WO2000008026A2 - Hétérocycles bicycliques fondus fongicides - Google Patents

Hétérocycles bicycliques fondus fongicides Download PDF

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WO2000008026A2
WO2000008026A2 PCT/US1999/017707 US9917707W WO0008026A2 WO 2000008026 A2 WO2000008026 A2 WO 2000008026A2 US 9917707 W US9917707 W US 9917707W WO 0008026 A2 WO0008026 A2 WO 0008026A2
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alkyl
optionally substituted
haloalkyl
halogen
alkynyl
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PCT/US1999/017707
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WO2000008026A3 (fr
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James Francis Bereznak
Michael Paul Walker
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E.I. Du Pont De Nemours And Company
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Priority to AU55476/99A priority Critical patent/AU5547699A/en
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Publication of WO2000008026A3 publication Critical patent/WO2000008026A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • This invention relates to certain fungicidal fused bicyclic heterocycles, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formulae I and II including all geometric and stereoisomers, their N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides:
  • W is O, S(O) n or ⁇ R 5 ; n is 0, 1 or 2;
  • Q is O or S
  • Z is O, S or NR 5 ;
  • G is, together with the two linking carbons, an optionally substituted fused aromatic heterocyclic ring;
  • R 1 is hydrogen, C r C 10 alkyl; C 3 -C 6 cycloalkyl; C 3 -C 10 alkenyl; C 3 -C 10 alkynyl;
  • R 2 is C r C 10 alkyl; C 3 -C 7 cycloalkyl; C 3 -C 10 alkenyl; C 3 -C 10 alkynyl; C r C 10 haloalkyl; C -CI Q haloalkenyl; C 3 -C 10 haloalkynyl; C 2 -C 10 alkoxyalkyl; C 2 -C 10 alkylthioalkyl; C 2 -C 10 alkylsulfonylalkyl; C 4 -C 10 cycloalkylalkyl optionally substituted with R 8 , R 9 and R 10 ; C 4 -C 10 alkenyloxyalkyl; C 4 -C 10 alkynyloxyalkyl; C -C 10 alkenylthioalkyl; C -C 10 alkynylthioalkyl; C 2 -C 10 haloalkoxyalkyl; C -C ⁇ o alkoxy al
  • R 6 is hydrogen, C r C 4 alkyl, C r C 4 alkoxy or NR 3 R 4 ; each R 7 is independently halogen, C r C 4 alkyl, C r C 4 alkoxy, C r C haloalkyl, nitro or cyano each R 8 is independently Ci-Cg alkyl; Ci-Cg alkoxy; C1-C5 haloalkyl; halogen; C -C 8 alkynyl; C ⁇ -C 6 alkylthio; phenyl or phenoxy each optionally substituted with at least one R 7 ; cyano; nitro; C Cg haloalkoxy; Ci-Cg haloalkylthio; C -Cg alkenyl; C -C 6 haloalkenyl; acetyl; CO 2 Me; or N(C r C 2 alkyl) 2 ; each R 9 is independently methyl, ethyl, methoxy, methylthio
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, H-propyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl 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, hexynyl, heptynyl, octynyl, nonynyl and decynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. Examples of “trialkylsilyl” include (CH 3 ) 3 Si and (CH 3 CH 2 ) 3 Si.
  • Examples of “trialkylsilylalkyl” include (CH 3 ) 3 SiCH 2 and (CH 3 CH 2 ) 3 SiCH 2 CH 2 .
  • Examples of “trialkylsilylalkynyl” include (CH 3 ) 3 SiC ⁇ C and (CH 3 CH 2 ) 3 SiC ⁇ C.
  • Alkoxy includes, for example, methoxy, efhoxy, zi-propyloxy, isopropyloxy and the different butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , (CH 3 ) 2 CHOCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O. Examples of “alkynyloxyalkyl” include HC ⁇ CCH 2 OCH 2 , CH 3 C ⁇ CCH 2 OCH 2 CH 2 and CH 3 C ⁇ CCH 2 CH 2 OCH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • 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, hexylsulfonyl, heptylsulfonyl and octylsulfonyl isomers.
