is bonded to the pyrimidine ring and the carbon is bonded to J;
W is O, S or NR10;
X, Y, and Z are independently N or CR8;
R1 and R2 are independently H, halogen, cyano, Cj-C4 alkoxy, C1-C4 haloalkoxy, CrC4 alkyl, CrC4 haloalkyl, C2-C4 alkoxyalkyl, C3-C5 dialkoxyalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy, S(O)nR] 1, C2-C4 alkylthioalkyl, C2-C4 alkylsulfonylalkyl, Cj-C^ alkylamino or C2-C4 dialkylamino;
R3 is halogen, cyano, SF5, C1-C4 haloalkyl, C1-C4 alkoxy, C]-C4 haloalkoxy or S(O)nRH;
R4 is H, halogen, cyano, SF5, C1-C4 haloalkyl, C]-C alkoxy, C1-C4 haloalkoxy r or S(O)nRH; R5 is H, halogen, cyano, SF5, C1-C4 haloalkyl, C]-C4 alkoxy,
Figure imgf000005_0001
haloalkoxy or
S(O)nRH;
R6 is halogen, cyano, SF5, CJ-C4 haloalkyl, C]-C alkoxy, Cj-C haloalkoxy or S(O)nRH; each R7 is independently C1-C4 alkyl or C j-C haloalkyl; each R8 is independently H, halogen, cyano, C J-C4 alkoxy, Cj-C4 haloalkoxy, Cj-C alkyl, C C4 haloalkyl, C2-C4 alkoxyalkyl, C3-C4 alkenyl, C3-C alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy or S(O)nR1 1 ; R9 is H, CrC4 alkyl or CrC4 haloalkyl; R10 is H, CrC4 alkyl or CrC4 haloalkyl; each R1 1 is independently C J-C4 alkyl or C1-C4 haloalkyl; 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, tt-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=CHCH2CH2O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3C≡CCH2O and
CH3G≡CCH2CH2O. "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. "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy. "Alkylsulfmyl" includes both enantiomers of an alkylsulfmyl group. Examples of "alkylsulfmyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfmyl and hexylsulfmyl 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", "alkenylsulfmyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfmyl", "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 w-chloroperbenzoic acid (MCPBN), 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 m 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. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and
CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfmyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2,
CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. Examples of "haloalkoxyalkoxy" include CF3OCH2O, ClCH2CH2OCH2CH2O, Cl3CCH2OCH2O as well as branched alkyl derivatives. The total number of carbon atoms in a substituent group is indicated by the "C j-Cj" prefix where i and j are numbers from 1 to 5. 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 compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)__j. then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R8 or R10, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention thus include compounds Formula I, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof. The compounds of the 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. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, geometric and stereoisomers thereof,
N-oxides thereof, and agriculturally suitable salts thereof, wherein W is O or ΝR10 when X, Y, and Z are CR8. Preferred 2. Compounds of Preferred 1 wherein Q is O; R1 and R2 are independently H, C1-C4 alkyl or Cj-C alkoxy;
R3 is halogen, Cj-C haloalkyl, Cj-C haloalkoxy or C1-C4 haloalkylthio; R4 and R5 are each independently H or F;
R6 is C]-C haloalkyl, Cj-C4 haloalkoxy or CrC4 haloalkylthio; and R8 is halogen, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 haloalkylthio or CrC4 alkylthio.
Preferred 3. Compounds of Preferred 2 wherein W is O or S; and X is CH or Ν. Preferred 4. Compounds of Preferred 3 wherein R2 is H; and
R3 is C1-C4 haloalkyl or C1-C4 haloalkoxy. Preferred 5. Compounds of Preferred 4 wherein J is J-l, J-5 or J-6. Most preferred are compounds of Formula I above selected from the group: (a) 5-methyl-2-[5-(trifluoromethyl)-l ,3,4-oxadiazol-2-yl]-4-[3-
(trifluoromethyl)phenoxy]pyrimidine;
(b) 5-methyl-4-[[l-methyl-3-(trifluoromethyl)-lH-pyrazol-5-yl]oxy]-2-[5- (trifluoromethyl)-l,3,4-oxadiazol-2-yl]pyrimidine; (c) 5 -methyl-4- [3 -(trifluoromethyl)phenoxy] -2- [5 -(trifluoromethy 1)- 1,3,4- thiadiazol-2-yl]pyrimidine;
(d) 5-methyl-4-[[l-methyl-3-(trifluoromethyl)-lH-pyrazol-5-yl]oxy]-2-[5- (trifluoromethyl)-l,3,4-thiadiazol-2-yl]pyrimidine; and (e) 5 -methyl-4- [3 -(trifluoromethy l)phenoxy] -2- [4-(trifluoromethy l)-2- thiazolyl]pyrimidine. 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 1-7. The definitions of J, Q, A, R1, and R2 in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention.
Scheme 1 illustrates the preparation of compounds of Formula I wherein a substituted chloropyrimidine of Formula 1 is coupled with a heterocyclic trialkylstannane or a heterocyclic boronic acid in the presence of a palladium(O) catalyst such as tetrakis(triphenylphospine)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, dimethoxy ethane, acetonitrile or tetrahydrofuran. Reaction temperatures range from 20 °C to 130 °C.
Scheme 1
Figure imgf000009_0001
1 Ra is alkyl
Scheme 2 illustrates the preparation of chloropyrimidines of Formula 1 wherein a substituted 2,4-dichloropyrimidine of Formula 2 is allowed to react with a compound of Formula 3 (wherein Q is O, S, ΝHR10 or CH2O) in the presence of a suitable base such as potassium carbonate, potassium hydroxide or sodium hydride in a solvent such as NN- dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 °C to 130 °C. Scheme 2
Figure imgf000010_0001
Dichloropyrimidines of Formula 2 can be obtained commercially or are 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. Heteroaryl stannanes and boronic acids can also be readily prepared by methods known in the art; for example, see 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, 1993, volume 60, pp 330-365.
An alternative method for preparing compounds of Formula I is illustrated in Scheme 3. Coupling of a pyrimidinylstannane of Formula 4 (where Ra is alkyl) with a heteroaryl halide of Formula A-G (where G is halogen) in the presence of a palladium(O) catalyst such as tetrakis(triphenylphospine)palladium(0) in a solvent such as dimethoxyethane or tetrahydrofuran at temperatures ranging from room temperature to heating at reflux affords compounds of Formula I. Scheme 3
Figure imgf000010_0002
G is halogen
As illustrated in Scheme 4, pyrimidinylstannanes of Formula 4 can be prepared by reaction of a chloropyrimidine of Formula 1 with a metal starmane of Formula 6 (where M is a metal such as sodium or potassium and Ra is alkyl) in a suitable solvent such as tetrahydrofuran at temperatures ranging from -78 °C to room temperature. Scheme 4
M+Sn-(Ra)3 6
Compounds of Formula I can also be prepared as shown in Scheme 5 by reaction of a methanesulfonyl-substituted pyrimidine of Formula 7 with a compound of Formula 3 (wherein Q is O, S, NHR10 or CH2O) in the presence of an alkali or alkaline metal base such as potassium carbonate, potassium hydroxide or sodium hydride in a suitable solvent such as NN-dimethylformamide, acetonitrile or tetrahydrofuran at temperatures ranging from 0 to 130 °C.
Scheme 5
Figure imgf000011_0001
Compounds of Formula 7 can be prepared from compounds of Formula 8 by treatment with an oxidizing agent such as w-chloroperoxybenzoic acid or Oxone® (potassium peroxymonosulfate) in a suitable solvent such as dichloromethane or ethanol (Scheme 6).
Scheme 6
oxidation
Figure imgf000011_0002
Compounds of Formula 8 (where N is a heterocycle of Formula A-l or A-2) can be readily prepared from 2-cyanopyrimidines of Formula 9 by the methods taught in WO 96/06096 (Scheme 7). Compounds of Formula 9 can be made from 2-chloropyrimidines of Formula 10 by treatment with trimethylamine in a solvent such as diethyl ether or tetrahydrofuran (in some cases under pressure) to give amine salts of Formula 11 which can then be treated with tetrabutylammonium cyanide in dichloromethane or with potassium cyanide in a solvent such as NN-dimethylformamide or acetonitrile. Pyrimidines of Formula 10 can be prepared by reaction of a dichloropyrimidine of Formula 2 with sodium or potassium thiomethoxide in a solvent such as tetrahydrofuran at temperatures ranging from 0 to 100 °C.
Scheme 7
Figure imgf000012_0001
10 11
