EP0640083A1 - Substituted pyrido 1,2-a]pyrimidinone derivatives as fungicides - Google Patents

Substituted pyrido 1,2-a]pyrimidinone derivatives as fungicides

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Publication number
EP0640083A1
EP0640083A1 EP93911028A EP93911028A EP0640083A1 EP 0640083 A1 EP0640083 A1 EP 0640083A1 EP 93911028 A EP93911028 A EP 93911028A EP 93911028 A EP93911028 A EP 93911028A EP 0640083 A1 EP0640083 A1 EP 0640083A1
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EP
European Patent Office
Prior art keywords
alkyl
haloalkyl
alkoxy
alkenyl
alkynyl
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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EP93911028A
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German (de)
French (fr)
Inventor
Thomas Paul Selby
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP0640083A1 publication Critical patent/EP0640083A1/en
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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
    • C07D491/12—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 three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • This invention relates to certain substituted pyrido[1,2*-a]pyrimidinone compounds useful as fungicides, their agriculturally suitable salts and compositions, and methods of their use as general or selective fungicides, in particular for the control of wheat powdery mildew both preventive and curative- Urban et al., Helv. Chi . Acta, 1970, 53, 905, disclose pyrido[1,2-a]pyrimidinones of Formula i and their use as analgesics and antiinflammatory agents.
  • This invention comprises compounds of Formula ⁇ including all geometric and stereoisomers, N-oxides, agriculturally-suitable salts thereof, agricultural compositions containing them and method of use of said compounds, salts, or compositions as fungicides,
  • Q is 0 or S; is O; S; S(O) ; S(0) 2 ; NH; or NR 9 ;
  • X is CR 3 or N;
  • Y is CR 4 or N;
  • CR 5 N;
  • N CR 6 ;
  • S O; or NR 7 ;
  • having the directionality of the CR 5 CR 6 r
  • R 1 is C- j ⁇ -C- L ⁇ alkyl; C 3 -C 7 cycloalkyl; C 2 -C 18 alkenyl; C 2 -C 18 alkynyl; C-L-C-- ⁇ haloalkyl; C 2 -C 1 8 haloalkenyl; C 2 -C 18 haloalkynyl; C 2 -C 18 alkoxyalkyl; C 2 -C 18 alk lthioalkyl; C 2 -C 18 alkylsulfinylalkyl; C 2 -C 18 alkylsulfonylalkyl;
  • C 4 -C 18 cycloalkylalkyl C 4 -C 18 alkenyloxyalkyl; C 4 -C 18 alkynyloxyalkyl; C 4 -C 18 cycloalkyloxy- alkyl; C 4 -C 18 alkenylthioalkyl; C 4 -C 18 alkynyl- thioalkyl; C 6 -C 18 cycloalkylthioalkyl; C 2 -C 18 haloalkoxyalkyl; C 3 -C 18 haloalkenyloxyalkyl;
  • R 3 and R 5 are each independently hydrogen; halogen; C ! -C 4 alkyl; C 1 -C 4 haloalkyl; C 1 -C alkoxy; or C 2 -C haloalkoxy; R 4 and R 6 are each independently hydrogen; halogen; c ⁇ -c 8 alkyl; C 3 -C 8 cycloalkyl; C 2 -C 8 alkenyl;
  • R 8 and R 9 are each independently O -C ⁇ alkyl;
  • R 10 and R 11 are each independently H or C x -C 4 alkyl;
  • R 12 is C- L -Cg alkyl;
  • R 8' and R 10 can be taken together to form -CH 2 CH 2 CH 2 CH 2 -, -CH 2 (CH 2 ) 3 CH 2 -,
  • R 5 and R 6 is equal to or less than 16; iii) the total number of nitrogen atoms incorporated into the bicyclic framework is less than or equal to four; iv) R 3 and R 4 are not both hydrogen; and v) X and Y are not both nitrogen.
  • Preferred for reasons of ease of synthesis or greater fungicidal activity are compounds of Formula I, denoted as Preferred 1, wherein: ' is 0; S; NH; or NR 9 ; X is CR 3 ; Y is CR 4 ;
  • R 1 is C-i-Cs alkyl; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 1 -C 8 haloalkyl; C 2 -C 8 haloalkenyl; C 2 -C 8 alkoxyalkyl; C -C 8 alkylthioalkyl; C 4 -C 8 cycloalkylalkyl; C 2 -C 8 cyanoalkyl; Ci-Ce alkoxy; C*-_-C 18 haloalkoxy; C 3 -C 8 alkenyloxy; C 3 -C 8 alkenylthio; or C 4 -C 8 alkenyloxyalkyl;
  • R 2 is C- j ⁇ -C ⁇ alkyl; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 1 -C 8 haloalkyl; C -C 8 haloalkenyl; C 2 -C 8 alkoxyalkyl; C 2 -C 8 alkylthioalkyl; C -C 8 cycloalkylalkyl; C 2 -C 8 cyanoalkyl; C 4 -C 8 alkenyloxyalkyl; or phenyl optionally substituted with R 13 ; and R 4 and R 6 are each independently hydrogen; halogen; C- ⁇ Cs alkyl; C 3 -C 8 cycloalkyl; - j ⁇ -Cs haloalkyl; C ⁇ C**** alkoxy; C- j ⁇ -Cs haloalkoxy; C- j ⁇ -Ce alkylthio; C 1 -C 8 alkyls
  • R 1 is C -C Q alkyl; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C- j ⁇ -Cs haloalkyl; or C 2 -C 8 haloalkenyl;
  • R 2 is C ⁇ -C Q alkyl; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C**_-C 8 haloalkyl; C 2 -C 8 haloalkenyl; or phenyl optionally substituted with R 13 ;
  • R 4 and R 6 are each independently hydrogen; halogen; C-L-C-3 alkyl; C 1 -C 8 haloalkyl; CJ ⁇ -C Q alkoxy; or C* j _-C 8 haloalkoxy.