  • alkenylthioalkyl alkylsulfonylalkyl
  • alkylthioalkenyl alkynylthioalkyl
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl cycloheptyl and cyclooctyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, etc. and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. 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 .
  • haloalkenyl “haloalkynyl”, “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to the term “haloalkyl”.
  • 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.
  • haloalkoxyalkyl examples include CF 3 OCH 2 , ClCH 2 CH 2 OCH 2 CH 2 , Cl 3 CCH 2 OCH 2 as well as branched alkyl derivatives.
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • optionally substituted fused aromatic heterocyclic rings include the ring systems illustrated in Exhibit 1.
  • the term "optionally substituted” in connection with these rings refers to rings which are unsubstituted or have, on the series of three to four atoms not common to the ring containing Z, at least one non-hydrogen substituent that does not extinguish the fungicidal activity possessed by the unsubstituted analog.
  • the nitrogen atoms which require substitution to fill their valence are substituted with hydrogen or with R 1 1 or R 12 .
  • R 1 * and or R 12 groups are shown in the structures G-1 to G-21, it is noted that they do not need to be present since they are optional substituents.
  • R 11 include halogen, Ci -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C ⁇ -C 8 haloalkyl, C 3 -C 8 haloalkenyl, C 3 -C 8 haloalkynyl, C r C 8 alkoxy, C r C 8 haloalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, C ⁇ -C 8 alkylthio, C r C 8 alkylsulfonyl, C 2 -C 8 alkoxyalkyl, C 3 -C 8 trialkylsilyl, nitro,
  • the wavy line indicates that the G ring is fused to the heterocyclic ring as illustrated below.
  • Examples of a 3-, 4-, 5- or 6-membered heterocyclic ring wherein said heterocyclic ring is optionally substituted with R 8 , R 9 and R 10 include the ring systems illustrated in Exhibit 2. As with the carbon atoms in the ring, the nitrogen atoms which require substitution to fill their valence are substituted with hydrogen or with R 8 , R 9 or R 10 . Although the R 8 , R 9 and or R 10 groups are shown in the structures Y-l to Y-78, it is noted that they do not need to be present since they are optional substituents.
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 10.
  • C ⁇ -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
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • Formulae I or II 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.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formulae I and II, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • 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 for reasons of better activity and or ease of synthesis are: Preferred 1. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein
  • G is a fused thiophene, furan, thiazole, pyridine, pyrazine, pyridazine or pyrimidine ring optionally substituted with R 11 and R 12 ;
  • R 11 is halogen, C r Cg alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C -C 8 alkynyl, C ⁇ C 8 haloalkyl, C 3 -C 8 haloalkenyl, C 3 -Cg haloalkynyl, C r C 8 alkoxy, C Cg haloalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, C ⁇ -C 8 alkylthio, C r C 8 alkylsulfonyl, C 2 -C 8 alkoxyalkyl, C 3 -C 8 trialkylsilyl, nitro, NR 3 R 4 , C 5 -C 8 trialkylsilylalkynyl, SF 5 , B(OH) 2 , SCN, C r C 8 haloalkylthio, or phenyl optionally substituted
  • G is a fused thiophene, thiazole, pyridine or pyrimidine ring optionally substituted with R 1 * and R 12 ;
  • R 1 is H; C r C 8 alkyl; C 3 -C 5 cycloalkyl; C 3 -C 8 alkenyl; C 3 -C 8 alkynyl; C r C 8 haloalkyl; C 3 -C 8 haloalkenyl; C 2 -C 8 alkoxyalkyl; C 2 -C 8 alkylthioalkyl; C 4 -C 8 cycloalkylalkyl; C 4 -C 8 alkenyloxyalkyl; C r C 8 alkoxy; C1-C4 alkyl substituted with a 5- or 6-membered heterocyclic ring wherein said heterocyclic ring is optionally substituted with R 8 , R 9 and R 10 ; phenyl, pyridinyl, furanyl or thien
  • G is a fused thiophene or pyridine ring optionally substituted with R 11 and
  • R12; R 1 is H; C r C 6 alkyl; C 3 -C 5 cycloalkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C r C 6 haloalkyl; C 3 -C 6 haloalkenyl; C 2 -C 8 alkoxyalkyl; C 4 -C 8 cycloalkylalkyl; C1-C4 alkyl substituted with a furan, tetrahydrofuran, isoxazoline and pyridine wherein said heterocyclic ring is optionally substituted with R 8 , R 9 and R 10 ; or phenyl optionally substituted with R 8 and R 9 ; R 2 is C r C 6 alkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C r C 6 haloalkyl; C 3 -C 6 haloalkenyl; C 2 -C 6 alkoxy
  • R 1 is H; C , -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl C 3 -C 6 haloalkenyl; or C -C 8 cycloalkylalkyl;
  • R 2 is C r C 6 alkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C r C 6 haloalkyl; C 3 -C 6 haloalkenyl; C 4 -C 6 cycloalkylalkyl; or phenyl optionally substituted with R 8 ;
  • R 1 1 is halogen; and
  • R 1 is halogen.
