EP0623125A1 - Fongicides heterocycliques pontes - Google Patents

Fongicides heterocycliques pontes

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Publication number
EP0623125A1
EP0623125A1 EP93902842A EP93902842A EP0623125A1 EP 0623125 A1 EP0623125 A1 EP 0623125A1 EP 93902842 A EP93902842 A EP 93902842A EP 93902842 A EP93902842 A EP 93902842A EP 0623125 A1 EP0623125 A1 EP 0623125A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
alkoxy
independently
ring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP93902842A
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German (de)
English (en)
Inventor
John Powell Daub
Bruce Lawrence Finkelstein
Daniel Anthony Kleier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
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Publication of EP0623125A1 publication Critical patent/EP0623125A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems

Definitions

  • the disclosed invention generally is directed to the field of fungicidal compounds and compositions.
  • This invention comprises compounds of Formula I including all geometric and stereoisomers and
  • X is N or CR 4 ;
  • Y is N or CR 5 ;
  • Z is N or CR 6 ;
  • Q is a fused benzene, naphthalene, thiophene,
  • R 1 , R 2 , R 3 and R 4 are independently H; halogen; cyano; hydroxy; C 1 -C 6 alkyl; C 1 -C 4 haloalkyl; C 1 -C 4 alkylthio; C 1 -C 4 alkylsulfinyl; C 1 -C 4 alkylsulfonyl; C 3 -C 6 cycloalkyl optionally substituted with 1-2 methyl groups; C 1 -C 4 alkoxy; C 1 -C 4 haloalkoxy; C 2 -C 4 alkoxyalkyl; C 2 -C 4 alkenyl; C 2 -C 4 haloalkenyl; C 2 -C 4 alkenyloxy; C 2 -C 4 alkynyl; C 2 -C 4 alkynyloxy;
  • R 1 and R 4 , R 2 and R 4 or R 2 and R 5 can be taken together to form -(CH 2 ) 3 -, -(CH 2 ) 4 - or a fused phenyl ring;
  • R 5 and R 6 are independently H, halogen, C 1 -C 2
  • R 7 is halogen; cyano; nitro; hydroxy;
  • R 8 and R 14 are independently 1-2 halogen, 1-2 C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • R 9 , R 10 and R 11 are independently H or C 1 -C 2 alkyl
  • R 12 , R 13 , R 15 , R 16 , R 17 , and R 18 are independently H or C 1 -C 2 alkyl
  • R 12 and R 13 , R 15 and R 16 or R 17 and R 18 can be taken together with the nitrogen to which they are attached to form a piperidino, pyrrolidino or morpholino ring;
  • R 19 is halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • p 0, 1 or 2;
  • the compounds are other than 2-[4,6-bis(tri- chloromethyl)-1,3,5-triazin-2-yl]-1,10-phenanthroline or 2-(2-pyridinyl)-1,10-phenanthroline.
  • X is N or CR 4 ;
  • Y is N or CR 5 ;
  • Z is N or CR 6 ;
  • Q is a fused benzene, naphthalene, thiophene,
  • A is a bridge -G 1 -G 2 -G 3 -G 4 -, wherein G 1 , G 2 , G 3 or
  • G 4 are independently O, S(O) p , NR 9 , CR 10 R 11 ,
  • R 1 , R 2 , R 3 and R 4 are independently H; halogen; cyano; hydroxy; C 1 -C 6 alkyl; C 1 -C 4 haloalkyl; C 1 -C 4 alkylthio; C 1 -C 4 alkylsulfinyl; C 1 -C 4 alkylsulfonyl; C 3 -C 6 cycloalkyl optionally substituted with 1-2 methyl groups; C 1 -C 4 alkoxy; C 1 -C 4 haloalkoxy; C 2 -C 4 alkoxyalkyl; C 2 -C 4 alkenyl; C 2 -C 4 haloalkenyl; C 2 -C 4 alkenyloxy; C 2 -C 4 alkynyl; C 2 -C 4 alkynyloxy; NR 12 R 13; phenyl or phenoxy optionally
  • R 1 and R 4 , R 2 and R 4 or R 2 and R 5 can be taken together to form -(CH 2 ) 3 -, -(CH 2 ) 4 - or a fused phenyl ring;
  • R 5 and R 6 are independently H, halogen, C 1 -C 2
  • R 7 is halogen; cyano; nitro; hydroxy;
  • alkylsulfinyl C 1 -C 4 alkylsulfonyl; (C 1 -C 4 alkyl) 3 silyl; C 3 -C 6 cycloalkyl; C 2 -C 5
  • alkylcarbonyl C 2 -C 4 alkenyl; C 2 -C 4
  • R 8 and R 14 are independently 1-2 halogen, 1-2 C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • R 9 , R 10 and R 11 are independently H or C 1 -C 2 alkyl
  • R 12 , R 13 , R 15 , R 16 , R 17 , and R 18 are independently H or C 1 -C 2 alkyl; or R 12 and R 13 , R 15 and R 16 or
  • R 17 and R 18 can be taken together with the nitrogen to which they are attached to form a piperidino, pyrrolidino or morpholino ring;
  • R 19 is halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy; p is 0, 1 or 2;
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” denotes straight chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl or n-hexyl.