  • compounds of Preferred 3 wherein said compounds are
  • alkyl used either alone or in compound words such as “alkylthio,” “haloalkyl,” or “alkylthioalkyl” denotes straight-chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers.
  • Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkyl- oxyalkyl denotes the cycloalkyl groups linked through an oxygen atom to an alkyl chain. Examples include cyclopentyloxymethyl and cyclohexyloxybutyl.
  • the ter ⁇ i "cycloalkylthioalkyl” are the cycloalkyl groups linked through a sulfur atom to an alkyl chain; e.g., cyclo- propylthiopentyl .
  • Cycloalkylalkyl denotes a cycloalkyl ring attached to a branched or straight- chain alkyl; e.g. cyclopropylmethyl and cyclohexyl- butyl .
  • Alkenyl denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc. isomers. Alkenyl also denotes polyenes such as 1, 3-hexadiene and 2, 4, 6-heptatriene.
  • Alkenyl also denotes polyenes such as 1, 3-hexadiene and 2, 4, 6-heptatriene.
  • Alkenyl denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers.
  • Alkynyl can also denote moieties comprised of multiple triple bonds; e.g., 2, 7-octadiyne and 2, 5, 8-deca
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers.
  • alkylthioalkenyl and "alkylthioalkynyl.”
  • alkylthioalkenyl and "alkylthioalkynyl.”
  • alkenyloxyalkyl denotes groups in which the alkenyloxy moiety is attached to an alkyl group.
  • Alkynyloxy denotes straight or branched alkynyloxy moieties. Examples include HC ⁇ CCH 2 0,
  • Alkynylthioalkyl denotes alkynylthio moieties bonded to alkyl groups.
  • Alkylthio denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio groups attached to an alkyl chain; e.g., CH 3 CH 2 SCH 2 CH(CH 3 ) and (CH 3 ) 2 CHSCH 2 .
  • Alkylsulfinyl denotes both enantiomers of an alkylsulfinyl group. For example, CH 3 S (0) , CH 3 CH 2 S (0) , CH 3 CH 2 CH 2 S (0) , (CH 3 ) 2 CHS(0) and the different but lsulfinyl, pentylsulfinyl and hexylsufinyl isomers.
  • Alkylsulfinylalkyl denotes alkylsulfinyl groups attached to an alkyl chain; e.g., CH 3 CH 2 S(0)CH 2 CH(CH 3 ) and (CH 3 ) 2 CHS(0)CH 2 .
  • alkylsulfonyl examples include CH 3 S(0) 2 , CH 3 CH 2 S(0) 2 , CH 3 CH 2 CH 2 S(0) 2r (CH 3 ) 2 CHS (O) 2 and the different butylsulfonyl, pentylsulfonyl and hexyl- sulfonyl isomers.
  • Alkylsulfonylalkyl denotes alkyl- sulfonyl groups attached to an alkyl chain; e.g., CH 3 CH 2 S(0) 2 CH 2 CH(CH 3 ) and (CH 3 ) 2 CHS (0) 2 CH 2 .
  • halogen either alone or in compound words such as “haloalkyl”, denotes 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 CF 2 . Examples of
  • Examples of “haloalkynyl” include HC ⁇ CCHCl, CF 3 C---C,
  • Haloalkoxyalkyl denotes haloalkoxy groups bonded to straight-chain or branched alkyl groups; e.g., CF 2 HCH 2 CH 2 0CH 2 CH 2 , CC1 3 CH 2 0CH(CH 3 ) and CF 3 OCH 2 .
  • Trialkylsilyl designates a group with three alkyl groups bonded to silicon; e.g., (CH 3 ) 3 Si and t-Bu(CH 3 ) 2 Si.
  • "Trialkylsilylalkyl” denotes trialkylsilyl groups bonded to another straight-chain or branched alkyl group. Examples include (CH 3 ) 3 SiCH 2 and t-Bu(CH 3 ) 2 SiCH 2 CH(CH 3 )CH 2 .
  • the total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 20.
  • C 1 -C 3 alkyl- sulfonyl designates methylsulfonyl through propyl- sulfonyl
  • C 2 alkoxyalkoxy designates CH 3 OCH 2 0
  • C 3 alkoxyalkoxy designates, for example, CH 3 OCH CH 2 0 or
  • CH 3 CH 2 OCH 0; and C 4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 0, and CH 3 CH 2 OCH 2 CH 2 0.