  • G is a fused thiophene, furan, thiazole, pyridine, pyrazine, pyridazine or pyrimidine ring optionally substituted with R 1 1 and R 12 ;
  • R 1 1 is halogen, C r C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 8 haloalkenyl, C 3 -C 8 haloalkynyl, C r C 8 alkoxy, C ⁇ -C 8 haloalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, C r C 8 alkylthio, C r C 8 alkylsulfonyl, C 2 -C 8 alkoxyalkyl, C 3 -C 8 trialkylsilyl, nitro, NR 3 R 4 , C 5 -C 8 trialkylsilylalkynyl, SF 5 , B(OH) 2 , SCN, C r C 8 haloalkylthio, or phenyl
  • G is a fused thiophene, thiazole, pyridine or pyrimidine ring optionally substituted with R 1 and R 12 ;
  • Rl is H; C r C 8 alkyl; C 3 -C 5 cycloalkyl; C 3 -C 8 alkenyl; C 3 -C 8 alkynyl; C r C 8 haloalkyl; C 3 -C 8 haloalkenyl; C 2 -C 8 alkoxyalkyl; C 2 -C 8 alkylthioalkyl; C 4 -C 8 cycloalkylalkyl; C 4 -C 8 alkenyloxyalkyl; C ⁇ -C 8 alkoxy; C ⁇ -C 4 alkyl substituted with a 5- or 6-membered heterocyclic ring wherein said heterocyclic ring is optionally substituted with R 8 , R 9 and R 10 ; phenyl, pyridinyl, furanyl or thieny
  • R 9 is methyl, ethyl, methoxy, methylthio, halogen or trifluoromethyl; and R 1 1 is halogen, C r C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkynyl, C r C 8 haloalkyl, C r C 8 alkoxy, C C 8 haloalkoxy, C r C 8 alkylthio, C r C 8 alkylsulfonyl, C 2 -C 8 alkoxyalkyl, C5-C 8 trialkylsilylalkynyl, SF 5 ; B(OH) 2 , SCN or C r C 8 haloalkylthio.
  • G is a fused thiophene or pyridine ring optionally substituted with R 1 1 and
  • R12; R 1 is H; C r C 6 alkyl; C 3 -C 5 cycloalkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C r C 6 haloalkyl; C 3 -C 6 haloalkenyl; C 2 -C 8 alkoxyalkyl; C 4 -C 8 cycloalkylalkyl; C r C 4 alkyl substituted with a furan, tetrahydrofuran, isoxazoline and pyridine wherein said heterocyclic ring is optionally substituted with R 8 , R 9 and R 10 ; or phenyl optionally substituted with R 8 and R 9 ; R 2 is C r C 6 alkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C r C 6 haloalkyl; C 3 -C 6 haloalkenyl; C 2 -C 6 alkoxy
  • R 1 is H; C r C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C r C 6 haloalkyl C 3 -C 6 haloalkenyl; or C 4 -C 8 cycloalkylalkyl;
  • R 2 is C ⁇ -C 6 alkyl; C 3 -C 6 alkenyl; C 3 -C 6 alkynyl; C , -C 6 haloalkyl; C 3 -C 6 haloalkenyl; C -CG cycloalkylalkyl; or phenyl optionally substituted with R 8 ;
  • Most preferred are compounds of Preferred 4 selected from the group:
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • fungicidal compositions comprising fungicidally 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 plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein).