Compounds of Formula I wherein Q is S(O)n and n is 1 or 2 can be prepared from compounds of Formula I wherein Q is S(O)n and n is 0 by treatment with an oxidizing reagent such as m-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. lH 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-(methylthio pyrimidine Sodium thiomethoxide (5.0 g, 71 mmol) was added to a stirred solution of 2,4- dichloro-5-methylpyrimidine (10.0 g, 61 mmol) in 200 mL of tetrahydrofuran, and the mixture was stirred at room temperature overnight. The reaction mixture was then partitioned between 200 mL of ethyl acetate and 200 mL of water. The separated organic layer was washed twice with water and brine, dried over magnesium sulfate, and evaporated in vacuo to give a white solid which was suspended in a minimal amount of hexanes and filtered. Additional solid was filtered from the filtrate several times and all of the crops combined to give 9.3 g of the title compound of Step A as a solid melting at 75-77 °C. ^H NMR (CDCI3): δ 8.02 (s,lH), 2.60 (s, 3H), 2.17 (s, 3H). Step B: Preparation of N.N.N, 5-tetramethyl-4-(methylthio -2-pyrimidinaminium chloride To a solution of the title compound of Step A (10 g, 57 mmol) stirring in a dry mixture of 100 mL of tetrahydrofuran and 100 mL of acetone was added 8 mL of trimethylamine via a gas addition funnel equipped with a cold-finger condenser. After stirring overnight, the reaction mixture was evaporated in vacuo to a wet paste which was triturated with diethyl ether to yield a solid. The solid was filtered, washed with diethyl ether and dried to give 2.9 g of a slightly impure sample of the title compound of Step B which was used directly in the next step. 1H NMR ((CD3)2SO): δ 8.6 (s,lH), 3.6 (s, 9H), 2.65 (s, 3H), 2.25 (s, 3H). Step C: Preparation of 5-methyl-4-(methylthio -2-pyrimidinecarbonitrile
Tetrabutylammonium cyanide (3.5 g, 13 mmol) was added to a mixture of the title compound of Step B (2.75 g, 12 mmol) stirring in 60 mL of dichloromethane. After stirring overnight at room temperature, the reaction mixture was heated at reflux for 1 h. Most of the dichloromethane was removed in vacuo and the residue was partitioned between ethyl acetate and water. The organic layer was separated, washed with water and brine and dried over magnesium sulfate. The solvent was removed in vacuo and chromatography on silica gel provided 1.05 g of the title compound of Step C as a white solid melting at 103-105 °C. iH NMR (CDC13): δ 8.2 (s,lH), 2.6 (s, 3H), 2.25 (s, 3H). Step D: Preparation of 5-methyl-4-(methylthio -2-pyrimidinecarbothioamide To a solution of the title compound of Step C (1.5 g, 9 mmol) stirring in 20 mL of ethanol, approximately 3 mL of hydrogen sulfide were added and the reaction mixture stirred at room temperature overnight. The solvent was allowed to evaporate and the remaining solid residue suspended in 20% diethyl ether in hexane and filtered to give 1.6 g of the title compound of Step D as a yellow solid melting with decomposition at 173-175 °C. ^H NMR (CDCI3): δ 9.2 (br s,lH), 8.35 (s, 1H), 8.00 (br s, 1H), 2.65 (s, 3H), 2.25 (s, 3H). Step E: Preparation of 5-methyl-4-(methylthio -2-[4-(trifluoromethyl -2- thiazolyllpyrimidine A solution of the title compound of Step D (1.5 g, 7.4 mmol) and 3-bromo- 1,1,1 - trifluoropropanone (1.7 g, 8.9 mmol) in 35 mL of methanol was heated at reflux for several hours. The reaction mixture was partitioned between ethyl acetate and water. The organic layer was separated and washed with water, saturated aqueous sodium bicarbonate and brine. After drying over magnesium sulfate, the solvent was removed in vacuo and chromatography on silica gel (25-30% ethyl acetate in hexane) afforded 1.35 g of a yellow solid melting at 91-97 °C). A solution of 0.6 g of the solid obtained above and 140 mg of/?-toluenesulfonic acid in 10 mL of toluene was heated at reflux overnight. The reaction mixture was then partitioned between ethyl acetate and water. The organic layer was separated and washed with water, saturated aqueous sodium bicarbonate and brine. After drying over magnesium sulfate, the solvent was removed in vacuo and chromatography on silica gel (15-20% ethyl acetate in hexane) afforded 0.35 g of the title compound of Step E as a yellow-tinted solid melting at 166-168 °C. *H NMR (CDCI3): δ 8.35 (s,lH), 7.9 (s, 1H), 2.7 (s, 3H), 2.3 (s, 3H).
Step F: Preparation of 5-methyl-4-(methylsulfonylV2- 4-(trifluoromethylV2- thiazolyllpyrimidine To a solution of the title compound of Step E (0.35 g, 1.2 mmol) stirring in 5 mL of dichloromethane, w-chloroperoxybenzoic acid (1 g, 57-86%) was added. A solid slowly precipitated and the white slurry was stirred for 3 h at room temperature. The reaction mixture was filtered and the solid washed with dichloromethane. After washing the filtrate twice with aqueous sodium bisulfite, aqueous sodium carbonate and brine, the organic layer was dried over magnesium sulfate. The solvent was removed in vacuo to give a yellow- tinted solid which was suspended in hexane and filtered to give 0.31 g of the title compound of Step F as a solid melting at 162-164 °C. lH NMR (CDCI3): δ 8.95 (s,lH), 8.0 (s, 1H), 3.5 (s, 3H) 2.75 (s, 3H). Step G: Preparation of 5-methyl-4-r3-(trifluoromethyl')phenoxyl-2- 4-(trifluoromethylV2- thiazolyllpyrimidine A mixture of the title compound of Step F (0.3 g, 1 mmol), 3 -trifluoromethy lphenol (0.2 g, 1.2 mmol) and potassium carbonate (0.33 g, 2.4 mmol) in 4 mL of N,N- dimethylformamide was stirred at room temperature for 1 h. The reaction mixture was partitioned between diethyl ether and water. The organic layer was separated and washed with 1 Ν aqueous sodium hydroxide and brine. After drying over magnesium sulfate, the solvent was removed in vacuo. The residue was purified by chromatography on silica gel (25-30%) ethyl acetate in hexane) to afford 320 mg of the title compound of Step G, a compound of this invention, as a white solid melting at 126-128 °C. lH ΝMR (CDCI3): δ 8.65 (s, 1H), 7.8 (s, 1H), 7.6 (m, 3H), 7.45 (m, 1H), 2.45 (s,3H).
EXAMPLE 2 Step A: Preparation of 5-methyl-4-(methylthio -2- 5-(trifluoromethyl)-l,2,4-oxadiazol-3- yllpyrimidine A mixture of 5-methyl-4-(methylthio)-2-pyrimidinecarbonitrile ( 1.5 g, 9 mmol), hydroxylamine hydrochloride (1 g, 14 mmol) and powdered potassium carbonate (2.5 g, 18 mmol) was stirred in 20 mL of methanol at room temperature for 3 h. The reaction mixture was concentrated in vacuo and 15 mL of water was added. The pH was adjusted to 7-8 by the dropwise addition of concentrated hydrochloric acid. The resulting precipitate was filtered, washed with water and diethyl ether, and oven dried to give 1.6 g of a white solid. To 1.5 g of the solid obtained above stirring in 20 mL of tetrahydrofuran at 0 °C, 1.5 mL of trifluoroacetic anhydride (11 mmol) were added followed by the dropwise addition of 2.5 mL of triethylamine (18 mmol). The reaction mixture was allowed to reach room temperature and stirred overnight. The reaction mixture was partitioned between diethyl ether and water. The organic layer was separated, washed with water and brine, and dried over magnesium sulfate. The solvent was removed in vacuo and the remaining solid residue suspended in hexane and filtered to give 0.9 g of the title compound of Step A as a white solid melting at 110-112 °C. *H ΝMR (CDCI3): δ 8.3 (s, 1H), 2.7 (s, 3H), 2.3 (s,3H). Step B: Preparation of 5-methyl-4-(methylsulfonylV2-r5-(trifluoromethyl l .2.4- oxadiazol-3-yllpyrimidine
To a solution of the title compound of Step A (0.9 g, 3.2 mmol) stirring in 20 mL of dichloromethane, m-chloroperoxybenzoic acid (2.8 g, 57-86%) was added. A solid slowly precipitated and the white slurry stirred 4 h at room temperature. The reaction mixture was filtered and the filtrate evaporated in vacuo to give a residue which was dissolved in 100 mL of ethyl acetate. After washing twice with aqueous sodium bisulfite, three times with aqueous sodium bicarbonate and brine, the organic layer was dried over magnesium sulfate. The solvent was removed in vacuo to give a white solid which was suspended in hexane and filtered to give 0.7 g of the title compound of Step B as a solid melting at 122-123 °C. ^H NMR (CDCI3): δ 9.0 (s, 1H), 3.5 (s, 3H), 2.8 (s,3H).
Step C: Preparation of 5-methyl-2-[5-(trifluoromethyl -l ,2,4-oxadiazol-3-yl"l-4-|"3- (trifluoromethvDphenoxylpyrimidine A mixture of the title compound of Step B (0.7 g, 2.2 mmol), 3- trifluoromethylphenol (0.35 mL, 2.7 mmol) and powdered potassium carbonate (0.7 g, 5 mmol) in 10 mL of NN-dimethylformamide was stirred at room temperature for 1 h. The reaction mixture was partitioned between ethyl acetate and water. The organic layer was separated and washed with water, 1 Ν aqueous sodium hydroxide and brine. After drying over magnesium sulfate, the solvent was removed in vacuo. to a solid which was suspended in hexane and filtered to afford 120 mg of the title compound of Step C, a compound of this invention, as a white solid melting at 104-105 °C. ΪH ΝMR (CDCI3): δ 8.6 (s, 1H), 7.6-7.5 (m, 4H), 2.4 (s,3H).
EXAMPLE 3 Step A: Preparation of methyl 5-methyl-4-(methylthioV2-pyrimidinecarboxylate Thionyl chloride (22 mL) was added dropwise to 5-methyl-4-(methylthio)-2- pyrimidinecarbonitrile (5 g, 30 mmol) stirring in 150 mL of methanol, keeping the temperature below 5 °C by cooling in an ice bath. After the addition of thionyl chloride, the ice bath was removed and the reaction was stirred at room temperature for 5 days. The reaction mixture was concentrated in vacuo and the residue partitioned between ethyl acetate and water. The biphasic system was slowly neutralized by addition of solid sodium bicarbonate. The organic layer was separated, washed with water and brine, and dried over magnesium sulfate. After removing the solvent in vacuo, a solid was triturated from hexane. Filtration and drying afforded 4.7 g of the title compound of Step A as a white solid melting at 116-117 °C. lH ΝMR (CDCI3): δ 8.3 (s,lH), 4.05 (s, 3H), 2.7 (s, 3H), 2.25 (s, 3H).