  • alkoxyalkyl include CH 3 0CH 2 , CH 3 0CH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Compounds of Formula I can be prepared using one or more of the reactions and techniques described in Schemes 1-4 hereinafter, or by following the procedures given in Examples 1-6.
  • G 0, S,NH, NR 3
  • Bromination of compounds of Formula Ig with bromine or N-bromosuccinimide (NBS) yields brominated adducts of Formula VII which can be coupled with stannanes of Formula R 14 Sn(CH 3 ) 3 in the presence of a palladium catalyst such as tetrakis (triphenylphosphine)- palladium(O) or bis (triphenylphosphine)palladium(II) chloride to afford products of Formula If.
  • a palladium catalyst such as tetrakis (triphenylphosphine)- palladium(O) or bis (triphenylphosphine)palladium(II) chloride to afford products of Formula If.
  • Bromoheterocycles of Formula VII can also be coupled with terminal alkynes using palladium catalysis in the presence of base (such as triethylamine) and cuprous iodide.
  • Salts of compounds of Formula I can be formed by treating the free base of Formula I with strong acids such as hydrochloric or sulfuric acid.
  • N-oxides of compounds of Formula I can be made by oxidizing compounds of Formula I with a strong oxidizing agent such as jneta-chloroperoxybenzoic acid.
  • reaction mixture was partitioned between 150 mL of water and 200 mL of ethyl acetate and the organic layer separated followed by washing with water (3 times) and brine. After drying over magnesium sulfate, the solvent was evaporated in vacuo to give a yellow solid residue which was flash chromatographed on silica gel (10:1-5:1-3:1 hexane/ethyl acetate) to afford 5.2 g of the title compound as a white solid, m.p.
  • t - is tertiary OMe - is ethoxy s - is secondary SEt - is ethylthio n - is normal CN - is cyano i - is iso TMS - is trimethylsilyl Me - is methyl S(0)Me - is methylsulfinyl Et - is ethyl S(0) Me - is methylsulfonyl Ph - is phenyl
  • compositions of this invention comprise an effective amount of a 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 include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • 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 100 weight percent.
  • Weight Percent weight percent
  • 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 and solvents 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, etc.
  • 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. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4,
  • 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 3 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Compound 3 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
  • Example C Extruded Pellet Compound 3 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Compound 3 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds and compositions of this invention are usef l 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, to the media in which the plant to be protected is growing, or to the plant seed or seedling an effective amount of a compound of Formula I, an N-oxide thereof, an agriculturally suitable salt thereof, or a fungicidal composition containing said compound, N-oxide, or salt.
  • 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, 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 fuliginea, Fusarium
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, 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 monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathio ⁇ -methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, 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, methoxych
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the plant or 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.
  • The'following Tests demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection a forded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.
  • 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
  • test suspensions were then used in the following tests.
  • 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
  • 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.
  • 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. TEST D The test suspension was sprayed to the point of run-off on tomato seedlings.
  • 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 F The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the 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 C.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls) .
  • NT Not Tested.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Substituted pyrido[1,2-a]pyrimidinone compounds of formula (I) wherein Q is O or S; W is O; S; S(O); S(O)2; NH; or NR9; X is CR3 or N; Y is CR4 or N; Z is CR?5=CR6; CR5¿=N; N=CR6; S; O; or NR?7; and R1, R2, R3, R4, R5, R6 and R7¿ are various groups; and agricultural compositions containing one or more such compounds useful as fungicides for control of diseases in plants are disclosed.

Description

TITLE SUBSTITUTED PYRIDO ( 1 ,2-A) PYRIMIDINONE DERIVATIVES AS FUNGICIDES
This invention relates to certain substituted pyrido[1,2*-a]pyrimidinone compounds useful as fungicides, their agriculturally suitable salts and compositions, and methods of their use as general or selective fungicides, in particular for the control of wheat powdery mildew both preventive and curative- Urban et al., Helv. Chi . Acta, 1970, 53, 905, disclose pyrido[1,2-a]pyrimidinones of Formula i and their use as analgesics and antiinflammatory agents.
U.S. 3,755,582 issued August 28, 1973 and U.S. 3,867,384 issued February 18, 1975, each disclose 4 (3H)-quinazolinones of Formula ii and their use as agricultural fungicides.