  • a fungicidally effective amount 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.
  • G, Q, Z, W, R 1 , R 2 and R 5 in the compounds of Formulae 1-12 below are as defined above in the S mmary of the Invention.
  • Compounds of Formulae la-If are various subsets of the compounds of Formula I, and all substituents for Formulae la-If are as defined above for Formula I.
  • Compounds of Formulae Ila-IIb are various subsets of the compounds of Formula II, and all substituents for Formulae Ila-IIb are as defined above for Formula II.
  • lb la n 1 or 2
  • the reaction may be run either in neat R 2 WH or in an inert solvent (dioxane acetonitrile or tetrahydrofuran) at temperatures from 25 °C-200 °C.
  • bases such as sodium hydride, sodium hydroxide, sodium alkoxides, or trialkyl amines may be employed to facilitate the reaction.
  • Workup and purification may be achieved by dilution with a water-immiscible solvent, partitioning with water or dilute bicarbonate solution, separation of organic phase, and concentrated in vacuo. Chromatographic purification would yield the desired material la.
  • the sulfinyls/sulfones lb may be prepared through oxidation of the methylthio compounds Ic (Scheme 2) using well-known methods for the oxidation of sulfur compounds (see, for example, March, J., Advanced Organic Chemistry; 3 rd ed., John Wiley, New York (1985), p 1089).
  • R 2 is other than methyl
  • compounds of Formula lb where R 2 is other than methyl can also be prepared in a likewise fashion from the corresponding alkylthio precursors.
  • Compounds of Formula la may also be accessed from Ic in a manner similar to that described from lb.
  • Compounds of Formula Ic can be assembled from precursors of Formula 1 by analogy to methods described in Eiden, F., et al., Arch. Pharm., 316 (1), (1983), p 34 and Bantick, J., et al., J. Heterocycl, Chem., (1981), 18, p 679. (Scheme 3).
  • Condensation of 1 with carbon disulfide may be conducted in solvents such as dimethyl sulfoxide or benzene at temperatures ranging from about 0 °C-120 °C.
  • Suitable bases include sodium or potassium hydroxides, alkoxides or hydrides.
  • Workup to deliver intermediate 2 is optional and can be achieved as described by Bantick, J., et al., J. Heterocycl Chem., (1981), 18, p 679. Alkylation and purification of 2 can be subsequently be accomplished using procedures outlined in the above-cited references.
  • Precursors of Formula 1 are known in the art and can be prepared in a variety of ways by the skilled practioner (e.g. Kraus, et al., J. Org. Chem., (1978), 43, p 2072; Dalgaard, L., et al., Tetraheron, (1974), 30, p 93, Blount, j., et al., J. Org. Chem., (1978), 43, p 3821).
  • One particularly useful approach for preparing certain precursors 1 involves displacement of halogen from compounds of Formula 3 (Scheme 4).
  • the reaction may be conducted in aqueous media using excess (1-50 equivalents) of acid or nucleophile at temperatures ranging from 20 °C-150 °C. Workup can be accomplished by concentrating the reaction to dryness followed by recrystallization or trituration to obtain pure 1.
  • Ketones of Formula 3 can be prepared from the widely-available halides 4 in Scheme 5 using well-known methods (see Trecourt, F., et al., J. Chem. Soc, Perkin Trans. 1, (1990), p 2409; Marsais, F., et al., J. Organomet. Chem., (1981), 261 (2), p 139; Murata, N., et al., Syn. Lett., (1997), p 298; Couture, A., Synthesis, (1989), 6, p 456; Quallich, G., J. Org Chem., (1992), 57 (2), p 761; Buu-Hoi, L., J. Chem. Soc, (1958), p 1721; Steinkopf, K., Justus Liebigs Ann. Chem., (1937), 532, p 250).