Step B: Preparation of 5-methyl-4-(methylthio)-2-pyrimidinecarboxylic acid hydrazide
Hydrazine monohydrate (0.54 mL, 11 mmol) was added to the title compound of Step A (2 g, 10 mmol) stirring in a mixture of 10 mL of methanol and 2.5 mL of water. After stirring overnight at room temperature, a thick precipitate formed. The reaction mixture was partitioned between dichloromethane and water. The organic layer was separated, washed with brine, and dried over magnesium sulfate. A wet paste was obtained after the solvent was removed in vacuo, and was triturated with 50% diethyl ether in hexane to yield a solid which was filtered and dried to provide 1.8 g of the title compound of Step B as a white solid melting at 149-152 °C. ΪH ΝMR (CDCI3): δ 8.9 (br s,lH), 8.3 (s, 1H), 4.15 (s, 2H), 2.65 (s, 3H), 2.25 (s, 3H). Step C: Preparation of 5-methvI-4-(methylthioV2-[5-(trifluoromethvD-l .4-oxadiazol-2- yllpyrimidine Trifluoroacetic anhydride (1.1 g, 5.2 mmol) was added to the title compound of Step B (0.85 g, 4.3 mmol) stirring in 20 mL of tetrahydrofuran, keeping the temperature below 5 °C by cooling in an ice bath. After the addition of trifluoroacetic anhydride, the ice bath was removed and the reaction mixture stirred 0.5 h. The reaction mixture was partitioned between ethyl acetate and 1 N aqueous hydrochloric acid. The separated organic layer was dried over magnesium sulfate and evaporated in vacuo. A solid (0.6 g) was obtained after triturating the residue with 50% diethyl ether in hexane and filtering. Phosphorous trichloride (0.34 g, 2.5 mmol) was added to 10 mL of NN- dimethylformamide at 0 °C. After stirring for 1 hr, the solid obtained above (0.6 g) was added at 0 °C. The reaction mixture was allowed to warm to room temperature and stirred overnight. Ice water was added and the aqueous mixture neutralized with aqueous sodium carbonate. After extracting with ethyl acetate, the organic layer was washed with brine, dried over magnesium sulfate and evaporated in vacuo. From the residue, a solid was triturated from 50% diethyl ether in hexane and filtered to afford 360 mg of the title compound of Step C. lU ΝMR (CDC13): δ 8.4 (s, 1H), 2.7 (s, 3H), 2.35 (s,3H). Step D: Preparation of 5-methyl-2-[5-(trifluoromethylVl .3,4-oxadiazol-2-yl1-4-[3- (trifluoromethvDphenoxylpyrimidine To a solution of the title compound of Step C (0.35 g, 1.3 mmol) stirring in 10 mL of dichloromethane, /w-chloroperoxybenzoic acid (1.1 g, 57-86%) was added. A solid slowly precipitated and the white slurry was stirred for 1 h at room temperature. The solvent was evaporated in vacuo to give a residue which was dissolved in ethyl acetate. After washing twice with aqueous sodium bisulfite, twice with aqueous sodium carbonate and brine, the organic layer was dried over magnesium sulfate. The solvent was removed in vacuo to give 350 mg of a white solid residue. This residue was dissolved in 5 mL of NN- dimethylformamide and 3 -trifluoromethy lphenol (0.2 g, 1.3 mmol) and powdered potassium carbonate (0.3 g, 2 mmol) were added. After stirring at room temperature for 1.5 h, the reaction mixture was partitioned between diethyl ether and water. The organic layer was separated, washed with brine, dried over magnesium sulfate and evaporated in vacuo. Chromatography on silica gel (25% ethyl acetate in hexane) afforded 330 mg of the title compound of Step D, a compound of this invention, as a white solid melting at l l6-117 °C. !H ΝMR (CDCI3): δ 8.7 (s, 1H), 7.6 (m, 3H), 7.5 (m,lH), 2.5 (s, 3H).
EXAMPLE 4 Step A: Preparation of 5-methyl-4-(methylthio -2-ι^5-(trifluoromethyl -l,3,4-thiadiazol-2- yllpyrimidine Phosphorous pentasulfide (2.4 g, 5.5 mmol) was added to 5-methyl-4-(methylthio)-2- pyrimidinecarboxylic acid hydrazide (0.9 g, 4.6 mmol) stirring in 10 mL of pyridine and the reaction mixture heated at reflux for 40 minutes. Ice water was added and the solid filtered, washed with water, and oven dried.
Trifluoroacetic anhydride (0.4 mL, 3 mmol) was added to a suspension of the above solid (0.5 g) stirring in 25 mL of tetrahydrofuran. The reaction mixture was stirred at room temperature overnight followed by heating at reflux for 6 h. The reaction mixture was partitioned between ethyl acetate and water. The separated organic layer was washed with brine, dried over magnesium sulfate and evaporated in vacuo. The residue was passed through a plug of silica gel (25% ethyl acetate in hexane) to provide 300 mg of the title compound of Step A as a tan solid. H NMR (CDCI3): δ 8.35 (s, 1H), 2.7 (s,3H), 2.3 (s, 3H).
Step B: Preparation of 5-methyl-4- 3-(trifluoromethyl)phenoxyl-2- 5-(trifluoromethyl - 1.3.4-thiadiazol-2-yl"|pyrimidine To a solution of the title compound of Step A (0.3 g, 1 mmol) stirring in 10 mL of dichloromethane, /τ.-chloroperoxybenzoic acid (0.9 g, 57-86%) was added. A solid slowly precipitated and the white slurry was stirred for 1 h at room temperature. The solvent was evaporated in vacuo to give a residue which was dissolved in ethyl acetate. After washing twice with aqueous sodium bisulfite, twice with aqueous sodium carbonate and brine, the organic layer was dried over magnesium sulfate. The solvent was removed in vacuo to give 250 mg of a tan solid residue. This residue was dissolved in 5 mL of NN- dimethylformamide and 3 -trifluoromethy lphenol (0.14 g, 0.9 mmol) and powdered potassium carbonate (0.2 g, 1.5 mmol) were added. After stirring at room temperature for 1.5 h, the reaction mixture was partitioned between diethyl ether and water. The organic layer was separated, washed with brine, dried over magnesium sulfate and evaporated in vacuo. Chromatography on silica gel (25% ethyl acetate in hexane) afforded 250 mg of the title compound of Step B, a compound of this invention, as a white solid melting at 125-
126 °C. iH ΝMR (CDCI3): δ 8.65 (s, 1H), 7.6 (m, 2H), 7.55 (s, 1H), 7.45 (m, 1H), 2.45 (s, 3H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 14 can be prepared.
Table 1
Figure imgf000018_0001
W is O. X and Z are Ν Rl R3 R8 Rl R3 R8
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
W is O. X is N. and Z is CH3
Rl Rl R8 Rl R! R8
CH3 CF3 CF3 CH2CH3 CF3 CF3
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
o o
00 m
Figure imgf000027_0001
o o 5 O 0 O o o o O 00
O o O O CΛ O t/ _ o o O o
( to o ( _ o o 0 l o to "fl t o to o O O
►fl Tj •fl o O
►f I F 00
"fl a u o fl U to a " a o t o
O to o t o a o a δ f
•f a O to to o O l
•A δ "f a O "A to to to a to to a l to to a to a "l to to t t-
O O O o O O O O O O O O O O O O O O O O O a O O O O a to a to a to a to a to a to a t a to a to a to a to a t a to a to to a to a to a to a to a to a to a to a to a to a t a to a
O O O O O O O O O O O O O O O O O O O O O O O IF a a a a a a a a a a a a a a a a a a a a a a a
CO CO CO
Figure imgf000027_0002
O O 00 o CΛ O 00 o O 00 O O t J O O o CΛ o O
O δ "fl O £ to O o o O a o a O to to O o O
O ► to o O O
►fl a O t? t O O O δ ►fl I IF o 00 a O t o to o ( _
O TJ a O to - a δ ►fl to o to a δ a to to to - a TJ to to ~ a to "fl to
Figure imgf000028_0001
W is O. X and Z are CH
Rl Rl RS Rl R! R8
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
W is S. X is CH. and Z is N
Rl Ri Ri Rl Ri Ri
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
CH3 CF3 C F5 CH2CH3 CF3 C2F5 oO oO oO oO oO oO oO oO oO oO oO o n o o o o n n o o n o n o o n n o n n o o o n o o n
O O O O O CΛ CΛ CΛ CΛ CΛ CΛ O O O O O O o n O O O O O o ►fl o ►fl ►fl ►fl ►fl ►fl CO CO 03 CO 00 00 O O O O O O O O O O O o o o o o o o y y O
►fl
UJ J UJ UJ UJ
Figure imgf000034_0001
t o 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 a a a a a a a a a a a to a to a to a to a to a to a to a to to 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 to to to to
O O O O O O a n a a a a a a a a O O O O O a a a a a a a a a a a a a
O O O O O CΛ ΓΛ ΓΛ ΓΛ 00 ΓΛ
O O O O O O
Tj J Tj Tj T UJ j ►A TJ O
►fl ►fl ►fl o o O
O O O O O o HH O O O O O CO CO CO CO CO CO O oO oO Oo O o n j o oO G ^ nG UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000034_0002
Figure imgf000035_0001
o o O O O O o O O O O O o O O O o a to a to a to a to a to a to a to a to a to a to a to a to a to a to a to a
O O O O O O O O O O O O O O O O X X X X X X X HH HU X X X X HH X X a a a a a a a a a a a a a a a a PS
o o o o o o o o 00 CΛ 00 CΛ 00 00 o o o o o o o o o o O
TJ •fl •fl ►fl IF DO DO DO DO DO CO O O O O
UJ Tj j j Tj o ►fl TJ — O O O O O UJ UJ UJ UJ UJ Q Ω — TJ
UJ
Figure imgf000035_0002
Figure imgf000036_0001
o o o o o to to to to to UJ UJ UJ UJ UJ
DO DO DO 00 CO
Figure imgf000037_0001
CΛ O o CΛ O
O O o o O o 00 O o CΛ O o CΛ O o O to o t O O J a Ω to O O O a TJ o O t O O O to O
►fl T o t O δ TJ l o O to O to O O O
►fl TJ o to o O o fl a δ to o
"fl δ a O to O O
•fl δ "f f a •fl
TJ TJ δ a "fl to Tj •fl δ to to ► to a lf a to "fl to • a to to ■l to PS o to O to a to ►fl