11
wherein: is 0; S or NH; and Z is 0 or S. SUMMARY OF THE INVENTION This invention comprises compounds of Formula ϊ including all geometric and stereoisomers, N-oxides, agriculturally-suitable salts thereof, agricultural compositions containing them and method of use of said compounds, salts, or compositions as fungicides,
wherein:
Q is 0 or S; is O; S; S(O) ; S(0)2; NH; or NR9; X is CR3 or N; Y is CR4 or N; Z is CR5=CR6; CR5=N; N=CR6; S; O; or NR7; having the directionality of the CR5=CR6 r CR5=N and N=CR6 linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;
R1 is C-j^-C-Lβ alkyl; C3-C7 cycloalkyl; C2-C18 alkenyl; C2-C18 alkynyl; C-L-C--^ haloalkyl; C2-C 18 haloalkenyl; C2-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alk lthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl;
C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxy- alkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynyl- thioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl;
C -C18 haloalkynyloxyalkyl; C4-C18 alkoxy- alkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthio- alkenyl; C4-C18 alkylthioalkynyl; C -C18 trialkylsilylalkyl; C1-C1 Q alkyl substituted with NR8R10, cyano, or nitro; C1-C8 alkyl substituted with C02R8; C-L-C-LS alkoxy; C^C;**^ haloalkoxy; C3-C18 alkynyloxy; C3-C18 alkenyl- oxy; C-*_-C18 alkylthio; C3-C18 alkenylthio; or C3-C18 alkynylthio; R2 is Ci-C*-^ alkyl; C3-C7 cycloalkyl; C3-C18 alkenyl; C3-C18 alkynyl; C1-C18 haloalkyl; C 3~C18 haloalkenyl; C3-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl; C -C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxy- alkyl; C4-C18 alkenylthioalkyl; C -C18 alkynyl- thioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl; C -C18 haloalkynyloxyalkyl; C4-C18 alkoxy- alkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthio- alkenyl; C -C18 alkylthioalkynyl; C4-C18 trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10; C2-C18 cyanoalkyl; C2-C18 nitroalkyl; C1-C8 alkyl substituted with C02R8; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R13; or
R1 and R2 can be taken together along with the C=C-W fragment to which they are attached to form a 5-7 membered ring in which the R1-R2 bridge is a saturated, all-carbon chain optionally substituted with C-L-C**^ alkyl;
R3 and R5 are each independently hydrogen; halogen; C!-C4 alkyl; C1-C4 haloalkyl; C1-C alkoxy; or C2-C haloalkoxy; R4 and R6 are each independently hydrogen; halogen; cι-c8 alkyl; C3-C8 cycloalkyl; C2-C8 alkenyl;
C -C8 alkynyl; Ci-Cs haloalkyl; C3-C8 halo- alkenyl; C3-C8 haloalkynyl; C-L-C**-* alkoxy; C-L-Cg haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkynyloxy; C1-C8 alkylthio; C3-C8 alkenylthio; C3-C8 alkynylthio; C-^-OQ alkylsulfinyl; C-^-Cβ alkyl- sulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkylthio- alkyl; C2-C8 alkylsulfinylalkyl; C2-C8 alkyl¬ sulfonylalkyl; C4-C8 cycloalkylalkyl; C3-C8 trialkylsilyl; cyano; nitro; carbomethoxy; carboethoxy; or NR^R12; R7 is C1-C4 alkyl or C-*_-C4 haloalkyl;
R8 and R9 are each independently O -C^ alkyl; R10 and R11 are each independently H or Cx-C4 alkyl; R12 is C-L-Cg alkyl;
R8' and R10, or the groups R11 and R12, can be taken together to form -CH2CH2CH2CH2-, -CH2 (CH2)3CH2-,
-CH2CH20CH2CH2-, -CH2CH(Me) CH2CH(Me)CH2- r or -CH2CH(Me)OCH(Me) CH2-; and R13 is halogen; Cx-C4 alkyl, C1-C alkoxy, or C1-C haloalkyl; provided that: i) when Z is CR5=CR6, then at least one substituent selected from the group consisting of R3, R4, R5 and R6, is hydrogen; and ii) the total number of carbons in R3, R4,
R5 and R6 is equal to or less than 16; iii) the total number of nitrogen atoms incorporated into the bicyclic framework is less than or equal to four; iv) R3 and R4 are not both hydrogen; and v) X and Y are not both nitrogen. Preferred for reasons of ease of synthesis or greater fungicidal activity are compounds of Formula I, denoted as Preferred 1, wherein: ' is 0; S; NH; or NR9; X is CR3; Y is CR4;
R1 is C-i-Cs alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C2-C8 haloalkenyl; C2-C8 alkoxyalkyl; C -C8 alkylthioalkyl; C4-C8 cycloalkylalkyl; C2-C8 cyanoalkyl; Ci-Ce alkoxy; C*-_-C18 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkenylthio; or C4-C8 alkenyloxyalkyl;
R2 is C-j^-Cβ alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C -C8 haloalkenyl; C2-C8 alkoxyalkyl; C2-C8 alkylthioalkyl; C -C8 cycloalkylalkyl; C2-C8 cyanoalkyl; C4-C8 alkenyloxyalkyl; or phenyl optionally substituted with R13; and R4 and R6 are each independently hydrogen; halogen; C-^Cs alkyl; C3-C8 cycloalkyl; -j^-Cs haloalkyl; C^C**** alkoxy; C-j^-Cs haloalkoxy; C-j^-Ce alkylthio; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C -C8 alkylthioalkyl; C4-C8 cycloalkylalkyl; C3-C8 trialkylsilyl; or cyano. More preferred are compounds denoted as Preferred f the above Preferred 1, wherein: Q is 0; is 0; S; NH; or NMe; Z is CR5=CR6; CR5=N; S; or 0; R1 is C-j^-Ce alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C*]_-C8 haloalkyl; C2-C8 halo¬ alkenyl; Ci-Cs alkoxy; C2-C8 alkoxyalkyl; or C3-C8 alkenyloxy; R2 is C-±-CQ alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C*-_-C8 haloalkyl; C -C8 halo- alkenyl; C2-C8 alkoxyalkyl; or phenyl optionally substituted with R13; and R4 and R6 are each independently hydrogen; halogen; C-L-C-J alkyl; C1-C8 haloalkyl; c l _c 8 alkoxy; Cx-C8 haloalkoxy; C3-C8 trialkylsilyl; or cyano. Even more preferred are compounds denoted as Preferred 3, of the above Preferred 2, wherein: Z is CR5=CR6 or S; R1 is C -CQ alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C-j^-Cs haloalkyl; or C2-C8 haloalkenyl; R2 is C±-CQ alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C**_-C8 haloalkyl; C2-C8 haloalkenyl; or phenyl optionally substituted with R13; and R4 and R6 are each independently hydrogen; halogen; C-L-C-3 alkyl; C1-C8 haloalkyl; CJ^-CQ alkoxy; or C*j_-C8 haloalkoxy. Specifically preferred are compounds of Preferred 3 wherein said compounds are:
7-bromo-3- (n-propyl)-2-(n-propyloxy)-4H- pyrido[1Λ2-a]pyrimidin-4-one; 7,9-dibromo-3-(n-propyl) -2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one; or
7-iodo-3- (-α-propyl)-2-(n-propyloxy)-4H- pyrido[l,2-a]pyrimidin-4-one.