  • Alkenyl denotes straight chain or branched alkenes; e.g., vinyl, 1-propenyl, 2-propenyl, 3- propenyl and the different butenyl isomers.
  • CH 2 CHCH 2 CH 2 O.
  • Alkynyl includes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl isomers.
  • Alkynyloxy denotes straight or branched
  • alkynyloxy moieties examples include HC ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 O.
  • Alkylthio includes methylthio, ethylthio, and the different propylthio and butylthio isomers.
  • Alkylsilyl includes (CH 3 ) 2 (t-C 4 H 9 ) Si, (CH 3 ) 3 Si and (CH 3 CH 2 ) 3 Si.
  • alkylsulfinyl examples include CH 3 S(O),
  • 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 isomers.
  • Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • 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 CF 3 , CH 2 Cl, CH 2 CF 3 and CF 2 CF 3 . Examples of “haloalkoxy” include CF 3 O, Cl 3 CCH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 6. For example, C 1 -C 3
  • alkylsulfonyl designates methylsulfonyl
  • C 2 alkoxyalkoxy designates CH 3 OCH 2 O
  • C 3 alkoxyalkoxy designates, for example, CH 3 OCH 2 CH 2 O
  • C 4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 and
  • alkoxycarbonyl examples include CO 2 CH 3 , CO 2 CH 2 CH 3 , CO 2 CH 2 CH 2 CH 3 , CO 2 CH(CH 3 ) 2 and the different butoxycarbonyl isomers.
  • salts of the compounds of the invention include those formed with organic or inorganic bases when the compound contains an acidic group such as a carboxylic acid, phenol, or mercapto group.
  • the metal complexes of the compounds of the invention include complexes with metal salts such as copper, zinc, manganese, and iron salts. These complexes can be prepared prior to formulating the compound or can be prepared by adding the appropriate metal salt to the formulation.
  • Preferred compounds of Formula I for reasons of greatest fungicidal activity and/or ease of synthesis are:
  • X is N or CR 4 ;
  • Y is N or CR 5 ;
  • Z is N or CR 6 ;
  • Q is a fused benzene, naphthalene, thiophene, furan, pyrrole, pyridine or pyrimidine ring each optionally substituted with R 7 and R 8 ;
  • A is a bridge selected from the group
  • R 1 , R 2 , R 3 and R 4 are independently H; halogen; cyano; hydroxy; C 1 -C 6 alkyl; C 1 -C 4
  • alkylsulfinyl C 1 -C 4 alkylsulfonyl; C 3 -C 6 cycloalkyl optionally substituted with 1-2 methyl groups; C 1 -C 4 alkoxy; C 1 -C 4
  • R 4 , R 2 and R 4 or R 2 and R 5 can be taken together to form -(CH 2 ) 3 -, -(CH 2 ) 4 - or a fused phenyl ring;
  • R 5 and R 6 are independently H, halogen, C 1 -C 2 alkyl or C 1 -C 2 alkoxy;
  • R 7 is halogen; cyano; nitro; hydroxy; hydroxy- carbonyl; C 1 -C 6 alkyl; C 1 -C 4 haloalkyl;
  • R 9 , R 10 and R 11 are independently H or C 1 -C 2
  • R 12 , R 13 , R 15 , R 16 , R 17 , and R 18 are
  • R 12 and R 13 , R 15 and R 16 or R 17 and R 18 can be taken together with the nitrogen to which they are attached to form a piperidino,
  • R 19 is halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • p 0, 1 or 2;
  • X is CR 4 ;
  • Y is N or CH
  • Z is N or CH
  • A is a bridge selected from the group
  • Q is a fused benzene, thiophene, furan or
  • A is selected from the group consisting of
  • R 1 , R 2 , R 3 and R 4 are independently H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, cyclopropyl,
  • R 7 is halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 2 -C 4 alkoxyalkoxy.