  • Precursors of Formula 3 may also be used to access compounds of Formula Id, where Q is O and Z is S (Scheme 6).
  • Compounds of Formula Ic may be alternatively prepared through cyclization of compounds of Formula 5 or 6 (Scheme 7) utilizing methods similar to those described by Kuo, S., et al, Chem. Pharm. Bull, (1988), 36 (11), p 4403; Kuo, S., et al., J. Heterocycl. Chem., (1989), 26, p 605; Monti, L., et al., Gazz. Chim. Ital., (1963), 93, p 991; or Watthey, J., et al., J. Org. Chem., (1982) 47 (9), p 1755.
  • the cyclizations may be conducted in diphenyl ether, polyphosphoric acid [PPA], polyphosphoric ester [PPE], (see Kuo, J. Heterocycl. Chem., (1989), 26, 605 and Burkhardt, et al. J. Am. Chem. Soc,, (1965), 87, 591), or sulfuric acid at temperatures from about 100 °C - 250 °C for 0.1 - 24 hours.
  • the reaction if conducted in diphenyl ether, may be treated with hexanes in diethyl ether to precipitate crude Ic.
  • reaction mixture is diluted with an excess of water, neutralized and the product extracted into a water-immiscible solvent. Drying (e.g., anhydrous Na 2 SO 4 ,) and concentration of this fraction affords crude Ic. Further purification can be achieved via recrystallization or silica gel chromatography. Compound Ic so obtained may further be manipulated as previously described to deliver compounds of Formula la.
  • Acyclic esters of Formula 5 can be assembled using procedures similar to those described by Kuo, S., et al., Chem. Pharm. Bull, (1988), 36 (11), p 4403 (Scheme 8).
  • NR 5 in an inert solvent at temperatures ranging from 20 °C-100 °C for 1-24 hours affords the acyclic Precursor 5.
  • Suitable solvents for this reaction include tetrahydrofuran, dioxane, dimethyl sulfoxide, N,N-dimethylformamide or acetonitrile.
  • Workup can be achieved by pouring the reaction into water and collecting the precipitated product of Formula 5. Further purification can be obtained by recrystallization or silica gel chromatography.
  • Heterocycles of Formula 8 are either commercially available or easily prepared using known methods (see Heuf, W., et al., J. Amer. Chem.
  • Acyclic acids of Formula 6 are accessible from the corresponding esters of Formula 5 as shown in Scheme 9.
  • the hydrolysis and workup may be conducted under conditions similar to those employed by Kim, et al., in hydrolyzing similar esters (J. Med. Chem., (1997), 40 (15), p 2363).
  • Alkyl bis-(dimethylthio)acrylates of Formula 7 are well-documented in the literature and may be synthesized from commercially available compounds of Formula 9 as shown in Scheme 10 and cited by Kim, et al., in J. Med. Chem., (1997), 40 (15), p 2363.
  • Preferable solvents for this conversion include benzene, toluene and xylene.
  • the reagents and solvents are combined and heated at temperatures ranging from 50 °C to 250 °C for 12-24 h.
  • the reaction mixture is concentrated in vacuo and the residue so obtained may be purified via recrystallization or silica gel chromatography to provide compounds of Formula If.
  • Chloro species of Formula 10 are prepared by treatment of compounds of Formula 11 with chlorinating agents such as POCl 3 , PC1 5 , SOCl 2 or SO 2 Cl 2 (Scheme 13) in a manner similar to that cited by Darbarwar, M., et al., Synthesis, (1982), p 337.
  • chlorinating agents such as POCl 3 , PC1 5 , SOCl 2 or SO 2 Cl 2 (Scheme 13) in a manner similar to that cited by Darbarwar, M., et al., Synthesis, (1982), p 337.
  • the compounds of Formula 11 may be treated with neat chlorinating agent, or with 1-50 eq of chlorinating agent in an inert solvent at temperatures ranging from 20 °C-150 °C for 1-48 h. Suitable solvents for this transformation are benzene, toluene or xylenes. Upon completion, the reaction may be diluted with water, neutralized, and extracted with a water-immiscible solvent. This organic phase may be dried and concentrated to deliver the crude compound 10 which may be used without further purification.