DETAILED DESCRIPTION OF THE INVENTION In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio," "haloalkyl," or "alkylthioalkyl" denotes straight-chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers. "Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkyl- oxyalkyl" denotes the cycloalkyl groups linked through an oxygen atom to an alkyl chain. Examples include cyclopentyloxymethyl and cyclohexyloxybutyl. The terπi "cycloalkylthioalkyl" are the cycloalkyl groups linked through a sulfur atom to an alkyl chain; e.g., cyclo- propylthiopentyl . "Cycloalkylalkyl" denotes a cycloalkyl ring attached to a branched or straight- chain alkyl; e.g. cyclopropylmethyl and cyclohexyl- butyl . "Alkenyl" denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc. isomers. Alkenyl also denotes polyenes such as 1, 3-hexadiene and 2, 4, 6-heptatriene. "Alkynyl" denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers. "Alkynyl" can also denote moieties comprised of multiple triple bonds; e.g., 2, 7-octadiyne and 2, 5, 8-decatriyne.
"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers. "Alkoxyalkenyl" and "alkoxy- alkynyl" denoted groups in which the alkoxy group is bonded throught the oxygen atom to an alkenyl or alkynyl group, respectively. Examples include CH3OCH2CH=CH and (CH3)2CH0CH2C=CCH2. The corresponding sulfur derivatives are denoted "alkylthioalkenyl and "alkylthioalkynyl." Examples of the former include CH3SCH2CH=CH and CH3CH2SCH2 (CH3) CH=CHCH2, and an example of the latter is CH3CH2CH2CH2SCH2C=C.
"Alkenyloxy" denotes straight chain or branched alkenyloxy moieties. Examples of alkenyloxy include H2C=CHCH20, (CH3)2C=CHCH20, (CH3) CH=CHCH20, (CH3)CH=C(CH3)CH20 and CH2=CHCH2CH20. "Alkenylthio" denotes the similar groups wherein the oxygen atom is replace with a sulfur atom; e.g., H2C=CHCH2S and (CH3)CH=C(CH3)CH2S. The term "alkenyloxyalkyl" denotes groups in which the alkenyloxy moiety is attached to an alkyl group. Examples include H2C=CHCH20CH2CH2, H2C=CHCH2OCH(CH3)CH2Λ etc. "Alkenylthioalkyl" denotes the alkenylthio moieties bonded to an alkyl group. Examples include H2C=CHCH2SCH(CH3) CH(CH3) and (CH3) CH=C(CH3) CH2SCH2.
"Alkynyloxy" denotes straight or branched alkynyloxy moieties. Examples include HC≡CCH20,
CH3C=CCH20 and CH3C-=CCH2CH20. "Alkynyloxyalkyl" denotes alkynyloxy moieties bonded to alk l groups; e.g., CH3C≡CCH2OCH2CH2 and HC=CCH2OCH(CH3) CH2. "Alkynylthioalkyl" denotes alkynylthio moieties bonded to alkyl groups. Example include CH3C≡CCH2SCH CH2 and CH3C=CCH2CH2SCH(CH3)CH2.
"Alkylthio" denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio groups attached to an alkyl chain; e.g., CH3CH2SCH2CH(CH3) and (CH3)2CHSCH2.
"Alkylsulfinyl" denotes both enantiomers of an alkylsulfinyl group. For example, CH3S (0) , CH3CH2S (0) , CH3CH2CH2S (0) , (CH3)2CHS(0) and the different but lsulfinyl, pentylsulfinyl and hexylsufinyl isomers. "Alkylsulfinylalkyl" denotes alkylsulfinyl groups attached to an alkyl chain; e.g., CH3CH2S(0)CH2CH(CH3) and (CH3)2CHS(0)CH2.