  • Q is a fused benzene ring optionally
  • a method of controlling fungus disease in plants that comprises treating the locus to be
  • X is N or CR 4 ;
  • Y is N or CR 5 ;
  • Z is N or CR 6 ;
  • Q is a fused benzene, naphthalene, thiophene, furan, pyrrole, pyridine or pyrimidine ring each optionally substituted with R 7 and R 8 ;
  • A is a bridge selected from the group consisting of: -CR 10 R 11 -; -G-;
  • a taken together with the attached atoms forms a 5-8 membered ring; and the directionality of A may be that the left side of A is bonded to the Q ring and the right side is bonded to the pyridyl
  • R 1 , R 2 , R 3 and R 4 are independently H;
  • halogen cyano; hydroxy; C 1 -C 6 alkyl; C 1 -C 4 haloalkyl; C 1 -C 4 alkylthio; C 1 -C 4 alkylsulfinyl; C 1 -C 4 alkylsulfonyl; C 3 -C 6 cycloalkyl optionally substituted with
  • R 1 and R 4 , R 2 and R 4 or R 2 and R 5 can be taken together to form -(CH 2 ) 3 -, -(CH 2 ) 4 - or a fused phenyl ring;
  • R 5 and R 6 are independently H, halogen, C 1 -C 2 alkyl or C 1 -C 2 alkoxy;
  • R 7 is halogen; cyano; nitro; hydroxy;
  • alkylsulfinyl C 1 -C 4 alkylsulfonyl; (C 1 -C 4 alkyl) 3 silyl; C 3 -C 6 cycloalkyl; C 2 -C 5 alkylcarbonyl; C 2 -C 4 alkenyl; C 2 -C 4 alkenyloxy; C 2 -C 4 alkynyl; C 2 -C 4
  • R 8 and R 14 are independently 1-2 halogen, 1-2 C 1 -C 3 alkyl, C 1 - C2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • R 9 , R 10 and R 11 are independently H or C 1 -C 2 alkyl
  • R 12 , R 13 , R 15 , R 16 , R 17 , and R 18 are independently H or C 1 -C 2 alkyl; or R 12 and R 13 , R 15 and R 16 or R 17 and R 18 can be taken together with the nitrogen to which they are attached to form a piperidino, pyrrolidino or morpholino ring;
  • R 19 is halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl,
  • p 0, 1 or 2;
  • X is CR 4 ;
  • Y is N or CH
  • Z is N or CH
  • A is a bridge selected from the group consisting of: -(CR 10 R 11 -CR 10 R 11 )-;
  • Q is a fused benzene, thiophene, furan or pyridine ring each optionally substituted with R 7 and R 8 ;
  • A is selected from the group consisting of:
  • R 1 , R 2 , R 3 and R 4 are independently H,
  • R 7 is halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4
  • haloalkyl C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 2 -C 4 alkoxyalkoxy.
  • Q is a fused benzene ring optionally
  • Preferred for greatest fungicidal activity and/or ease of synthesis is a method according to Preferred 4 wherein the compound is 6,7-dihydro-2- (4-methyl-2-pyrimidinyl)-5-H-benzo[6,7]cyclohepta[1,2- b]pyridine.
  • Compounds of Formula I when Y is N and X is CR 4 , can be prepared by the reaction of amidines of Formula II with Formula III compounds in the presence of a suitable base as illustrated in Scheme 1.
  • Typical reactions involve the combination of an amidine II or its conjugate acid salt (such as a hydrochloride) with 1 to 1.5 equivalents of a Formula III compound in an inert solvent in the presence of a catalytic amount to 2.5 equivalents of base.
  • Typical bases include alkali metal alkoxides (such as sodium methoxide and sodium ethoxide) and organic amine bases (such as
  • Typical solvents include alcohols (such as methanol and ethanol), cyclic ethers (such as tetrahydrofuran and dioxane), pyridine, and dimethylformamide.
  • the reaction temperature typically ranges from 50°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in 1 to 6 h. This method is not applicable when R 1 or R 2 are substituents which are attached through a heteroatom such as alkoxy and halogen.
  • Compounds of Formula III are known in the art or can be prepared by related methods.
  • R 20 is C 1 -C 4 alkyl
  • Typical reactions involve the combination of an amidine II or its conjugate acid salt (such as a hydrochloride) with 1 to 1.5 equivalents of a Formula IV compound in an inert solvent in the presence of 0 to 2.5 equivalents of base.
  • Typical bases include alkali metal alkoxides (such as methoxide and sodium ethoxide) and organic amine bases (such as triethylamine and diethylaniline).
  • Typical solvents include alcohols (such as methanol and ethanol), cyclic ethers (such as tetrahydrofuran), pyridine, and dimethylformamide.
  • the reaction temperature typically ranges from 50°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in 24 h. This method is not applicable when R 1 and R 2 are
  • Typical reactions involve the combination of an amidine of
  • Formula II or its conjugate acid salt (such as a
  • Typical bases include alkali metal alkoxides (such as sodium methoxide and sodium ethoxide) and organic amine bases (such as triethylamine and diethylaniline).
  • Typical solvents include alcohols (such as methanol and ethanol), cyclic ethers (such as tetrahydrofuran and dioxane), pyridine, and dimethyIformamide.