o o O O O O o o O O O O o o O O O O O O O O O O O O O O O to a to a to a to 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 to a to a to a to a to a to a to a to a to a
O O O 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 a a a a a a a a a a a a a a a ps a a X X a a a a a a a a a a a a a a a
oo oo oo oo oo oo O
DO DO DO DO DO O ►fl Oj O OTJ OTJ OTj oH— oi—. O O O O o oO Oo oO oO oO Gn O O
TJ TJ "fl "fl O CO CO CO CO CO UJ UJ UJ UJ J UJ TJ TJ TJ TJ Tj TJ UJ UΩ o J |F D
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000038_0002
ro rs CN CN CN CN CN CN CN CN to m to ιrι to to n to cn to o t sn ot sn o to sn to U ot a to U to to υ to a _ to cn to U to a t 00 1 cn u a U rs u a cn to U to X - a t
C _ (J o U to rs u u u U U u u ,c u a u U o a cn o
CN r r-s. U o U u 00 υ a t o U y u u U o Ό U u CΛ o u CΛ y ^ 00 u a o U u U u o υ rs u U
u cn m cn cn cn cn cn n m to to to to α to to to to to to -rs i cn cn cn
03 U U U U U u δ δ δ δ δ y υ -, U ζ-, (-) υ y y y y y y o3 a oa o3 Hq o3 <A, to to to
O O O O O O N «l U U U O
Os 00
^o
IΛ
00
Os m cn m cn cn cn rn cn cn cn cn cn cn cn cn cn m cn cn cn cn cn cn cn cn cn cn cn cn cn
TH to to to to to to to to to to to to HM to to to to a to a t X u u u u u u u u υ u u u u u u o f^\ x x x
O O O O O O O O O O O O O O O uO uO uO uO uO uO uO uO uO υO uO uO υO uO uO GO' Wl y u U
Oo Oo O O O a o O a oa o O O a o O a o O o o O a a a oa oO O O 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 a o a to to to to to to to to ot to to to to to to to to to to to to to to to to to
UJ J UJ UJ UJ UJ UJ J
Figure imgf000039_0001
Figure imgf000039_0002
^~
O O O O o O o o O n to to to to a O a a a O a a a a a a a a a a a a to to a to a to a to a to a to a to a to a to a to a o to to to a to a to a to to a to a to a to a to a
O O O O O O O O
U a O J a O a a U aJ U aJ U aJ aJ U aJ U aJ U aJ a O
U aJ U aJ U aJ a U aJ aJ U aJ U aJ U aJ UJ U aJ U aJ U aJ aJ U aJ
o o o o o o ) n o Λ 00 00 00 00 00 O O O O O O
TJ oTJ oTJ ,l D_.Or DO DO DO DO DO O Of
UJ UJ UJ ^ Tj OTj OTj OTj OTj OTj O■— O— O O O O O O UJ UJ UJ UJ UJ J — — ' OTJ OTJ OTJ OTJ O"fl "fl TJ "l UJ UJ UJ UJ UJ UJ UJ J
Figure imgf000039_0003
Figure imgf000039_0004
Figure imgf000040_0001
00 00 00 CΛ 00 00 \ to o
O O O O O O
cn cn cn cn cn cn cn m cn m cn cn n n cn cn a a a a a a a a X a a a a a a a to to to to to to to to to to to to to to to to to to -^ 1 u u u υ u u u u u υ u u u u u u
&Ά CN CN CN rs CN CN CN rs rs CN CN CN ^ rs CN rs a a a a a a a a a a a a a a a a u u u u u u u u u u u u u u u u oo
Figure imgf000040_0002
u u u υ ,u ■ u > •u ι —u
Figure imgf000040_0003
&
Os N 00 O cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn m to to to o to to to cn en en en en en en en en cn cn en en
O u u u u to tou ot X en cn c u tou t n u to uo u to to to to to t co' H
O O O O O O O O O O Ou Ou Ou Ou Ou Ou Ou uO tfl u X Xo uHH' Xu Xu αH Xu Xu oX αX oX HuH Xu Xu Xj Xu
Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Og Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo oO Oo Oo O O O O O O O O O O O O O to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
CΛ CΛ CΛ CΛ CΛ CΛ o nG G oo oo 00 00 00 00 w Ω Ω Ω Ω Ω Ω o o o o o o Oo Oo Oo Oo Oo O O O O O
Tj TJ Tj Tj DO DO DO DO DO DO O O O
►fl •fl ►fl ►fl ►fl Ω ►fl o —
Figure imgf000041_0001
o o o o o a a o oo o o o o o
X x X X X X X X X X X X X X X X X X x x x x to to a to a to a to to a too aa to a a o to a to a to a to to a
O a a O O n a a a a aa a a a a a a
Figure imgf000041_0002
Figure imgf000041_0003
Figure imgf000042_0001
Figure imgf000042_0002
Oo Oo Oo Oo Oo Oo Oo Oo oO oO Oo Oo Oo Oo Oo Oo Oo Oo Oo oO Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo to a a a to to to to to to to to to to to to to to to to to to to to to to to to to to J UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000043_0001
oo oo o oo 00 00 O O O O O O 00
00 DO DO DO DO 00 O O O G O O O O O O j ΩTJ oH- O— O O 03
TJ Tj TJ TJ T O O O O O O O O TJ 00 DO CO CO O
UJ UJ — j UJ
Figure imgf000043_0002
to HM HM to to to to to to to
Figure imgf000043_0003
00 00 00 00 00 00 O DO DO DO DO O O O O O O O OO OO O o
O O O O O O O O Oθ o CΛ
CO C 3 Q nτj 0 0 0
Tj Tj Tj j Tj Tj ►fl j ►fl 03 DO DO DO DO CO O
UJ UJ UJ
Figure imgf000043_0004
Figure imgf000044_0001
Figure imgf000044_0002
t o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o to to to to to to to t a a a a to to to to to to to to to to to to to to to to to to to too to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O IF to to to to HH to to to to to to to to to to to to to to to to to to to to to to to a to
UJ UJ UJ UJ UJ UJ UJ J UJ UJ UJ J UJ UJ UJ UJ UJ UJ
o o Λ oo oo 00 00 00
►fl o •fl o ►fl J DO DO DO 00 DO DO O O O
"fl IF J UJ J TJ "fl TJ O O O O O O O O O J Tl ,7 ,7 ,7 -7 ,7 ,7 w ω w w ^° w
Figure imgf000044_0003
Figure imgf000045_0001
Figure imgf000045_0002
O O O O O O O O O o to toa toto toto toto toto toto toto toto O O O O O O O O O IF a a a a a a a a a a a a a a a a a a a a a a a a a a X X x
O o o oo oo oo oo oo oo o o O O O O O O O O O O O O l IF 00 CO C
Tj TJ o Tj ►fl "f O 00 CO 00
T O
"flj O Tj O Tj O
" Tflj O Tl O Tj O •— O O O O O O O O "fl O O O
"fl "fl HH Tl "fl
Figure imgf000045_0003
Figure imgf000046_0001
cn cn cn cn cn cn cn cn cn to to to — u u u u u u u u .υ— to u tu u to ffl s- cn cn cn cn cn cn ΓT c^n cn cn cn cn t to ot to to ™ to to to to to
CQ 03 03 03 03 ot o 0 0 0 υ u to u to to o u u u u υ u u u u u u u —u —u —u —u
O O O O O O
Figure imgf000046_0002
cn cn cn cn cn cn cn cn cn cn en en cn en en to to to u u u o to to to to cn cn cn cn cn cn r__ _τ_ r__, r__ to to , u u u u u u to t
03 oa 03 oa CQ oa o to 0 0 0 u 00 u 00 u CΛ u CΛ u 00 u 00 u t υto uto to tou ng go g go ug og oυ u u u
Os
acn aen aen acn en aen acn aen acn acn acn acn ou ou ou ou ou ou ou oυ oy yo oy oy
Figure imgf000046_0003
Figure imgf000047_0001
cn cn cn en cn en en en cn cn cn en cn cn m cn cn en cn a a a a a a a a a a a a a a a a a a a to to to to to to to to to to to to to u u
Figure imgf000047_0002
rs u u u u rs u u u rs u u u u u u u u u u a a a a a a a a a a a a a a a a a a a u u u u u u u u u u u u u u u u u u u u u s
Figure imgf000047_0003
— u
Figure imgf000047_0004
en cn en en en cn cn cn cn en en cn en en cn cn en cn en en Xu u uHH Xυ u υ u u uHH u u u u uX
Figure imgf000047_0005
uX u Xu u Xu u
oO oO oO oO oO oO oO T' oO T oO T oO T oO T oO T oO hfl oO T oO O Hfl oμfl oO T T oO T, oO T< oO T oO >fl oO oO oO oO oO oO oO oO oO G Ωn Ω Ω, n , o O
T T T T "fl < >fl T T "fl T T T T to to to to Ωto Gto to to ot to to HH HL to to to to HM to ot HL to HL to to to to to to to to to to to to to u uj UJ UJ UJ UJ U aJ aJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ
ΓΛ 00 00 00 CΛ CΛ O O O O O O ΓΛ CΛ
CO CO 00 DO CO CO O O O O O T O HΓH
TJ f ►fl ►fl ►ofl o o o Ω Q O O O O . OT. TOJ OTJ O CO CO CO CO CO DO O
►fl •l J UJ UJ J — TJ J T| TJ ) _ UJ UJ UJ •fl Tj
UJ UJ U TJ TJ T
UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000048_0001
o o o o o o o o a a a a
X X X X X X X X X X X X X X X X X X X X X X X X x x x x x to to to t a to a t a to to a a O O O a a a a a a a
CΛ CΛ 00 00 00 00 O O O O O O
CO CO DO DO CO CO O O O O O O O O O O O O O O O O O O O O
Mi "fl j Tj o O 00 00
""l J Tj TJ Tj TJ Tj CO CO CO O O
■fl f TJ TJ TJ ►fl ►l ►fl CO CO 03
Tj UJ UJ UJ UJ UJ UJ UJ -i -i Tj TJ UJ UJ UJ
Figure imgf000048_0002
Figure imgf000049_0001
Figure imgf000049_0002
4 - o o o o o o o o o o o o o o o o o o o o o o o o n o o o o o a a a a to a to a to a to a to a to a to a to a to 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 to a to a to a to a to a to a to a
O O O n O IF a a a a a a a U aJ U aJ U aJ U aJ a a a a a a a U aJ U aJ aJ U aJ a a a a U aJ U aJ U aJ U aJ
o o O CΛ ΓΛ 00 00 ΓΛ ΓΛ O O O O O O
►fl •fl ►fl ►fl CO CO DO 00 DO 00 O O O O O O O O O O O O O
►fl ►fl ►fl ►fl ►fl O Tj OTj OTj OTj OTJ OTj
UJ UJ J f IF.
UJ J UJ •l
UJ UJ UJ
Figure imgf000049_0003
Figure imgf000050_0001
0
IF X X X X X X x x x x x x x x x x x x x x x x x x x x
Figure imgf000050_0002
δ δ δ o CΛ 00 00 00 00 00 O O O O O O G G 'fli o^ oTi oTi oTj oTj IF CO CO CO CO CO CO Oj OTj OJ OTj Oj O"lf o■—■ O O O O O O O O O O O f
UJ UJ UJ UJ UJ UJ "fl "l J
Figure imgf000050_0003
Figure imgf000051_0001
H υ
CL en en en en en en cn cn en en cn cn en en cn to to to < ι i H-, i u u u u u u u u u to to to to to to ι_ cn cn c en cn en rr- to to to to to , , , . ι - u u u u υ u cQ CQ 03 03 03 03 to to to ft . ^ o o o CΛ O 00 00 00 o u u u u u ^ u U U U U U U U U U U
O O O O O O
cn en cn en u to to to to to to to to to to to to X X X X X X X X eN uCN uCN urS uCN uCN uCN uCN υCN uCN uCN uCN u CN uCN uCN uCN uΓS uCN uCN uCN uCN a a a a a a a a a a a a a a a to uto uto uto uto uto uto uto uHL uto ua uto to to to to to to to to to
U U U U U U U U U
ON
Figure imgf000051_0002
Figure imgf000051_0003
Os 00 t^ SO IΛ cn m en en en en en cn cn en en cn en cn en cn
00 en en en en c en cn en en en en cn en cn c c cn en en en en to to ^ ^ ^ w w i τ W T W [fl W i p
Os a a a a a a a a a a a a a a a a a a a a a n r. r_ . r, i ri ri ri o c_ ci c_ c_> u u u u u u u u u u u u u u u u u u u u u ^ ^ ^ ^ ^ ^ g ^ ^ ^ ^ ^ ^ ^ g ^