  • lb 11 n 1 or 2
  • the reaction may be conducted in dilute aqueous base ( ⁇ aOH or KOH) as described in similar cases by Bantick, j., et al., J. Heterocycl Chem., (1981), 18, p 679.
  • the compounds of Formula lb may be prepared using methods described previously in this disclosure (Scheme 2).
  • compounds of Formula 11 can also be assembled by cyclization of the previously-cited compounds of Formula 8 with malonates of Formula 12 (Scheme 16).
  • Analogous methods are known in the literature for preparing benzo-fused variants of Formula 11 (coumarins), and these methods may be applied in the synthesis of compounds of Formula 11 from compounds of Formulae 8 and 12.
  • the reaction can be conducted under a variety of conditions (e.g. neat, in diphenyl ether, in PPA, in the presence of A1C1 3 ) as cited by Sekiba., T., Bull. Soc. Chem. Jpn., (1973), 46, p 577; Kappe, et al., J. Heterocycl. Chem., (1989), 26 (6), p 1555; Yamaguchi, S., et al., (1990), 27, p 999; Mohamed, E., J. Chem.
  • Malonate esters of Formula 12 are either commercially available or easily prepared as cited in March, J., Advanced Organic Chemistry, 3 rd ed., John Wiley; New York (1985), p 419.
  • Compounds of Formula lib a subset of compounds of Formula II wherein Q is S (Scheme 17), can be prepared from compounds of Formula Ila in a manner similar to the previously-described preparation of compounds If from compounds of Formula la using phosphorous pentasulfide (P 2 S5) or Lawesson's reagent.
  • P 2 S5 phosphorous pentasulfide
  • Lawesson's reagent can be prepared from compounds of Formula Ila in a manner similar to the previously-described preparation of compounds If from compounds of Formula la using phosphorous pentasulfide (P 2 S5) or Lawesson's reagent.
  • syntheses of compounds of the present invention are not limited solely to the procedures and methods described herein.
  • Other potentially useful routes exist (i.e., El-Abadelah, M., Heterocycles, (1997), 45 (2), p 255; McCombie, S., ibid, 35 (1) (1993), p 93; Cieslak, et al, Rocz. Chem., (1959), 33, p 349 (Chem. Abstr., 1960:3404)) which can be adapted by the skilled practitioner to deliver certain compounds of Formulae I and II as well. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formulae I and II may not be compatible with certain functionalities present in the intermediates.
  • Step D Preparation of 7-bromo-2-(metfaylsulfonyl -4H-thiopyranor2.3-blpyridin-4- one A solution of 0.75 g of the intermediate for Step C, 1.55 g of 75% meta- chloroperbenzoic acid and 30 mL of methylene chloride was stirred at room temperature overnight.
  • Step B Preparation of l-(2-bromo-3-pyridinyl)-l-pentanone
  • Step C Preparation of l-(2-hvdroxy-3-pyridinyl -l-pentanone
  • Step D Preparation of l-(2-hvdroxy-5-iodo-3-pyridinyl)-l-pentanone A mixture of 4.0 g of l-(2-hydroxy-3-pyridinyl)-l-pentanone and 5.5 g of
  • N-iodosuccinimide in 40 ml methylene chloride was stirred at room temperature overnight.
  • the reaction mixture was then diluted with methylene chloride, washed with water, and the organic phase separated, dried (anhydrous sodium sulfate), and concentrated in vacuo.
  • W is O.
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • W is O.
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy ⁇ 4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions 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 12 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B Granule Compound 12 10.0% attapulgite granules (low volatile matter
  • Example C Extruded Pellet Compound 26 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Emulsifiable Concentrate
  • Compound 26 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.
  • the compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops.
  • pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuligine
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene
  • insecticides such as abamectin, acep
  • Preferred for better control of plant diseases caused by fungal plant pathogens e.g., lower use rate or broader spectrum of plant pathogens controlled
  • resistance management are mixtures of a compound of this invention with a fungicide selected from the group azoxystrobin, benomyl, cymoxanil, epoxiconazole, fenpropidin, fenpropimorph, flusilazole, fosetyl-aluminum, kresoxim methyl and mancozeb.