  • the reaction temperature typically ranges from 50°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in 24 h. This method is not
  • R 1 is a substituent which is attached through a heteroatom such as alkoxy and halogen. This method also is not applicable when R 2 is a better leaving group than L 1 since the latter would be retained in the product.
  • Compounds of Formula V are well known in the art or can be prepared by related methods (Abdulla et al., Tetrahedron, 1979, 35,
  • heteroatom such as alkoxy and halogen.
  • R 20 is C 1 -C 4 alkyl.
  • hydrogen can be prepared by reductive removal of a halogen, alkylthio, alkylsulfinyl, or alkylsulfonyl group as outlined in Scheme 5.
  • a catalyst such as palladium on carbon under hydrogen gas in an inert solvent such as water, an alcohol (such as methanol or ethanol), ethyl acetate, or toluene at 25° to 50°C.
  • the dehalogenation can be conducted in the presence of an equivalent of a base (such as ammonia, sodium hydroxide, sodium carbonate, or sodium acetate) to neutralize the liberated hydrogen halide.
  • the reaction is typically conducted as above using Raney nickel as the catalyst in the absence of base and optionally under hydrogen gas.
  • Compounds of Formula I when R 1 or R 2 are alkyl or haloalkyl, can be prepared by the reaction of compounds of Formula I, where R 1 or R 2 are leaving groups such as halogen, alkylsulfinyl, or alkylsulfonyl, with dialkyl malonates of Formula VII in the presence of base followed by hydrolysis and decarboxylation as outlined in Scheme 6.
  • the first reaction is carried out by combining a compound of Formula I, where R 1 or R 2 are leaving groups, with 1 to 2 equivalents of a Formula VII compound in the presence of 1 to 4 equivalents of a suitable base in an inert solvent.
  • Typical bases include alkali metal hydrides (such as sodium hydride and potassium hydride), alkyllithiums (such as
  • alkali metal amides such as lithium diisopropylamide
  • alkali metal hydroxides such as sodium hydroxide
  • Typical solvents include nitriles (such as acetonitrile), ethers (such as diethyl ether and tetrahydrofuran), halohydrocarbons (such as
  • the reaction temperature typically ranges from 0°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in 0.5 to 24 h.
  • the hydrolysis reaction is typically carried out in water with an optional organic cosolvent (such as methanol, ethanol, tetrahydrofuran, or
  • reaction temperature typically ranges from 0°C to the reflux temperature of the solvent mixture being used and the hydrolysis is usually complete after 0.2 to 24 h.
  • the hydrolysis product (malonic acid intermediate) need not be
  • R 20 is C 1 -C 4 alkyl
  • R 21 is C 1 -C 5 alkyl or C 1 -C 3 haloalkyl.
  • R 1 or R 2 when R 1 or R 2 are cyano, hydroxy, alkylthio, alkoxy, haloalkoxy, alkenyloxy, alkynyloxy, (di) alkylamino, or substituted phenoxy, can be prepared by the reaction of compounds of Formula I, where R 1 or R 2 are leaving groups such as halogen, alkylsulfinyl, or alkylsulfonyl, with a nucleophile L 2 - M 1 in the presence of an optional base as outlined in Scheme 7.
  • Typical reactions involve the combination of a compound of Formula I, where R 1 or R 2 are a leaving group, with 1 to 2 equivalents of a L 2 -M 1 compound in an inert solvent.
  • Typical bases include alkali metal hydrides (such as sodium hydride), alkali metals (such as sodium), and alkyllithiums (such as butyllithium).
  • Typical solvents include alcohols (such as methanol and ethanol), ethers (such as diethyl ether, tetrahydrofuran, and dioxane), nitriles (such as acetonitrile), dimethylformamide, and dimethyl sulfoxide.
  • Potentially nucleophilic solvents, such as alcohols should be used only when they will not compete with the nucleophile L 2 -M 1 .
  • the reaction temperature typically ranges from 0°C to the reflux temperature of the particular solvent used, and the reaction is usually complete within 2 days.
  • L 2 -M 1 represent common reagents such as sodium alkoxides, alcohols, phenols, sodium cyanide, sodium hydroxide, (di) alkylamines, and the like.
  • Catalysts such as copper, copper(I) chloride, copper (II) chloride, and copper (II) oxide may be added to facilitate the reaction.
  • L 2 is cyano, hydroxy, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, NR 12 R 13 , or phenoxy substituted with R 14 ;
  • M 1 is H or alkali metal.
  • alkylsulfinyl or alkylsulfonyl can be prepared by the oxidation of compounds of Formula I, where R 1 or R 2 are alkylthio, as outlined in Scheme 8.