O O to
O—'
Figure imgf000052_0001
Figure imgf000052_0002
O O O O O O O O O O O O O O O O O O O O O O to to toa toto toa toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto
O O O O O O O O O O O O O O O O O O O O O O IF to to to to to to to to to to to to to to a to a to to to to to to to to to to to HH to to to HH to
00 00 00 00 O O O O O O 00 CΛ CΛ 00 00 00
O O O O O O O O O O O O O O O O
Ω G G G G Ω ^ ^ ^ ^ ^ F CO CO CO CO CO CO o o o O O O O
J1 cjJ, ? cj ? cj? w ω ω ω ω
Figure imgf000052_0003
oO Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo oO Oo Oo Oo Oo oO Oo Oo Oo Oo Oo Oo Oo ^n gn ^n g ^ ^ yn ^nj .a . UJ U.aJ U.aJ .aJ .a .a UJ U.toJ UtoJ U.toJ .to x to X X a a a a a a a a a a a a j UJ J J UJ UJ J
00 CΛ ΓΛ CΛ CΛ CΛ O O O O O O
CO CO CO CO CO l o O O o O O O oo oo ff Tj TJ TJ Tj O TJ O TJ CO CO CO CO DO DO O O
►fl Tj ►fl TJ O TJ O TJ O — O O O O O
— — o Tj o o TJ o TJ o Tj o Tj J UJ UJ UJ UJ UJ UJ UJ Tj Tj
UJ UJ UJ UJ UJ UJ UJ UJ
Figure imgf000053_0001
o o o o o o o o
X X X X X X X X X X X X X X X X X X X X X X X X X X x toa toa toa toa toa toa ta toa
O o O a a a a a a a a
CΛ CΛ 00 CΛ CΛ 00 O O O O O O 00 00
CO CO CO 00 DO DO Oj OTJ OTj OTj OTj OTj O>—* O O O O O O O O O O O O O O O O O f TJ J ►fl Tj DO DO CO CO 00 00 O
►l ►fl Tj Tj j T
UJ UJ UJ UJ J O Tj
UJ J UJ J
Figure imgf000053_0002
Figure imgf000054_0001
O O O O O O 00 00 00 CΛ 00 CΛ u u u
r
Figure imgf000054_0002
u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u
Figure imgf000054_0003
m I en cn cn cn cn c- en cn cn en en cn cn en cn en en en to to to to to to to to to to to cn en c Oil to to to to u U U U U U u u u u u u υ u u u u u
O O O O O O u to u to to to to to
CΛ 00 u 00 u 00 u CΛ u ra 03 03 oa oa 03 Q CΛ u u υ
<υ
53
N O IΛ
00
OS X en cn en cn en en cn cn en cn en cn en cn en en en en cn cn cn en cn en en cn en cn en en cn en en c
X u uX uX uX Xu uX uX Xu Xu Xu uX uX Xu Xu X X co' u u uX Xu Xu uX uX Xu uX Xu X X a a a a u u Xu uX Xu uX u u u u
O O O O
Figure imgf000055_0001
Figure imgf000055_0002
0 0 0 0 O 0 0 0 to a to a to a to a to a to a to a to a to a
0 0 0 0 0 0 0 0 0 PS HH MH X X X X H X MH X X X vX MH X MH I X G "X MM *J-i X a a a a a a a a a
Figure imgf000055_0003
Figure imgf000055_0004
Figure imgf000056_0001
Figure imgf000057_0001
O O O O O O O O O O O O O O O O O O O O O to to to a a a a
Figure imgf000057_0002
Figure imgf000058_0001
H υ CL en cn cn en en en cn en en cn cn cn en cn en cn en to to υ 3 CQ 03 to to to to to to fi to to to to to to — to to to to to to tΛ C υ CQ 03 03 0 Λ υ u u u υ υ υ u u υ υ υ υ u u υ υ u 03 03 03 03
O O O O O O u υ CQ
00 00 0 υ0 υ CΛ υ CΛ υ 00
en cn en cn cn cn cn cn a a a a a X a a υ υ rs u u υ rs u υ rs υ a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a υ u υ u u υ υ u
Figure imgf000058_0002
en en cn cn en cn en en en cn en en en cn cn cn en to to j~ t to to to to to — υ υ oa t υ to to to to to to -
03 03 CQ CQ CQ to
CΛ CΛ u υo υ to toto o .o o υ υ tot ^ u υ υ υ υ u υ υ υ υ υ υ υ υ υ υ υ υ oa CQ CQ CQ CQ
O O O O O O CΛ CΛ CΛ CΛ CΛ CΛ
cn en en en en en cn en en en cn en en en cn en
Figure imgf000058_0003
υa aυ aυ υa υa υa υa υa aυ ua υa a O O O O O O Oυ a Oυ υa a a O O O O O O Oυ Ou
Figure imgf000059_0001
o O O O O O O O O O O O O O O O O a a a a a t a t a to a to a t a to a to a to a to a to to a to a to a to a O O to a to a to a to a t a to a O to a O O O to a O to a to a to a to a O to a O O to a to a O to
O O O O O O O O O O O O a O O O O O O O O O O O IF a a U aJ U aJ U aJ U aJ aJ U aJ U aJ U aJ U aJ aJ UJ U aJ U aJ U a O O J UJ J U aJ U aJ U aJ U aJ aJ U aJ U aJ aJ U aJ U aJ U aJ U aJ C aJ U aJ
O
Figure imgf000059_0002
Figure imgf000059_0003
Figure imgf000060_0001
Figure imgf000060_0002
O O O O O O O O O to to to to to to to HM to o to to to to to to to to
O O O O O O O O O IF X X X X X X X X X X X X X X X X X X X X X X X X X to to to to to to to HM to
O o o o o o O O O O n
Ω o ^ O O O
TJ DO DO O O O O O O O O O O O O
Tl IF 00 DO DO OO o o o o o o τ
Figure imgf000060_0003
Figure imgf000061_0001
υ
C cn en en en en en cn en en en en en e to to to — — to to to to to to >- cn en en en en n cn o to to to rcn en to to to to to to — υ υ υ υ υ υ υ υ υ u υ υ υ υ u 0 CQ CQ CQ 03 CQ t . ft ^ . υ υ υ υ υ υ u o o o 00 00 00 00 00 00 υ υ υ υ υ υ υ υ υ o o o o o o
Figure imgf000061_0002
en en en cn en cn cn en en cn en en cn en en en en cn en cn en rr. rτ. rτ. rτ. υ υ υ υ υ r υ ft υ ft utf
O Oυ υO υ υ υ υ CΛ CυΛ CΛ CυΛ CυΛ CυΛ m m m m cQ ø υ ft υ ft υ ft 0 υ 0 υ υ0 0 υ 0 υ 0 u u υ υ υ
Os
Figure imgf000061_0003
Figure imgf000062_0001
∑. to to to to S to
Figure imgf000062_0002
OHH
Figure imgf000062_0003
Figure imgf000062_0004
Figure imgf000063_0001
υ to cn en cn cn en en en en _T cn en en en cn en cn en en t to to to to to to to ot I- u υ 03 03 CQ CQ 03 03 to to to to to o oo oo υ υ u υ υ υ υ υ υ u u u υ υ υ υ ϋ υ υ υ υ υ υ υ cQ m (≤ CQ 03 o o o o o o
. a a a a a a a a a a a a a a a a a a a a a a a a a a a a a
Figure imgf000063_0002
SO
Figure imgf000063_0003
en en cn en en cn to s- tπ ι~ cn cn cn cn en cn en en en cn to to to (to to cn t to to to to
0 υ0 υ00 cQ υ uQ υQ υ υ υ υ υ u to o CQ ca pa oa oa ft ftCJ ft ftCJ ft ftU uQ υQ υQ Q OuO υCΛ υOO υOO υ CQ m 03 CQ 03 OO υCΛ
o o 0 ^ cn en en cn cn en en cn en en en en en en en en en cn rn en en s en en en en m a cn . men .ern, . rers ^' ^ -.f1 ^1 ^n ^ en cn cn en ' - ^ - ^ -• ^ - .. ^ -- ^ -. ^ -. ^ -. ^ -. ^ -. ^ _. p _H. ^ _. ^ _. ^_. p_H.H H-^. H.^. ^_. y^ u a' u a υ a oυ oϋ oυ oυ oυ ou oυ oυ oυ oυ oϋ oυ oυ ou oϋ oυ oυ ou ou υo oϋ oυ oυ oυ o_ yHH. y^ y y υ a υ υ a υ a υ a o_ o_ o^ o=
Figure imgf000064_0001
a a a a
Figure imgf000064_0002
Figure imgf000064_0003
cn .en cn cn cn c ^ ^ ^ p_ ^ t^ _H __ _ „ „ ^ ^ ^ c n c > m ^ m u HMI ft υ ftυ ftu ftu ftυ ftυ o0 δ0 υ0 0υ 0u u0 υ ϋ υ υ ϋ υ ft d ftoo υo υoo fto υoo m m m m m ffl ft u ftυ ftu ftυ ω .3
OS N
Figure imgf000064_0004
Figure imgf000065_0001
Figure imgf000066_0001
CH3 OCF3 C F5 CH2CH3 OCF C2F5
Figure imgf000067_0001
Figure imgf000067_0002
Figure imgf000068_0001
CH3 OCF3 CC1CF2 CH2CH3 OCF3 CC1CF2
CH3 OCF3 C F5 CH2CH3 OCF3 C2F5
W is S. X ar id Z are CH
Rl Ri Ri Rl Ri Ri
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
CH3 CF3 C F5 CH2CH3 CF3 C F5
CH3 OCF3 CF3 CH2CH3 OCF3 CF3
CH3 OCF3 CC1CF2 CH2CH3 OCF3 CC1CF2
CH3 OCF3 C2F5 CH2CH3 OCF3 C F5
Table 4
Figure imgf000069_0001
W is O. X and Z are N
Rl Ri Ri Rl Ri Ri
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
CH3 CF3 C2F5 CH2CH3 CF3 C2F5
CH3 OCF3 •CF3 CH2CH3 OCF3 CF3
CH3 OCF3 CC1CF2 CH2CH3 OCF3 CC1CF2
CH3 OCF C2F5 CH2CH3 OCF3 C2F5
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000080_0002
W is S. X and Z are CH
Rl Ri Ri Rl Ri Ri
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
CH3 CF3 C F5 CH2CH3 CF3 C2F5
CH3 OCF3 CF3 CH2CH3 OCF3 CF3
CH3 OCF3 CC1CF2 CH2CH3 OCF3 CC1CF2
CH3 OCF3 C F5 CH2CH3 OCF3 C2F5
Table 7
Figure imgf000080_0003
W is O. X and Z are N
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000085_0002
Figure imgf000086_0001
Figure imgf000086_0002
WisS.XisN. and Z is CH
Rl Ri Ri Rl Ri Ri
CH3 CF3 CF3 CH2CH3 CF3 CF3
CH3 CF3 CC1CF2 CH2CH3 CF3 CC1CF2
CH3 CF3 C2F5 CH2CH3 CF3 C F5
CH3 OCF3 CF3 CH2CH3 OCF3 CF3
CH3 OCF3 CC1CF2 CH2CH3 OCF3 CC1CF2
CH3 OCF3 C F5 CH2CH3 OCF3 C2F5
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000089_0002
WisS.XisCH.andZisN
Figure imgf000090_0001
Table 10
Figure imgf000091_0001
W is O. X is N. and Z is CCN
Rl R8 Rl R8
Figure imgf000092_0001
W is S. X is N. and Z is CC1
Rl R8 Rl R8
Figure imgf000093_0001
O O o o
O o o o
X a a to a t a a a to a a TJ fl to toι t o o a o a O a O o a X X IF
Figure imgf000093_0002
Figure imgf000094_0001
S t o O O O O O o 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 . to to to to to to to to to to a to to to a toa to a to a to a to a to a to to to to to to to to to to to to to to to to to to a
O O "" O O O IF g o o o o o o o o o o o O O O O O IF t a to a to a to a to a to
O O a a a a a a a a X X X X X X X X X X X X X X X X X X a O a a a a a
O O O O O O O O IT. O O O O O O O O O o
►fl TJ TJ TJ TJ TJ TJ Tl - to to to to to to to to to o o o
TJ TJ Tj TJ TJ TJ Tj j TJ ►fl TJ TJ "fl "fl •fl •fl "fl TJ t to o to o to o to n t n j Tj Tj Tj Tj CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ O LO LO UJ LO O LO O I IF O Tj T /l Ll LΛ L/i LΛ LΛ
Figure imgf000095_0001
to O
Figure imgf000095_0002
S
CJ o o o o O O O O O O O O O O O O O O o o a a a a O o O O o o o o to to to to to a toto toto toto toto toto toto toto to to to to to to to to to to to to to a to a o a to a a a a a to a to a to a to a to a to a
O O O O IF O O O O O O O O O O O O O O O O O IF to to to to
O O Ci O O a a a X X X X X X X X a a a a 1- a a a a a a a a a a
Figure imgf000095_0004
Figure imgf000095_0003
Figure imgf000096_0001
S
-
Figure imgf000096_0002
O O O O O O O O O 0 O O O O O O O O O O to to to to to to to to to 0 to to to to to to to to to 0 O O
"fl Tj Tj Tj TJ TJ TJ TJ ►fl ►fl TJ f TJ "fl l
CΛ CΛ CΛ CΛ CΛ LO LO TJ TJ TJ ►fl TJ
L LO TJ "l "fl o "f O UJ O LO LO LO I IF σs "fl "fl "fl Tj Tj Tj TJ TJ TJ LO LO LO LO