Examples of "alkylsulfonyl" include CH3S(0)2, CH3CH2S(0)2, CH3CH2CH2S(0)2r (CH3)2CHS (O)2 and the different butylsulfonyl, pentylsulfonyl and hexyl- sulfonyl isomers. "Alkylsulfonylalkyl" denotes alkyl- sulfonyl groups attached to an alkyl chain; e.g., CH3CH2S(0)2CH2CH(CH3) and (CH3)2CHS (0)2CH2. The term "halogen", either alone or in compound words such as "haloalkyl", denotes 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 F3C, C1CH2, CF3CH2 and CF3CF2. Examples of
"haloalkenyl" include (Cl)2C=CHCH2 and CF3CH2CH=CHCH2. "Haloalkenyloxyalkyl" denotes haloalkenyl groups bonded to oxygen and in turn bonded to alkyl groups. Examples include CF3CH2CH=CHCH20CH2 and (Cl) 2C=CHCH20CH2CH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C---C,
CC13C≡C and FCH2C≡CCH2. "Haloalkynyloxyalkyl" denotes haloalkynyl groups bonded through an oxygen atom to an alkyl moiety. Examples include CF3C≡CCH2OCH2CH2, C1CH2C=CCH2CH20CH(CH3) , etc. Examples of "haloalkoxy" include CF30, CC13CH20, CF2HCH2CH20 and CF3CH20.
"Haloalkoxyalkyl" denotes haloalkoxy groups bonded to straight-chain or branched alkyl groups; e.g., CF2HCH2CH20CH2CH2, CC13CH20CH(CH3) and CF3OCH2.
"Trialkylsilyl" designates a group with three alkyl groups bonded to silicon; e.g., (CH3)3Si and t-Bu(CH3)2Si. "Trialkylsilylalkyl" denotes trialkylsilyl groups bonded to another straight-chain or branched alkyl group. Examples include (CH3)3SiCH2 and t-Bu(CH3)2SiCH2CH(CH3)CH2. The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 20. For example, C1-C3 alkyl- sulfonyl designates methylsulfonyl through propyl- sulfonyl; C2 alkoxyalkoxy designates CH3OCH20; C3 alkoxyalkoxy designates, for example, CH3OCH CH20 or
CH3CH2OCH 0; and C4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH3CH2CH2OCH20, and CH3CH2OCH2CH20. Examples of "alkoxyalkyl" include CH30CH2, CH30CH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. Compounds of Formula I can be prepared using one or more of the reactions and techniques described in Schemes 1-4 hereinafter, or by following the procedures given in Examples 1-6. The variables , X, Y, and Z and substituents R1-R13 in the compounds of Formulae
Ia-Ig and II-VII illustrated in Schemes 1-4 hereinafter are defined as for compounds of Formula I above.
The general method for preparing compounds of Formula la is shown in Scheme 1. Based on a known synthetic method (A. E. Tschitschibabin, Chem. Ber. , 1924, 57, 168; G. R. Lappin, et. al., J. Org. Chem., 1950, 15, 377; A. R. Katritzky and A. J. Waring, J. Chem. Soc , 1962, 1544; J. Klosa, J. Prakt . Chem. , 1964, 26, 150; K. E. Schulte and J. Witt, Arch . Pharm., 1958, 252, 298) , heating substituted aminoheterocycles of Formula II with substituted malonates of Formula III neat at 150-250°C or by heating in a high boiling solvent such as diethylbenzene (and allowing for the evaporation or distillation of ethanol formed in the reaction) gives zwitterionic intermediates of Formula IV. Substituted aminoheterocycles of Formula II and malonates of Formula III are known and in many cases are commercially available. Reaction of heterocycles of Formula IV with alkylating agents in the presence of base can give rise to alkylation on both oxygen and nitrogen (R. Urban, Helv. Chim. Acta, 1970, 53, 905) . However, alkylation of heterocycles of Formula IV with reagents of Formula R2L wherein L is Cl, Br, I, OTs or OMs, in the presence of a mild base, such as potassium carbonate, in a polar aprotic solvent, such as dimeth lformamide, affords predominantly the desired O-alkylated product of Formula la with only a small amount of the more polar (by thin layer chromatograph ) N-alkylated mesoionic adduct of Formula V being obtained. Products of Formulae la and V can be separated by chromatography. Scheme 1
II IV
As illustrated in Scheme 2, heating intermediates of Formula IV in thionyl chloride or phosphorous oxychloride furnishes chloro-substituted heterocycles of Formula VI. Displacement of the chloro substituent, by reacting heterocycles of Formula VI with nucleo- philic reagents of Formula R2GH (generally in the presence of base, e.g., sodium hydride or sodium methoxide, in a solvent such as tetrahydrofuran or dimethylformamide) gives products of Formula lb wherein G is 0, S, NH, or NR9. Oxidation of compounds of Formula lb wherein G is S with a suitable oxidizing agent such as meta-chloroperoxybenzoic acid furnishes products of Formula Ic. Scheme 2
lb Ic n=l or 2
G=0, S,NH, NR3
Thiation of heterocycles of Formula Id with phosphorous pentasulfide or Lawesson ' s reagent gives thiones of Formula Ie (Scheme 3) .