  • Typical reactions involve the combination of a compound of Formula I (R 1 or R 2 is alkylthio) with a suitable oxidant in an inert solvent.
  • R 1 or R 2 are alkylsulfinyl in the desired product I, 1 to 1.1 equivalents of oxidant are used, and when R 1 or R 2 are alkylsulfonyl in the product I, 2 to 2.2 equivalents of oxidant are used.
  • Typical oxidants are 3-chloroperoxybenzoic acid, magnesium monoperoxyphthalate, peracetic acid, hydrogen peroxide, and the like.
  • Typical solvents include halohydrocarbons (such as dichloromethane, 1,2- dichloroethane, and chloroform) and aromatic hydrocarbons (such as dichloromethane, 1,2- dichloroethane, and chloroform) and aromatic hydrocarbons (such as halohydrocarbons (such as dichloromethane, 1,2- dichloroethane, and chloroform) and aromatic
  • hydrocarbons such as toluene
  • R 20 is C 1 -C 4 alkyl .
  • Compounds of Formula I when R 1 or R 2 are halogen, can be prepared by the reaction of compounds of Formula I, where R 1 or R 2 are hydroxy, with a halogenating agent such as phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide, phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, phosgene, and the like as illustrated in Scheme 9.
  • Typical reactions involve the combination of compounds of Formula I, when R 1 or R 2 is hydroxy, with an excess of the halogenating agent ranging from 1.1 to 10 equivalents, with 2 to 4
  • reaction can be conducted in the absence of solvent or in the presence of a suitable inert solvent including aromatic hydrocarbons (such as benzene and toluene),
  • halohydrocarbons such as dichloromethane and
  • reaction temperature can range from -10°C to 200°C with 25°C to 100°C being preferred.
  • the reaction is
  • alkali metal alkoxides such as sodium methoxide and sodium ethoxide.
  • solvents include alcohols (such as methanol and
  • reaction temperature typically ranges from ambient temperature to the reflux temperature of the particular solvent being used and the reaction is usually complete in 1 to 24 h.
  • An example of this method is taught by Lafferty et al. (J. Org. Chem. 1967, 32, 1591-1596).
  • R 2 is attached through a heteroatom (such as alkoxy)
  • the product usually loses R 2 giving product I wherein R 2 is hydroxy
  • an example of this reaction using a dialkylmalonate VIII (R 2 is alkoxy) giving a dihydroxypyrimidine also may be found in the above reference by Lafferty et al.
  • reaction temperature can range from 0°C to 50°C (preferably ambient temperature) and the reaction is usually complete after 1 to 48 h.
  • the reaction is typically worked up by neutralizing with an acid (such as acetic acid), concentrating the reaction mixture, dissolving in an appropriate solvent (such as ether), filtering off the salt by-product (e.g., sodium
  • the intermediate amidines of Formula II can be prepared by the reaction of an imidate of Formula XII with 1.0 to 1.1 equivalents of an ammonium salt (such as ammonium chloride, ammonium bromide, ammonium acetate, and ammonium formate) in an alcohol
  • an ammonium salt such as ammonium chloride, ammonium bromide, ammonium acetate, and ammonium formate
  • the reaction temperature can range from ambient temperature to the reflux temperature of the particular solvent being used and the reaction is usually complete after 30 min to 5 h.
  • the reaction mixture is
  • amidine salt (HL 3 ) which is purified by recrystallization or trituration.
  • the amidine salts can be used in the previously described reactions or can be first converted to their conjugate bases.
  • amidines of Formula II can be prepared directly from carbonitriles XI by the reagent MeAl (Cl)NH 2 as described by Garigipati (Tetrahedron Lett., 1990, 31, 1969-1972).
  • the esters of Formula IX can be prepared from imidates of Formula XII by aqueous hydrolysis with an optional organic cosolvent.
  • Typical reactions involve the combination of an imidate XII with an excess of acid (such as sulfuric acid or hydrochloric acid) in an optional organic cosolvent (such as methanol, ethanol, tetrahydrofuran, and dioxane).
  • acid such as sulfuric acid or hydrochloric acid
  • an optional organic cosolvent such as methanol, ethanol, tetrahydrofuran, and dioxane
  • reaction is usually complete within 6 h.
  • R 20 is C 1 -C 4 alkyl
  • M 2 is an alkali metal
  • L 3 is a counterion such as Cl, Br, OAc, or OCHO.
  • N-oxide intermediates of Formula XIV can be prepared by oxidation of compounds of Formula XIII with 1 to 1.2 equivalents of a suitable oxidizing reagent such as 3-chloroperoxybenzoic acid, magnesium
  • Typical solvents include
  • halohydrocarbons such as dichloromethane, 1,2- dichloroethane, and chloroform
  • aromatic hydrocarbons such as dichloromethane, 1,2- dichloroethane, and chloroform
  • reaction temperature can range from 0°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in 24 h.