Figure imgf000096_0003
Figure imgf000097_0001
to O toO toO toO toO toO toO Uo o o N o •> o N o N O O O O O O O O O O O O O O O O O j Tj Tj Tj TJ TJ T] . A TJ Tj Tj Tj Tj T oJ T oJ to to to to to to to to to O O j TJ Tj TJ TJ Tj Tj Tj j j j Tj Tj Tj CΛ CΛ CΛ CΛ CΛ CΛ CΛ ^ LO LO LO LO UJ | IF σs Tj TJ Tj Tj CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ LO LO LO LO LO LO LO LO LO IIFσs
Figure imgf000097_0002
Figure imgf000098_0001
υ υ
Figure imgf000098_0002
cn en cn cn cn cn n
CN CN N rs rs rs to to r- en en en υ a a a C t to cn cn cn a υ a υ a rs to to to en cn a cn a cn a c rs rs o to en en a a Pi υ a υ a a υ υ to o υ rs CN CN a a a rs CN υ υ υ X a a a υ υ υ υ a υ a υ a a υ a υ a l υ υ to t υ a a a υ υ a υ a CN rs υ rs a a υ a υ a υ a υ a υ a
Figure imgf000098_0003
o υ υ cn Pi υ t υto toυ toυ oυt υto toυ υto toυ υto toυ toυ υto toυ υto υto toυ toυ en ( υto υa υa toυ υa υa υa υto υto toυ υto
Figure imgf000099_0001
to to to to to to to υ υ υ υ υ Pi υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ Pi υ υ υ υ υ υ υ
Figure imgf000099_0002
Figure imgf000099_0003
Figure imgf000100_0001
cn en en en a a a a a a a a a a a a a a a υ a a a a a a a a a a a a a
CJ rs υ rs υ υ υ υ υ υ υ υ ">l υ u υ u u rs υ υ υ υ υ rs υ rs υ rs υ rs υ υ υ a υ υ a a rs υ a a a a a a a a a a pil a a a a a a a a a a a a a a a a a a Pil υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ a υ υ a a υ
Figure imgf000100_0002
m cn cn en cn cn cn cn en a a a rs rs (N to υ υ to to to cn cn cn a a o to cn cn a a (N to to to en a a X a υ υ υ υ υ rs a a a a a to t a υ cn a a υ υ a a a υ υ υ I a υ X υ υ υ υ υ CN CN rs a a a a υ υ a (N JN a υ a a υ SI υ a υ υ υ υ υ u a υ a ^ a u υ υ a a υ υ υ υ υ υ a υ
Figure imgf000100_0003
o t a ι a r ι en Pil υo υt toυ toυ oυ υ υto toυ υa toυ υto toυ υto υto υto υHH υto υto en Pil υ a a υ a υ
Figure imgf000101_0001
Figure imgf000101_0002
Figure imgf000102_0001
O O O O O O O O O O
Tj Tj Tj j Tj Tj Tj Tj Tj to to to to O O O O O O O O O O O O to to to LO LO LO LO LO LO LO LO LO I IF to O O O O O O O O to to to to os •fl J ►fl ►fl TJ TJ TJ Tj TJ "fl TJ "fl to to TJ Tj TJ Tj
CΛ CΛ CΛ CΛ CΛ CΛ LΛ CΛ I |F σs "fl
Figure imgf000102_0002
Figure imgf000102_0003
Figure imgf000103_0001
en en en en en en en en cn en en C a ) t a ) a rs (N CN r ) to to to en en a rs CN rs . en CN rs CN to n r ) to to to cn a en en a . to υ a υ a a υ rs rs CN a a a υ a a a e a en N υ a a a a a a a to υ υ υ υ υ a a a a υ a υ υ υ a υ υ υ υ a υ υ a CN υ a a r rss υ rs υ υ a a a a a υ υ υ O SI υ υ a υ υ υ υ a rs υ a C υ υ o a rs υ
Figure imgf000103_0002
SO IΛ
00 X X
O cn en cn en en en cn cn en
X X X X X HH X X X d X x x d X X X X υ υ υ υ υ υ υ υ υ υ X υ υ Xυ υX υ xυ Xυ υX xυ Xυ xυ Xυ υX Xυ Xυ υX Xυ e5 Pil υ υ υ υ
Figure imgf000104_0001
t o O o o o o O o o o o o o o o o o o o o o t to to to to to to to a to a a o to to a to a O o to a to a to a to a t to a a O to to to to to to o o a o to to a a O to to a o a o a O t to to a to to to to to to to to to to to to to O O O a O O O O a O O O a a a a a a O O a a O a a O a a a O a O a IF a O O O O O O O O O O O O O
X X X X X X X X X X X X X
O O O O O O O O O to to to to to to to to to O O O O
Figure imgf000104_0002
o o O O O
O o o a a a O to to a to a o a o o o o a Ω a *s κ> t a O to a o o o o
O O a O a O O to t a o
O o o o a a "fl a "fl o t to to to Tl o x a a a a a a a O a IF to
•fl a a t "fl a TI a a a t a to to to o a O a o o o a a " O a a •A Tl •A ( J to to to a
Figure imgf000104_0003
Figure imgf000105_0001
m en en en en cn en en cn cn en en cn cn en en cn cn c a a a a a a a a a a a a a a a a a a υ υ υ a a a a a a a a a a υ a a a a I υ CN υ CN υ CN υ CN υ CN CN υ CN υ CN υ CN υ CN υ rs υ rs υ rs υ CN υ rs υ CN υ υ υ π_S CN CN CN CN υ CN υ rs υ CN υ CN υ rs υ CN υ CN j.' rs π_N CN C
Figure imgf000105_0002
en en cn cn cn cn cn en en en en c en en en a a a rs CN CN C t to cn a a a CN CN N a CN CN C a a a
SI a a a υ o a X υ o ot a υ a N to to en cn υ υ υ CN υ t
CN υ o rs a a X a υ υ υ rs υ rs υ t
CN a a a a a a υ υ υ a a a υ υ υ g I υ υ υ a υ a υ a υ rs υ rs υ r υ υ υ υ υ υ υ a υ a a a υ υ a υ a υ υ υ a υ υ a" a u a υ
Figure imgf000105_0003
0 X X d cn en en en en cn en en cn cn en en en en en cn cn cn co' en en en en cn en cn m cn en en cn en cn e
Pil aυ wυ aυ aυ aυ aυ υa aυ aυ υa aυ aυ aυ υa aυ υa aυ υa Pil υ xυ xυ υE υ υ υ υ Xυ υ υ υ υ υ υ
Figure imgf000106_0001
8 19 8 319 8 19 8 3 P I 00 t9 TJ
Figure imgf000106_0002
Figure imgf000106_0003
Figure imgf000107_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 to to t to to to to o to to to to t to to to to a t a to a to a to a to a to a
O O O O O O O IF to to to to to to a to a o to a to a t a a a a
O O O O Ci O O O x x x x x x x X X X X X a O O O O O IF
X a a a a a a X X X X X a a a a a a a
O O O O O O O O Tj OTj Tj Tj OTj OTJ OTj to to to to to to to t to O O O O O O O O O o o to o to o LO LO LO LO LO LO LO F l ►fl •fl TJ
CΛ CΛ CΛ CΛ CΛτι ►fl ►lf to o to o to o
TJ ►f ►fl ►fl ►fl ►fl Tj "fl TJ "fl "fl J to o t
LΛ CΛ CΛ LO LO LO LO LO LO LO LO LO IF J "fl Tj j TJ TJ TJ
CΛ CΛ CΛ CΛ CΛ CΛ CΛ
Figure imgf000107_0002
L 3O
Figure imgf000107_0003
Figure imgf000108_0001
cn en cn cn en en en cn cn en en cn en en en en cn cn en en en en cn en cn en en a υ a a a a a a a a a a a a a a a a a .. . υ υ υ υ a υ a υ a υ a υ a. a υ a υ
Figure imgf000108_0002
toυ toυ υ to toυ toυ υ to toυ toυ toυ toυ toυ cn pil to to to to HM to a to a a a a to to to to ( a
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
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 emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible
("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
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 Emulsifiable 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 Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, 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. 4,172,714. 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. 7, 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 Table A. Example A
High Strength Concentrate
Compound 3 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
Example B
Wettable Powder
Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%,
Example C
Granule Compound 5 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 6 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 or equally tolerant to the above crops. 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, ami-role, 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, chloramben, 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- pyridinecarboxylic 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, flazasulfuron, 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, imazamox, 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-(trifluoromethyl)phenoxy]-2- nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6- dimethyl-2-pyrimidinyl)amino] carbonyl]amino] sulfonyl] - 1 -(2-pyridinyl)- 1 H-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), perfiuidone, 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 vemolate.
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 Table A 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
Cmpd Structure mp (°Q
Figure imgf000122_0001
Figure imgf000123_0001
BIOLOGICAL EXAMPLES OF THE INVENTION Test A
Seeds of bedstraw {Galium aparine), blackgrass {Alopecurus myosuroides), broadleaf signalgrass {Brachiaria decumbens), cocklebur {Xanthium strumarium), com {Zea mays), crabgrass {Digitaria sanguinalis), giant foxtail {Setariafaberii), lambsquarters {Chenopodium album), morningglory {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 fiatsedge {Cyperus difformis), duck salad
(Heteranthera limosa) and bamyardgrass {Echinochloa crus-galli) 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 A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
Table A COMPOUND Table A COMPOUND
Rate 500 g/ha 1 2 3 4 Rate 500 g/ha 1 2 3 4
Postemergence Preemergence
B. signalgrass - - 9 3 B. signalgrass - - 10 5
Bamyardgrass 5 0 7 0 Bedstraw 8 0 5 0
Bedstraw 9 6 10 4 Blackgrass 7 1 9 0
Blackgrass 7 2 9 2 Cocklebur 1 0 9 -
Cocklebur 7 6 10 8 Corn 1 0 2 0
Corn 3 2 5 2 Crabgrass 10 2 10 3
Crabgrass 9 4 9 2 Giant foxtail 10 7 10 5
Ducksalad 2 0 5 0 Morningglory 3 0 10 3
Giant foxtail 8 3 9 2 Nutsedge 0 0 1 0 Morningglory 8 3 9 7 Rape 3 0 10 l
Nutsedge 0 0 1 0 Redroot pigweed 10 0 10 7
Rape 9 4 9 4 Soybean 1 0 7 0
Redroot pigweed 9 4 9 7 Sugarbeets 10 1 10 9
Rice 3 0 5 0 Velvetleaf 3 0 10 6
S . Flatsedge 2 0 9 0 Wheat 2 0 7 0
Soybean 8 3 10 5 Wild oats 8 1 9 2
Sugarbeets 9 6 9 5
Velvetleaf 8 2 9 1
Wheat 2 0 5 0
Wild oats 6 0 8 1
Table A COMPOUND Table A COMPOUND
Rate 250 g/ha 1 2 3 4 5 6 7 Rate 250 g/ha 1 2 3 4 5 6 7
Postemergence Preemergence
B. signalgrass - - 9 0 3 4 - B. signalgrass - 10 3 9 9 3
Bamyardgrass 4 0 5 0 1 3 1 Bedstraw 8 0 4 0 7 8 3
Bedstraw 9 3 9 1 9 8 7 Blackgrass 6 0 9 0 3 6 1
Blackgrass 5 1 9 0 6 4 2 Cocklebur 0 0 7 0 2 6 0
Cocklebur 7 3 10 7 8 9 6 Corn 0 0 1 0 1 1 0
Corn 2 1 4 1 - 5 3 Crabgrass 9 1 10 2 10 9 3