Scheme 3
Id Ie
Compounds of Formula If can be made by the procedure illustrated in Scheme 4. Intermediates of Formula Ig can be initially prepared by the methods shown in Schemes 1 and 2 whereby diethylmalonate is used as the malonate starting material (i.e., compounds of Formula III wherein R1 = H) in Scheme 1. Bromination of compounds of Formula Ig with bromine or N-bromosuccinimide (NBS) yields brominated adducts of Formula VII which can be coupled with stannanes of Formula R14Sn(CH3)3 in the presence of a palladium catalyst such as tetrakis (triphenylphosphine)- palladium(O) or bis (triphenylphosphine)palladium(II) chloride to afford products of Formula If. Bromoheterocycles of Formula VII can also be coupled with terminal alkynes using palladium catalysis in the presence of base (such as triethylamine) and cuprous iodide.
Scheme 4
If
.14 alkenyl or alkynyl
Salts of compounds of Formula I can be formed by treating the free base of Formula I with strong acids such as hydrochloric or sulfuric acid. N-oxides of compounds of Formula I can be made by oxidizing compounds of Formula I with a strong oxidizing agent such as jneta-chloroperoxybenzoic acid. INTERMEDIATE 1
Preparation of 7-Chloro-2-hydroxy-4-oxo-3- (2-propenyl) - pyridoPI, 2-alpyrimidin-l-ium Hydroxide,, Inner Salt A mixture of 10.0 g (77.8 mmol) of 2-amino-5- chloropyridine and 23.0 g (115 mmol) of diethyl allyl- malonate in 60 mL of diethylbenzene was heated at reflux for 1 h with stirring. Ethanol generated during heating was removed by distillation. A solution initially formed followed by gradual precipitation of a yellow solid. On cooling, n-butyl chloride was added to enhance precipitation of this solid which was filtered, washed with -o-butyl chloride, and dried. A 13.5 g yield of the title compound (m.p. 284-287°C) was obtained and used in subsequent steps without further purification.
EXAMPLE 1 Preparation of 7-Chloro-2-methoxy-3- (2-propenyl)-4H- pyridofl.2-a-pyrimidin-4-onβ To 2.0 g (8.5 mmol) of 7-chloro-2-hydroxy-4-oxo-3- (2-propenyl)-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 3.5 g (25.4 mmol) of potassium carbonate stirring in 50 mL of NΛ N-dimethylformamide, 2.6 mL of iodomethane was added and the mixture was stirred at room temperature for 18 h. Excess water and 200 L of ethyl acetate were added. The organic layer was separated, washed with water (3 times) and brine, and dried over magnesium sulfate. The solvent was evaporated in vacυo to give a dark oil which was flash chromatographed on silica gel (1:1 hexane/ethyl acetate) to afford 0.7 g of the title compound, m.p. 139-141°C; ^-H NMR (CDC13) : δ 9.05 (d, 1H) , 7.65, 7.60 (dd, 1H), 7,45 (d, 1H) , 6.05-5.85 (m, 1H) , 5.15-4.95 (m, 2H) , 4.03 (s, 3H) , 3.40 (d, 2H) .
EXAMPLE 2 Preparation of 7-Chloro-3- (2-propenyl) -2-(2- propenyloxy) -4H-pyrido ϊl .2-a]pyrimidin-4-one To 1.0 g (4.2 mmol) of 7-chloro-2-hydroxy-4-oxo-3- (2-propenyl) -pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 1.5 g (10.8 mmol) of potassium carbonate stirring in 35 mL of NΛ N-dimethy1formamide, 0.9 mL of allyl bromide was added and the mixture stirred at room temperature for 15 h. Excess water was added and the aqueous mixture was extracted with 125 mL of ethyl acetate. The organic layer was then washed with water (3 times) and brine and dried over magnesium sulfate. Evaporating in vacuo gave a solid residue which was flash chromatographed on silica gel (3:1 followed by 1:1 hexane/ethyl acetate) to afford 0.55 g of the title compound, m.p. 104-105°C; 1H NMR (CDC13) : δ 9.07 (d, 1H) , 7.63 (broad d, 1H) , 7.42 (d, 1H) , 6.10-5.90 (m, 2H) , 5.42 (broad d, 1H) , 5.25, 5.23 (dd, 1H) , 5.13 (d, 1H) , 5.05-4.95 (m, 3H) , 3.42 (d, 2H) . INTERMEDIATE 2
Preparation of 7-Chloro-2-hydroxy-4-oxo-3-propyl- pyrido[1,2-alpyrimidin-1-ium Hydroxide, Inner Salt A mixture of 11.5 g (89.4 mmol) of 2-amino-5- chloropyridine and 49.0 g (242 mmol) of diethyl propyl- malonate was heated neat at 175°C for 3.5 h. Ethanol formed during heating was allowed to evaporate. A solution formed initially followed by gradual precipitation of a yellow solid. After cooling, 25 mL of hexane were added and the solid was filtered, washed with hexane, and dried to yield 8.0 g of the title compound. This solid (m.p. 298-305°C) was used without further purification in the subsequent steps .