  • Z is N
  • a mixture of N-oxides may be formed; both of these regioisomeric N-oxides can be used for the subsequent Fife cyanation to intermediates XI.
  • these compounds of Formula XIII, when Z is CR 6 can be prepared using -one of several pyridine annulation procedures known in the art. Two such procedures are outlined in Scheme 13.
  • Formula XV The starting ketones of Formula XV are known in the art or can be obtained by methods analogous to known procedures.
  • Formula XV compounds includes indanones, tetralones, benzosuberones, chromanones and homologs, thiochromanones and homologs, isochromanones, benzofuran-3-ones, and others.
  • ketones of Formula XV can be converted to compounds of Formula XIX, where L 4 is a leaving group, by methods known in the art.
  • R 20 is C 1 -C 4 alkyl
  • L 4 is a leaving group such as halogen, alkoxy, alkylthio, (di) alkylamino, (halo) alkylsulf onyloxy, and arylsulf onyloxy.
  • N-cyanoamidines of Formula XXII can be prepared by the reaction of imidates of Formula XII with
  • R 20 is C 1 -C 4 alkyl.
  • R 2 is a leaving group such as alkoxy in Formula XXIV, then R 2 will be hydroxy in the product which can be
  • R 20 is C 1 -C 4 alkyl.
  • Compounds of Formula I when X and Y are CR 4 and CR 5 , respectively, can be prepared from intermediate carbonitriles of Formula XI as outlined in Scheme 17. The addition of organometallic reagents to nitriles to give ketones represented by Formula XXVI is well known in the art. Ketones of Formula XXVI can be converted to intermediates of Formula XXVII by methods well known in the art.
  • M 3 is alkali or alkaline earth metal; and L 1 is hydrogen or a leaving group such as halogen, alkoxy, alkylthio, (di) alkylamino, (halo) alkylsulfonyloxy, and arylsulfonyloxy.
  • compounds of Formula I can be prepared by transition-metal catalyzed aryl coupling reactions as illustrated in Scheme 18.
  • Intermediates of Formula XXIX, when L 5 is halogen, can be prepared by the reaction of N-oxide intermediates of Formula XIV with a halogenating agent such as phosphorus
  • Aryltin intermediates of Formula XXX can be prepared from
  • Formula XXIX compounds by the displacement of L 5 with a trialkylstannylsodium reagent as taught by Wursthorn et al. (J. Am. Chem. Soc. 1978, 100, 2779-2789) or, when Z is CR 6 , by metal-halogen exchange with an alkyllithium (such as butyllithium) and reaction with a trialkyltin halide (such as tributyltin chloride).
  • an alkyllithium such as butyllithium
  • a trialkyltin halide such as tributyltin chloride
  • Typical palladium catalysts include tetrakis (triphenylphosphine) palladium (0) and bis (triphenylphosphine)palladium (II) chloride.
  • Typical solvents include aromatic hydrocarbons (such as benzene and toluene), cyclic ethers (such as tetrahydrofuran and dioxane), and dimethylformamide.
  • Related coupling reactions are known in the art as discussed by Solberg et al. (Acta Chem. Scand. 1989, 43, 62-68), Undheim et al. (Heterocycles 1990, 30, 1155-1193), Gronowitz et al. (Chem. Scripta 1986, 26, 305-309), Fu et al.
  • compounds of Formula I can be prepared by similar palladium-catalyzed couplings of intermediates of Formula XXIX with arylstannanes of Formula XXXII as illustrated in Scheme 18.
  • Compounds of Formula XXXI are well known in the art or can be prepared by analogous methods and compounds of Formula XXXII can be prepared from these compounds by
  • L 5 is a leaving group such as halogen
  • R 20 is C 1 -C 4 alkyl.
  • L 4 is a leaving group such as halogen, alkoxy, alkylthio, (di) alkylamino, (halo) alkylsulfonyloxy, and arylsulfonyloxy.
  • L 4 is a leaving group such as halogen, alkoxy, alkylthio, (di)alkylamino, (halo)alkylsulfonyloxy, and
  • halopyridines and halopyrimidines which are well known in the art or can be prepared by related methods.
  • Groups A 1 and A 2 are chosen so that a bond or bonds can be made between them to construct the particular bridge A.
  • lactonization using an activating agent gives compounds of Formulae XIII and I where A is -OC(O)CH 2 -.
  • an activating agent such as 1,3- dicyclohexylcarbodiimide
  • etherification by treatment with base gives compounds where A is -OCH 2 -
  • a 1 and A 2 are CH 2 C(O)H
  • acetal formation with 2,2-dimethoxypropane gives compounds where A is -OC(Me) 2 O-.
  • a specific example of the strategy in Scheme 21 is reported by Fu et al. (J. Org.