Crabgrass 9 3 9 2 6 7 8 Giant foxtail 10 7 10 3 10 10 7
Ducksalad 0 0 3 0 2 8 2 Morningglory 3 0 10 0 10 10 2
Giant foxtail 6 2 9 1 6 8 3 Nutsedge 0 0 0 0 2 0 0
Morningglory 8 2 8 7 8 9 6 Rape 2 0 9 1 10 10 1
Nutsedge - 0 1 0 - 2 0 Redroot pigweed 10 0 10 6 10 10 4
Rape 9 2 9 1 10 10 8 Soybean 1 0 7 0 1 3 0
Redroot pigweed 8 4 9 7 10 10 6 Sugarbeets 8 0 10 9 10 10 4
Rice 2 0 4 0 0 3 1 Velvetleaf 3 0 9 0 10 10 0
S . Flatsedge 0 0 9 0 8 9 5 Wheat 1 0 5 0 2 1 0
Soybean 6 2 10 2 8 8 5 Wild oats 6 1 9 0 7 8 3
Sugarbeets 9 2 9 3 10 10 7
Velvetleaf 7 1 9 1 8 8 7
Wheat 1 0 3 0 3 2 0
Wild oats 3 0 7 0 6 3 0
Table A COMPOUND Table A COMPOUND
Rate 125 g/ha 1 2 3 4 5 6 7 Rate 125 g/ha 1 2 3 4 5 6 7 Postemergence Preemergence
B. signalgrass - - 9 0 2 3 - B. signalgrass - - 9 2 9 8 2
Bamyardgrass 3 0 3 0 1 3 0 Bedstraw 2 0 4 0 4 8 1
Bedstraw 8 1 9 1 9 8 6 Blackgrass 4 0 9 0 3 5 0
Blackgrass 3 1 9 0 4 3 1 Cocklebur 0 0 6 0 1 - -
Cocklebur 5 1 9 1 8 6 6 Com 0 0 1 0 1 0 0
Corn 2 1 3 0 - 2 3 Crabgrass 4 0 9 1 8 7 2
Crabgrass 6 1 9 1 3 6 5 Giant foxtail 9 2 9 2 9 10 4
Ducksalad 0 0 2 0 0 3 0 Morningglory 1 0 10 0 10 10 0
Giant foxtail 3 0 9 1 2 5 3 Nutsedge 0 0 0 0 0 0 -
Morningglory 8 2 8 0 4 7 6 Rape 1 0 9 0 9 10 1
Nutsedge 0 0 1 0 0 0 0 Redroot pigweed 7 0 8 0 10 10 1
Rape 9 2 9 0 10 10 7 Soybean 0 0 6 0 0 2 0
Redroot pigweed 8 2 9 0 10 10 6 Sugarbeets 3 0 10 5 10 10 2
Rice 1 0 3 0 0 1 0 Velvetleaf 1 0 9 0 9 9 0
S . Flatsedge - 0 8 0 3 9 2 Wheat 0 0 4 0 0 0 0
Soybean 5 1 9 1 7 8 4 Wild oats 3 0 9 0 7 7 0
Sugarbeets 9 2 9 0 9 10 4
Velvetleaf 7 1 9 0 4 7 7
Wheat 1 0 3 0 2 2 0
Wild oats 3 0 6 0 3 3 0
Table A COMPOUND Table A COMPOUND
Rate 62 g/ha 1 2 3 4 5 6 7 Rate 62 g/ha 1 2 3 4 5 6 7
Posternergence Preemergence
B. signalgrass - - 6 0 2 2 - B. signalgrass - - 9 0 5 7 1
Bamyardgrass 2 0 3 0 1 2 0 Bedstraw 0 0 3 0 1 6 0
Bedstraw 7 - 8 0 8 8 3 Blackgrass 1 0 9 0 1 3 0
Blackgrass 3 0 7 0 2 3 0 Cocklebur 0 0 4 - 0 - 0
Cocklebur 4 0 9 0 8 6 4 Corn 0 0 0 0 0 - 0 0
Corn 2 1 3 0 - 2 2 Crabgrass 3 0 9 0 3 6 0
Crabgrass 4 1 9 0 2 4 5 Giant foxtail 9 0 9 2 6 9 1
Ducksalad 0 0 2 0 0 1 0 Morningglory 1 0 5 0 8 10 0
Giant foxtail 2 0 8 0 2 3 2 Nutsedge 0 0 0 0 0 0 0
Morningglory 6 1 8 0 3 7 6 Rape 0 0 9 0 4 9 0
Nutsedge 0 0 1 0 0 0 0 Redroot pigweed 2 0 8 0 10 10 0
Rape 8 1 9 0 8 10 5 Soybean 0 0 1 0 0 0 0
Redroot pigweed 8 1 9 0 9 10 5 Sugarbeets 0 0 9 3 10 10 1 Rice 0 0 3 0 0 1 0 Velvetleaf 0 0 8 0 6 7 0
S . Flatsedge 0 0 8 0 1 9 2 Wheat 0 0 2 0 0 0 0
Soybean 3 1 9 1 7 7 4 Wild oats 2 0 9 0 2 6 0
Sugarbeets 9 2 9 0 8 10 4
Velvetleaf 2 1 8 0 2 6 7
Wheat 0 0 3 0 2 1 0
Wild oats 2 0 5 0 2 2 0
Table A COMPOUND Table A COMPOUND
Rate 31 g/ha 5 6 7 Rate 31 g/ha 5 6 7
Postemergence Preemergence
B . signalgrass 2 B. signalgrass 4 5 0
Bamyardgrass 2 0 Bedstraw 1 2 0
Bedstraw 4 3 Blackgrass 1 1 0
Blackgrass 2 0 Cocklebur 0 - 0
Cocklebur 6 4 Corn 0 0 0
Corn 1 2 Crabgrass 1 4 0
Crabgrass 3 4 Giant foxtail 3 8 0
Ducksalad 1 0 Morningglory 1 7 0
Giant foxtail 2 Nutsedge 0 0 0
Morningglory 5 5 Rape 2 9 0
Nutsedge 0 0 Redroot pigweed 2 9 0
Rape 7 5 Soybean 0 0 0
Redroot pigweed 9 4 Sugarbeets 9 10 0
Rice 0 0 Velvetleaf 2 5 0
S . Flatsedge 0 8 0 Wheat 0 0 0
Soybean 6 7 3 Wild oats 2 2 0
Sugarbeets 7 9
Velvetleaf 2 2
Wheat 2 1
Wild oats 2 2
Test B
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). 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 arrowleaf sida {Sida rhombifolia), bamyardgrass {Echinochloa crus-galli), cocklebur {Xanthium strumarium), common ragweed {Ambrosia elatior), com 1 {Zea mays), cotton {Gossypium hirsutum), eastern black nightshade {Solanum ptycanthum), fall panicum {Panicum dichotomiflorum), field bindweed {Convolvulus arvensis), giant foxtail {Setariafaberii), hairy beggarticks {Bidens pilosa), ivyleaf morningglory {Ipomoea hederacea), johnsongrass {Sorghum halepense), ladysthumb smartweed {Polygonum persicaria), lambsquarters {Chenopodium album), large crabgrass {Digitaria sanguinalis), purple nutsedge {Cyperus rotundus), redroot pigweed {Amaranthus retroβexus), soybean l{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 B, 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 B COMPOUND Table B COMPOUND Table B COMPOUND
Rate 280 g/ha 3 Rate 140 g/ha 3 Rate 70 g/ha 3
PREEMERGENCE PREEMERGENCE PREEMERGENCE Arrowleaf sida 100 Arrowleaf sida 95 Arrowleaf sida 95 Bamyardgrass 100 Bamyardgrass 95 Bamyardgrass 35 Cocklebur 25 Cocklebur 10 Cocklebur 0
Common ragweed 100 Common ragweed 100 Common ragweed 100 Corn 1 20 Corn 1 10 Corn 1 5
Cotton 75 Cotton 30 Cotton 20
E . blacknightsh 95 E . blacknightsh 100 E . blacknightsh 100 Fall panicum 100 Fall panicum 95 Fall panicum 85
Field bindweed 100 Field bindweed 90 Field bindweed 95 Giant foxtail 100 Giant foxtail 100 Giant foxtail 95 H . beggarticks 100 H . beggarticks 80 H . beggarticks 70 I . morningglory 80 I . morningglory 75 I . morningglory 35 Johnsongrass 100 Johnsongrass 100 Johnsongrass 80
Ladysthumb 100 Ladysthumb 100 Ladysthumb 80
Lambsquarters 100 Lambsquarters 100 Lambsquarters 100 Large crabgrass 100 Large crabgrass 100 Large crabgrass 100 Purple nutsedge 10 Purple nutsedge 0 Purple nutsedge 0 Redroot pigweed 100 Redroot pigweed 100 Redroot pigweed 100 Soybean 1 35 Soybean 1 20 Soybean 1 15 Surinam grass 95 Surinam grass 95 Surinam grass 80 Velvetleaf 100 Velvetleaf 100 Velvetleaf 100 Wild poinsettia 100 Wild poinsettia 50 Wild poinsettia 100
Table B COMPOUND Table B COMPOUND
Rate 35 g/ha 3 Rate 17 g/ha 3 PREEMERGENCE PREEMERGENCE
Arrowleaf sida 90 Arrowleaf sida 70
Bamyardgrass 10 Bamyardgrass 10
Cocklebur 0 Cocklebur 0
Common ragweed 40 Common ragweed 10
Corn 1 0 Corn 1 5
Cotton 10 Cotton 0
E. blacknightsh 100 E. blacknightsh 10
Fall panicum 50 Fall panicum 10
Field bindweed 80 Field bindweed 65
Giant foxtail 60 Giant foxtail 10
H. beggarticks 65 H. beggarticks 0
I. morningglory 20 I. morningglory 10
Johnsongrass 40 Johnsongrass 10
Ladysthumb 25 Ladysthumb 40
Lambsquarters 95 Lambsquarters 100
Large crabgrass 100 Large crabgrass 70
Purple nutsedge 0 Purple nutsedge 0
Redroot pigweed 100 Redroot pigweed 95
Soybean 1 5 Soybean 1 0
Surinam grass 50 Surinam grass 25
Velvetleaf 10 Velvetleaf 10
Wild poinsettia 10 Wild poinsettia 0
TESTC
Seeds, tubers, or plant parts of alexandergrass {Brachiaria plantaginea), bermudagrass {Cynodon dactylon), common purslane {Portulaca oleracea), common ragweed {Ambrosia elatior), common groundsel {Senecio vulgaris), dallisgrass {Paspalum dilatatum), goosegrass {Eleusine indica), guineagrass {Panicum maximum), itchgrass {Rottboellia exaltata), Johnson grass {Sorghum halepense), large crabgrass {Digitaria sanguinalis), pitted morningglory {Ipomoea lacunosa), purple nutsedge {Cyperus rotundus), sandbur {Cenchrus echinatus), sourgrass {Trichachne insularis), Spanishneedles {Bidens bipinnata), 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 and postemergence to the plants. 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 C, 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 C COMPOUND Table C COMPOUND Table C COMPOUND
Rate 500 g/ha 3 Rate 250 g/ha 3 Rate 250 g/ha 3 POSTEMERGENCE POSTEMERGENCE PREEMERGENCE
Alexandergrass 75 Alexandergrass 35 Alexandergrass 100
Bermudagrass 30 Bermudagrass 10 Bermudagrass 100
C. purslane 98 C. purslane 65 C. purslane 100
C . ragweed 50 C . ragweed 40 Dallisgrass 100
Com. groundsel 75 Com. groundsel 65 Goosegrass 100
Dallisgrass 90 Dallisgrass 75 Guineagrass 100
Goosegrass 90 Goosegrass 65 Large crabgrass 100
Guineagrass 30 Guineagrass 30 P. morninglory 100
Itchgrass 50 Itchgrass 50 Purple nutsedge 0
Johnsongrass 35 Johnsongrass 35 Sandbur 100
Large crabgrass 80 Large crabgrass 35 Sourgrass 100
P. morninglory 65 P. morninglory 50 Spanishneedles 100
Purple nutsedge 20 Purple nutsedge 20 Surinam grass 100
Sandbur 35 Sandbur 10 Tall Mallow 100
Sourgrass 20 Sourgrass 20
Spanishneedles 50 Spanishneedles 40
Surinam grass 40 Surinam grass
Tall Mallow 98 Tall Mallow 80
Table C COMPOUND Table C COMPOUND Table C COMPOUND
Rate 125 g/ha 3 Rate 64 g/ha 3 Rate 32 g/ha 3 PREEMERGENCE PREEMERGENCE PREEMERGENCE
Alexandergrass 80 Alexandergrass 70 Alexandergrass 30
Bermudagrass 100 Bermudagrass 100 Bermudagrass 100
C. purslane 100 C. purslane 100 C. purslane 100
Dallisgrass 100 Dallisgrass 75 Dallisgrass 50
Goosegrass 100 Goosegrass 100 Goosegrass 100
Guineagrass 100 Guineagrass 80 Guineagrass 65
Large crabgrass 100 Large crabgrass 100 Large crabgrass 100
P. morninglory 80 P . morninglory 40 P. morninglory 20
Purple nutsedge 0 Purple nutsedge 0 Purple nutsedge 0
Sandbur 25 Sandbur 20 Sandbur 20
Sourgrass 100 Sourgrass 100 Sourgrass 100
Spanishneedles 50 Spanishneedles 0 Spanishneedles 0
Surinam grass 80 Surinam grass 50 Surinam grass 10
Tall Mallow 100 Tall Mallow 100 Tall Mallow 90
Table C COMPOUND Table C COMPOUND Rate 16 g/ha 3 Rate 16 g/ha 3 PREEMERGENCE PREEMERGENCE Alexandergrass 5 P . morninglory 0 Bermudagrass 70 Purple nutsedge 0 C. purslane 100 Sandbur 0 Dallisgrass 5 Sourgrass 90 Goosegrass 40 Spanishneedles 0 Guineagrass Surinam grass 5 Large crabgrass 35 Tall Mallow 80