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds can also be applied to the seed to protect the seed and seedling.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
  • BIOLOGICAL EXAMPLES OF THE INVENTION Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.
  • TEST A The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made.
  • TEST B The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Puccinia recondita the causal agent of wheat leaf rust
  • TEST C The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
  • Pyricularia oryzae the causal agent of rice blast
  • TEST D The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Phytophthora infestans the causal agent of potato and tomato late blight
  • TEST E The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made.
  • Plasmopara viticola the causal agent of grape downy mildew
  • test suspension was sprayed to the point of run-off on cucumber seedlings.
  • seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Botrytis cinerea the causal agent of gray mold on many crops
  • Results for Tests A-F are given in Table A.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls).
  • a dash (-) indicates no test results.
  • ND indicates disease control not determined due to phytotoxicity. # indicates significant activity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés des formules (I) et (II), leurs N-oxydes et leurs sels appropriés pour l'agriculture, ces composés s'utilisant comme fongicides. Dans les formules selon l'invention, W représente O, S(O)n ou NR5; Q représente O ou S; Z représente O, S ou NR5; G représente, pris ensemble avec les deux carbones de liaison, un noyau hétérocyclique aromatique éventuellement substitué; et R?1, R2, R5¿ et n sont comme définis dans l'invention. L'invention concerne également des compositions contenant le composés de la formule (I) ou de la formule (II), ainsi qu'un procédé de lutte contre des maladies végétales provoquées par des pathogènes fongiques de plantes, le procédé consistant à appliquer une quantité effective d'un composé de la formule (I) ou de la formule (II).
PCT/US1999/017707 1998-08-06 1999-08-03 Hétérocycles bicycliques fondus fongicides WO2000008026A2 (fr)

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WO2003027113A1 (fr) * 2001-09-26 2003-04-03 Bayer Pharmaceuticals Corporation Derives de 1,6-naphthyridine et leur utilisation dans le traitement du diabete et de troubles associes
JP2008540652A (ja) * 2005-05-17 2008-11-20 シェーリング コーポレイション 脂質異常症の処置のための、ニコチン酸受容体アゴニストとしての複素環
JP2010509397A (ja) * 2006-11-15 2010-03-25 シェーリング コーポレイション 窒素を含むヘテロ環化合物およびその使用方法
WO2011051212A1 (fr) * 2009-10-28 2011-05-05 Basf Se Utilisation de composés hétéroaromatiques en tant qu'herbicides
JP2012506886A (ja) * 2008-10-29 2012-03-22 ビーエーエスエフ ソシエタス・ヨーロピア 除草作用を有する置換ピリジン
JP2013177456A (ja) * 2013-06-14 2013-09-09 Ube Industries Ltd ペンタフルオロスルファニル基を有する複素環オリゴマー化合物
US8557807B2 (en) * 2008-01-24 2013-10-15 Signal Rx Pharmaceuticals, Inc. Thienopyranones as kinase inhibitors
US20170022165A1 (en) * 2014-04-03 2017-01-26 Helmholtz-Zentrum für Infektionsforschung GmbH Pqsr modulators
CN106810560A (zh) * 2016-12-23 2017-06-09 天津科技大学 一种8‑氮杂香豆素的合成方法及其在抗肿瘤药物中的应用
EP3573619A4 (fr) * 2017-01-27 2020-10-28 SignalRX Pharmaceuticals, Inc. Thiénopyranones et furanopyranones en tant qu'inhibiteurs de kinase, de bromodomaine et de points de contrôle