  • M 4 is a metallic group such as Sn(R 20 ) 3 , B(OH) 2 , B(OR 20 ) 2 ,
  • L 5 is a leaving group such as halogen
  • L6 is hydrogen or
  • a 1 and A 2 are suitable groups for creating bonds between them to construct bridge A.
  • Scheme 22 illustrates the strategy where the bridge A is first constructed using methods similar to those discussed for Scheme 21 .
  • Suitable synthetic methods include, but are not limited to,
  • the intermediate XXXIX can be converted by an intramolecular Ullman or related aryl coupling to compounds of Formula I or
  • L 5 and L 7 are independently leaving groups such as halogen
  • L 6 is hydrogen or and A 1 and A 2 are suitable groups for creating bonds between them to construct bridge A.
  • the metal complexes of the compounds of the invention include complexes with copper, zinc, iron, magnesium or manganese cations. These complexes can be made by combining the compound with the metal salt, either in aprotic solvents such as ether or
  • tetrahydrofuran or they can be generated in protic solvents such as methanol or mixtures of such solvents.
  • the complex may crystallize and precipitate from solution or the complex is crystallized as the solvent is removed.
  • N, N-dimethylhydrazine 37.51 g, 624.1 mmol
  • the reaction mixture is concentrated under reduced pressure.
  • the residue is dissolved in ethanol and reconcentrated; this is repeated once more with ethanol and twice more with dichloromethane to yield 32.65 g of the crude title hydrazone.
  • Step B 6-[ 2- (1,3-Dioxolan-2-yl)ethyl]-6,7,8,9- tetrahydro-5H-benzocyclohepten-5-one dimethylhydrazone
  • reaction mixture is then kept at -78°C for 1 h.
  • the reaction mixture is allowed to come to room temperature and is left at room temperature overnight.
  • the reaction mixture is slowly quenched with water and is then poured into water (250 mL).
  • the resulting mixture is extracted three times with diethyl ether.
  • Step E To a stirred solution of the product of Step E (8.25 g, 37.45 mmol) in methanol (75 mL) under a nitrogen atmosphere at room temperature is added a solution of sodium methoxide (3.0 mL of commercial 25 wt. % solution in methanol, 13.11 mmol) and the reaction is allowed to stir at room temperature
  • Step G 6,7-Dihydro-5H-benzo[6,7]cyclohepta[ 1 ,2- b ]pyridine-2-carboximidamide hydrochloride
  • To ar solution of the crude imidate from Step F (37.45 mmol) in absolute ethanol (48.3 mL) under a nitrogen atmosphere at room temperature is added a solution of ammonium chloride (2.003 g, 37.45 mmol) in water (18.3 mL) and the resulting mixture is heated under reflux for 3 h. The reaction mixture is allowed to cool, concentrated under reduced pressure and, finally, concentrated in vacuo .
  • Step H 6,7-Dihydro-2-(4-methyl-2-pyrimidinyl)-5H- benzo[ 6,7]cyclohepta[1,2-b]pyridine y
  • methanol 92 mL
  • acetylacetaldehyde dimethyl acetal 1.83 mL, 1.815 g, 13.74 mmol
  • Step B 2-(4,6-Dimethyl-2-pyrimidinyl)-6,7-dihydro- 5H-benzo[6,7]cyclohepta[1,2-b]pyridine
  • Step A 8-Bromo-6,7-dihydro-5H-benzo[6,7]cyolohepta- [1,2-b]pyridine and 10-bromo-6,7-dihydro-5H- benzo[6,7]cyclohepta[1,2-b]pyridine
  • 6-bromo-6,7-dihydro-5H- benzo[6,7]cyclohepta[1,2-b]pyridine To a stirred solution of 6,7-dihydro-5H- benzo[6,7]cyclohepta[1,2-b]pyridine (60.00 g,
  • Step B 8-Bromo-6,7-dihydro-2-(4-methyl-2- pyrimidinyl)-5H-benzo[6,7]cyclohepta[1,2-b]- pyridine
  • n- is normal CO 2 H is hydroxycarbonyl
  • NHEt is ethylamino n-Pr is normal-propyl
  • SPh is phenylthio t-Bu is tertiary-butyl
  • i-Pr isopropyl O-n-Bu is normal-butoxy
  • O-i-Pr is isopropoxy n-Bu is normal-butyl
  • Hex is hexyl sec-Bu is secondary-butyl
  • CN is cyano S-i-Pr is isopropylthio
  • OPh is phenoxy CO 2 Me is methoxycarbonyl
  • c-Hex is cyclo-hexyl S(O)Me is methylsulfinyl
  • NO 2 is nitro S(O) 2 Me is methylsulfonyl
  • SEt is ethylthio S(O) 2 Et is ethylsulfonyl
  • SMe is methylthio S(O) 2 -n-Bu is normal-butylsulfonyl OH is hydroxy
  • TBS is tertiary-butyldimethylsilyl OMe is methoxy Et is ethyl
  • c- is cyclo NMe 2 is dimethylamino Me is methyl NEt 2 is diethylamino Ac is acetyl
  • X and Z are CH; Y is N; R 1 is Me; R 2 , R 3 , R 7 and R' 8 are H
  • the fungicidal compositions of the present invention comprise an effective amount of at least one compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
  • Useful formulations can be prepared in conventional ways.