Claims

CLAIMS What 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 J is
Figure imgf000131_0002
J-l J-2 J-3
Figure imgf000131_0003
J-4 J-5 J-6
A is
Figure imgf000131_0004
A-l A-2
Q is O, S(O)n, NR10, CH2 or CH2O, wherein the orientation of the CH2O group is such that the oxygen is bonded to the pyrimidine ring and the carbon is bonded to J;
W is O, S or NR10; X, Y, and Z are independently N or CR8;
R1 and R2 are independently H, halogen, cyano, C1-C4 alkoxy, C1-C4 haloalkoxy,
CrC4 alkyl, CrC4 haloalkyl, C2-C4 alkoxyalkyl, C3-C5 dialkoxyalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy, S(O)nRn, C2-C4 alkylthioalkyl, C2-C alkylsulfonylalkyl, C C4 alkylamino or C2-C4 dialkylamino; R3 is halogen, cyano, SF5, Cj-C4 haloalkyl, C1-C4 alkoxy, Cj-04 haloalkoxy or
S(O)nRH; R4 is H, halogen, cyano, SF5, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or S(O)nRH;
R5 is H, halogen, cyano, SF5, Cj-C4 haloalkyl, C C4 alkoxy, Cj-C4 haloalkoxy or
S(O)nRH; R6 is halogen, cyano, SF5, Cj-C haloalkyl, CrC alkoxy, CrC haloalkoxy or
S(O)nRH; each R7 is independently Cj-C4 alkyl or C1-C4 haloalkyl; each R8 is independently H, halogen, cyano, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkyl, C]-C haloalkyl, C2-C alkoxyalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C3-C4 alkenyloxy, C3-C4 alkynyloxy or S(O)nRπ; R9 is H, CrC4 alkyl or C,-C4 haloalkyl; R10 is H, CrC4 alkyl or CrC4 haloalkyl; each R1 1 is independently Cj-C4 alkyl or C1-C4 haloalkyl; and each n is independently 0, 1 or 2.
2. The compounds of Claim 1 wherein W is O or NRl╬╕ when X, Y, and Z are CR8.
3. The compounds of Claim 2 wherein Q is O;
R1 and R2 are independently H, C1-C4 alkyl or -C4 alkoxy; R3 is halogen, CrC haloalkyl, Cj-C4 haloalkoxy or Cj-C haloalkylthio;
R4 and R5 are each independently H or F;
R6 is C1-C4 haloalkyl, C1-C4 haloalkoxy or C1-C4 haloalkylthio; and R8 is halogen, 0^04 haloalkyl, Cj-C4 haloalkoxy, Cj-C4 haloalkylthio or Cj-C alkylthio.
4. The compounds of Claim 3 wherein
W is O or S; and
X is CH or N.
5. The compounds of Claim 4 wherein R2 is H; and R3 is C1-C4 haloalkyl or CJ-C4 haloalkoxy.
6. The compounds of Claim 5 wherein J is J-l, J-5 or J-6.
7. The compound of Claim 6 which is selected from the group: (a) 5-methyl-2-[5-(trifluoromethyl)-l,3,4-oxadiazol-2-yl]-4-[3-
(trifluoromethyl)phenoxy]pyrimidine;
(b) 5-methyl-4-[[l-methyl-3-(trifluoromethyl)-lH-pyrazol-5-yl]oxy]-2-[5-
(trifluoromethyl)-l,3,4-oxadiazol-2-yl]pyrimidine;
(c) 5 -methyl-4- [3 -(trifluoromethyl)phenoxy] -2- [5 -(trifluoromethyl)- 1,3,4- thiadiazol-2-yl]pyrimidine;
(d) 5 -methyl-4- [[ 1 -methyl-3 -(trifluoromethyl)- 1 H-pyrazol-5 -y 1] oxy] -2- [5 - (trifluoromethyl)- 1 ,3, 4-thiadiazol-2-yl]pyrimidine; and e) 5-methyl-4-[3-(trifluoromethyl)phenoxy]-2-[4-(trifluoromethyl)-2- thiazolyljpyrimidine.
8. The herbicidal compositions 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.
9. The methods 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/US1998/011954 1997-06-10 1998-06-09 Pyrimidinyl azole herbicides WO1998056789A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU78313/98A AU7831398A (en) 1997-06-10 1998-06-09 Pyrimidinyl azole herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4928297P 1997-06-10 1997-06-10
US60/049,282 1997-06-10

Publications (1)

Publication Number Publication Date
WO1998056789A1 true WO1998056789A1 (en) 1998-12-17

Family

ID=21959021

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/011954 WO1998056789A1 (en) 1997-06-10 1998-06-09 Pyrimidinyl azole herbicides

Country Status (2)

Country Link
AU (1) AU7831398A (en)
WO (1) WO1998056789A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063183A1 (en) * 1999-04-15 2000-10-26 American Cyanamid Company Process for the preparation of substituted pyrimidines
EP1108720A1 (en) * 1999-12-08 2001-06-20 Basf Aktiengesellschaft Herbicidal 2-Pyrazolyl-6-Aryloxy-Pyri(mi)dines
US6281358B1 (en) 1999-04-15 2001-08-28 American Cyanamid Company Process for the preparation of substituted pyrimidines
US6528456B2 (en) 1999-12-08 2003-03-04 Basf Aktiengesellschaft Herbicidal 2-pyrazolyl-6-aryloxypyri(mi)dines
WO2003029243A2 (en) * 2001-09-24 2003-04-10 Basf Aktiengesellschaft 2-aryloxy-6-pyrazolyl-pyridines
WO2011010222A1 (en) 2009-07-24 2011-01-27 Addex Pharma S.A. Novel pyrazole derivatives and their use as positive allosteric modulators of metabotropic glutamate receptors
CN106008493A (en) * 2016-06-01 2016-10-12 西安近代化学研究所 2, 5-disubstituted-1, 3, 4-thiadiazole derivative and application thereof
CN106008489A (en) * 2016-06-01 2016-10-12 西安近代化学研究所 5-(2, 2-difluoro-1, 3-benzodioxole-4-yl)-1 - 3, 4-oxadiazole-2-thiol derivative and application thereof
WO2018080859A1 (en) 2016-10-24 2018-05-03 E. I. Du Pont De Nemours And Company Fungicidal oxadiazoles
WO2019074219A1 (en) * 2017-10-12 2019-04-18 한국화학연구원 Anti-viral compound, method for preparing same, and pharmaceutical composition containing same as active ingredient for prevention or treatment of viral disease
WO2020070610A1 (en) * 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
CN111747904A (en) * 2020-07-10 2020-10-09 南京工业大学 Polyfluoroalkenyl substituted oxazole compound and preparation method thereof
CN114585618A (en) * 2019-11-01 2022-06-03 优迈特株式会社 Fluorine-containing pyrimidine compound and method for producing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1168430A (en) * 1968-04-05 1969-10-22 Norwich Pharma Co Improvements in or relating to Nitrofuryl Quinazolines
WO1996006096A1 (en) * 1994-08-23 1996-02-29 Nissan Chemical Industries, Ltd. Pyridine derivative
EP0819690A2 (en) * 1996-07-15 1998-01-21 American Cyanamid Company Herbicidal 6-thienyl and 4-thienyl pyrimidines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1168430A (en) * 1968-04-05 1969-10-22 Norwich Pharma Co Improvements in or relating to Nitrofuryl Quinazolines
WO1996006096A1 (en) * 1994-08-23 1996-02-29 Nissan Chemical Industries, Ltd. Pyridine derivative
EP0819690A2 (en) * 1996-07-15 1998-01-21 American Cyanamid Company Herbicidal 6-thienyl and 4-thienyl pyrimidines

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063183A1 (en) * 1999-04-15 2000-10-26 American Cyanamid Company Process for the preparation of substituted pyrimidines
US6281358B1 (en) 1999-04-15 2001-08-28 American Cyanamid Company Process for the preparation of substituted pyrimidines
US6559307B2 (en) 1999-04-15 2003-05-06 Basf Aktiengesellschaft Process for the preparation of substituted pyrimidines
KR100781851B1 (en) * 1999-04-15 2007-12-03 바스프 악티엔게젤샤프트 Process for the Preparation of Substituted Pyrimidines
EP1108720A1 (en) * 1999-12-08 2001-06-20 Basf Aktiengesellschaft Herbicidal 2-Pyrazolyl-6-Aryloxy-Pyri(mi)dines
US6528456B2 (en) 1999-12-08 2003-03-04 Basf Aktiengesellschaft Herbicidal 2-pyrazolyl-6-aryloxypyri(mi)dines
WO2003029243A2 (en) * 2001-09-24 2003-04-10 Basf Aktiengesellschaft 2-aryloxy-6-pyrazolyl-pyridines
WO2003029243A3 (en) * 2001-09-24 2003-09-12 Basf Ag 2-aryloxy-6-pyrazolyl-pyridines
WO2011010222A1 (en) 2009-07-24 2011-01-27 Addex Pharma S.A. Novel pyrazole derivatives and their use as positive allosteric modulators of metabotropic glutamate receptors
US8513252B2 (en) 2009-07-24 2013-08-20 Addex Pharma S.A. Pyrazole derivatives and their use as positive allosteric modulators of metabotropic glutamate receptors
CN106008493A (en) * 2016-06-01 2016-10-12 西安近代化学研究所 2, 5-disubstituted-1, 3, 4-thiadiazole derivative and application thereof
CN106008489A (en) * 2016-06-01 2016-10-12 西安近代化学研究所 5-(2, 2-difluoro-1, 3-benzodioxole-4-yl)-1 - 3, 4-oxadiazole-2-thiol derivative and application thereof
WO2018080859A1 (en) 2016-10-24 2018-05-03 E. I. Du Pont De Nemours And Company Fungicidal oxadiazoles
WO2019074219A1 (en) * 2017-10-12 2019-04-18 한국화학연구원 Anti-viral compound, method for preparing same, and pharmaceutical composition containing same as active ingredient for prevention or treatment of viral disease
WO2020070610A1 (en) * 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
CN113195483A (en) * 2018-10-01 2021-07-30 Pi工业有限公司 Novel oxadiazole compound
CN114585618A (en) * 2019-11-01 2022-06-03 优迈特株式会社 Fluorine-containing pyrimidine compound and method for producing same
CN111747904A (en) * 2020-07-10 2020-10-09 南京工业大学 Polyfluoroalkenyl substituted oxazole compound and preparation method thereof

Also Published As

Publication number Publication date
AU7831398A (en) 1998-12-30

Similar Documents

Publication Publication Date Title
US6172005B1 (en) Heteroaryl azole herbicides
EP0862571B1 (en) Herbicidal sulfonamides
US5723411A (en) Herbicidal pyridazinones
US5750471A (en) Cyclic sulfonamide herbicides
WO1997046530A1 (en) Herbicidal pyridinyl and pyrazolylphenyl ketones
US20100298141A1 (en) Substituted pyridine n-oxide herbicides
EP0846112A1 (en) Bicyclic herbicides
US20060069132A1 (en) Azolecarboxamide herbicides
WO1997019087A1 (en) Tricyclic herbicidal heterocycles
US5633218A (en) Herbicidal benzodioxoles and benzodioxanes
WO1998056789A1 (en) Pyrimidinyl azole herbicides
US6525001B1 (en) Substituted pyrimidine and pyridine herbicides
EP0902028A1 (en) Tetrazoline herbicides
JP2001512460A (en) Herbicidal tetrazolinones
WO1996031517A1 (en) Herbicidal heteroaryl-substituted anilides
US5739326A (en) Heterobicyclic herbicides
EP0863142A1 (en) Heterocyclic herbicides
WO1998035954A1 (en) Bicyclic hydrazone herbicides
EP0860441A1 (en) Herbicidal derivatives of 1,4-dithiino(2,3c)benzothiopyran
WO1999048890A1 (en) Herbicidal tetrazolinones
US20130303369A1 (en) Fatty Amine Salts Of Herbicidal Pyrimidines
US5874382A (en) Cyclic sulfonamide herbicides
EP0977752A1 (en) Herbicidal pyrazoles
US20040033896A1 (en) Substituted pyrimidine and pyridine herbicides
AU7252698A (en) Herbicidal sulfonamides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AU AZ BA BB BG BR BY CA CN CU CZ EE GE GW HU ID IL IS JP KG KP KR KZ LC LK LR LT LV MD MG MK MN MX NO NZ PL RO RU SG SI SK SL TJ TM TR TT UA US UZ VN YU

AL Designated countries for regional patents

Kind code of ref document: A1

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

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

Ref country code: JP

Ref document number: 1999503116

Format of ref document f/p: F

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

Ref country code: CA