WO2021233800A1 (fr) 2020-05-20 2021-11-25 Merck Patent Gmbh Dérivés d'azacoumarines et d'azathiocoumarine destinés à être utilisés dans des dispositifs optiquement actifs
EP3827006A4 (fr) * 2018-07-23 2022-04-06 Signalrx Pharmaceuticals, Inc. Composés à molécule unique fournissant une inhibition multi-cible de btk et d'autres protéines et leurs méthodes d'utilisation
US11702396B2 (en) 2017-02-15 2023-07-18 Johnson & Johnson Surgical Vision, Inc. Hydrophobic compounds for optically active devices
US11753387B2 (en) 2017-02-15 2023-09-12 Johnson & Johnson Surgical Vision, Inc. Compounds for optically active devices
US11958819B2 (en) 2015-08-21 2024-04-16 Johnson & Johnson Surgical Vision, Inc. Compounds for optically active devices

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WO2003027113A1 (fr) * 2001-09-26 2003-04-03 Bayer Pharmaceuticals Corporation Derives de 1,6-naphthyridine et leur utilisation dans le traitement du diabete et de troubles associes
WO2003027112A1 (fr) * 2001-09-26 2003-04-03 Bayer Pharmaceuticals Corporation Derives 1, 8-naphtyridine utilises comme antidiabetiques
US6677352B1 (en) 2001-09-26 2004-01-13 Yamin Wang 1,6-naphthyridine derivatives and their use to treat diabetes and related disorders
US6964971B2 (en) 2001-09-26 2005-11-15 Bayer Pharmaceuticals Corporation 1,6-naphthyridine derivatives and their use to treat diabetes and related disorders
US7109196B2 (en) 2001-09-26 2006-09-19 Bayer Pharmaceuticals Corporation 1,8 Naphthyridine derivatives and their use to treat diabetes and related disorders
JP2008540652A (ja) * 2005-05-17 2008-11-20 シェーリング コーポレイション 脂質異常症の処置のための、ニコチン酸受容体アゴニストとしての複素環
JP2010509397A (ja) * 2006-11-15 2010-03-25 シェーリング コーポレイション 窒素を含むヘテロ環化合物およびその使用方法
US8557807B2 (en) * 2008-01-24 2013-10-15 Signal Rx Pharmaceuticals, Inc. Thienopyranones as kinase inhibitors
JP2012506886A (ja) * 2008-10-29 2012-03-22 ビーエーエスエフ ソシエタス・ヨーロピア 除草作用を有する置換ピリジン
WO2011051212A1 (fr) * 2009-10-28 2011-05-05 Basf Se Utilisation de composés hétéroaromatiques en tant qu'herbicides
JP2013177456A (ja) * 2013-06-14 2013-09-09 Ube Industries Ltd ペンタフルオロスルファニル基を有する複素環オリゴマー化合物
US20170022165A1 (en) * 2014-04-03 2017-01-26 Helmholtz-Zentrum für Infektionsforschung GmbH Pqsr modulators
US10472326B2 (en) * 2014-04-03 2019-11-12 Helmholtz-Zentrum für Infektionsforschung GmbH PQSR modulators
US11958819B2 (en) 2015-08-21 2024-04-16 Johnson & Johnson Surgical Vision, Inc. Compounds for optically active devices
CN106810560A (zh) * 2016-12-23 2017-06-09 天津科技大学 一种8‑氮杂香豆素的合成方法及其在抗肿瘤药物中的应用
EP3573619A4 (fr) * 2017-01-27 2020-10-28 SignalRX Pharmaceuticals, Inc. Thiénopyranones et furanopyranones en tant qu'inhibiteurs de kinase, de bromodomaine et de points de contrôle
US11702396B2 (en) 2017-02-15 2023-07-18 Johnson & Johnson Surgical Vision, Inc. Hydrophobic compounds for optically active devices
US11753387B2 (en) 2017-02-15 2023-09-12 Johnson & Johnson Surgical Vision, Inc. Compounds for optically active devices
EP3827006A4 (fr) * 2018-07-23 2022-04-06 Signalrx Pharmaceuticals, Inc. Composés à molécule unique fournissant une inhibition multi-cible de btk et d'autres protéines et leurs méthodes d'utilisation
WO2021233800A1 (fr) 2020-05-20 2021-11-25 Merck Patent Gmbh Dérivés d'azacoumarines et d'azathiocoumarine destinés à être utilisés dans des dispositifs optiquement actifs

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