  • 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
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent .
  • Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S.
  • Granules and pellets can be made by
  • Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in DE 3,246,493.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • 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
  • 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 are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides.
  • Puccinia striiformis Puccinia arachidis
  • Rhizoctonia solani Sphaerotheca fuliginea
  • Fusarium oxysporum Verticillium dahliae
  • Pythium aphanidermatum Phytophthora megasperma and other generea and species closely related to these pathogens.
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides,
  • insecticides such as monocrotophos, carbofuran, tetrachlorvinphos,
  • esfenvalerate permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate,
  • fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-A1, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole,
  • fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-A1, chlorothalonil, dichlor
  • ipconazole metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox,
  • nematocides such as aldoxycarb, fenamiphos and
  • bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis, baculovirus and avermectin B.
  • 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.
  • 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.
  • Trem ® 014 polyhydric alcohol esters
  • 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 suspension was sprayed to the point of run-off on wheat seedlings.
  • 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 suspension was sprayed to the point of run-off on rice seedlings.
  • 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 suspension was sprayed to the point of run-off on tomato seedlings.
  • 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 suspension was sprayed to the point of run-off on grape seedlings.
  • 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 Botrytxs 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.
  • Botrytxs cinerea the causal agent of gray mold on many crops
  • Couplings are designated by (s)-singlet, (d)-doublet, (t)- triplet, (q)-quartet, (p)-pentet, (m)-multiplet, (dd)-doublet of doublets. Samples dissolved in CDCl 3 unless otherwise indicated.

Abstract

Cette invention concerne des composés fongicides de formule (I).
EP93902842A 1992-01-15 1992-12-30 Fongicides heterocycliques pontes Withdrawn EP0623125A1 (fr)

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PE20080145A1 (es) 2006-03-21 2008-02-11 Janssen Pharmaceutica Nv Tetrahidro-pirimidoazepinas como moduladores de trpv1
WO2008013622A2 (fr) * 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Amides azocycliques fongicides
JP5058588B2 (ja) 2006-12-26 2012-10-24 キヤノン株式会社 アザフルオレン誘導体及びこれを用いた有機発光素子
PE20091102A1 (es) 2007-12-17 2009-07-25 Janssen Pharmaceutica Nv Moduladores imidazolo-, oxazolo-, y tiazolopirimidina del trpv1
WO2009081222A1 (fr) 2007-12-21 2009-07-02 Glenmark Pharmaceuticals, S.A. Pyrimidines ou pyridines tricycliques substituées ligands des récepteurs des vanilloïdes
US20120316184A1 (en) * 2010-02-24 2012-12-13 Syngenta Crop Protection Llc Novel microbicides
KR101840313B1 (ko) * 2011-02-14 2018-03-21 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
GB2503789A (en) * 2012-05-15 2014-01-08 Syngenta Participations Ag Quinazoline derivatives as antifungal agents
WO2013180376A1 (fr) * 2012-05-30 2013-12-05 Alpha Chem Co., Ltd. Nouveau matériau de transport d'électrons et dispositif organique électroluminescent l'utilisant
EP2738171A1 (fr) * 2012-11-30 2014-06-04 Syngenta Participations AG. Dérivés tricycliques de pyridyle avec un principe pesticide actif
AR095443A1 (es) * 2013-03-15 2015-10-14 Fundación Centro Nac De Investig Oncológicas Carlos Iii Heterociclos condensados con acción sobre atr
US9458156B2 (en) * 2014-12-23 2016-10-04 Bristol-Myers Squibb Company Tricyclic compounds as anticancer agents
LT3087071T (lt) * 2013-12-24 2018-11-12 Bristol-Myers Squibb Company Tricikliniai junginiai kaip priešvėžiniai agentai
JP7349551B2 (ja) * 2020-02-12 2023-09-22 ユニマテック株式会社 含フッ素ピリミジン化合物およびその製造方法
WO2023152063A1 (fr) * 2022-02-09 2023-08-17 Merck Patent Gmbh Matériaux pour dispositifs électroluminescents organiques
CN114258915B (zh) * 2022-02-16 2022-12-16 云南农业大学 9-菲酚在稻瘟病防治中的应用

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