EXAMPLE 3 Preparation of 7-Chloro-2-methoxy-3-propyl- 4H-pyridofl,2-a]pyrimidin-4-one
To 5.0 g (21.0 mmol) of 7-chloro-2-hydroxy-4-oxo-3- propyl-pyrido[l, 2-a]pyrimidin-l-ium hydroxide, inner salt and 4.3 g (31.2 mmol) of potassium carbonate stirring in 35 ml of N,N-dimethylformamide, 4.5 g (31.7 mmol) of iodomethane was added and the mixture was stirred at room temperature for 3 h. The reaction mixture was partitioned between 250 mL of water and 250 mL of ethyl acetate and the organic layer was separated followed by washing with water (3 times) and brine. After drying over magnesium sulfate, the solvent was removed in vacuo to give a yellow solid residue which was flash chromatographed on silica gel (5:1 followed by 3:1 hexane/ethyl acetate) to afford 2.8 g of the title compound, m.p. 135-137°C; ^-H NMR (CDC13) : δ 9.07 (d, IH), 7.65, 7.60 (dd, IH) , 7.45 (d, IH), 4.02 (s, 3H) , 2.63 (t, 2H) , 1.70-1.50 (m, 2H) , 0.97 (t, 3H) .
EXAMPLE 4 Preparation of 7-Chloro-3-propyl-2-propyloxy- 4H-pyridof r -a]pyrimidin-4-one To 7.0 g (29 mmol) of 7-chloro-2-hydroxy-4-oxo-3- propyl-pyrido[l,2-a]pyrimidin-l-ium hydroxide, inner salt and 5.7 g (41 mmol) of potassium carbonate stirring in 35 mL of N, N-dimethylformamide, 6.5 g (38 mmol) of n-propyl iodide was added and the mixture stirred at room temperature for 14 h. The reaction mixture was partitioned between 150 mL of water and 200 mL of ethyl acetate and the organic layer separated followed by washing with water (3 times) and brine. After drying over magnesium sulfate, the solvent was evaporated in vacuo to give a yellow solid residue which was flash chromatographed on silica gel (10:1-5:1-3:1 hexane/ethyl acetate) to afford 5.2 g of the title compound as a white solid, m.p. 105-107°C; XE NMR (CDC13) : δ 9.04 (d, IH) , 7.60 (dd, IH) , 7.42 (d, IH), 4.37 (t, 2H), 2.63 (t, 2H) , 1.80 (q, 2H) , 1.60 (q, 2H) , 1.10-0.90 (m, 6H) .
INTERMEDIATE 3 Preparation of 2f 7-Dichloro-3-propyl-4H- pyridofl ,2-alpyrimidin-4-one A mixture of 10.0 g (42 mmol) of 7-chloro-2- hydroxy-4-oxo-3-propyl-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt stirring in 80 mL of phosphorous oxychloride was heated at reflux for 88 h. The dark reaction mixture was poured onto a large excess of ice. After extracting the resulting aqueous mixture with
800 mL of ethyl acetate, the organic layer was washed with water (2 times) , saturated sodium bicarbonate and brine and dried over magnesium sulfate. Evaporating in vacuo gave dark oily/solid residue which was flashed chromatographed on silica gel (10:1-5:1-3:1 hexane/ethyl acetate) to give 1.8 g of the title compound, m.p. 169-171°C; 2H NMR (CDC13) : δ 8.99 (d, IH), 7.67 (dd, IH) , 7.55 (d, IH) , 2.80 (t, 2H) , 1.65 (q, 2H) , 1.02 (t, 3H) .
EXAMPLE 5 Preparation of 7-Chloro-3-propyl-2-propylthio-
4H-pyridoTl,2-a!pyrimidin-4-one To 0.5 g (2.0 mmol) of 2, 7-dichloro-3-propyl-4H- pyrido[1,2-a]pyrimidin-4-one and 0.43 g (3.1 mmol) of potassium carbonate stirring in 30 mL of N,JV-dimethyl- formamide at room temperature, 0.21 mL (2.3 mmol) of 1-propanethiol was added and the reaction was stirred at room temperature for 5 h. Water (75 mL) and ethyl acetate (125 L) were added and the organic layer was separated and washed with water (3 times) and brine followed by drying over magnesium sulfate. Evaporation of solvent in vacuo provided an oily solid residue which was flash chromatographed on silica gel (15:1-10:1 hexane/ethyl acetate) to yield 0.27 g of the title compound, m.p. 91-93°C; R NMR (CDC13) : δ 9.0 (d, IH) , 7.55 (dd, IH) , 7.44 (d, IH) , 3.22 (t, 2H) , 2.68
(t, 2H) , 1.75 (q, 2H) , 1.65 (q, 2H) , 0.99-1.07 (m, 6H) .
EXAMPLE 6 Preparation of 7-Chloro-3-propyl-2-propyloxy- 4H-pyridori-.2-a1pyrimidin-4-th.ione A mixture of 1.0 g (3.6 mmol) of 7-chloro-3-propyl- 2-propyloxy-4H-pyrido[l,2-a]pyrimidin-4-one and 4.7 g (11 mmol) of phosphorous pentasulfide was heated at reflux for 32 h. An additional 3.0 g (6.8 mmol) of phosphorous pentasulfide was added and the mixture was heated at reflux for an additional 16 h. After partitioning the reaction mixture between 150 mL of ethyl acetate and 10% aqueous hydrogen chloride, the organic layer was separated and washed with 10% aqueous hydrogen chloride (3 times with 100 mL) , saturated sodium bicarbonate, and brine. The organic layer was dried over magnesium sulfate and evaporated in vacuo to give a solid residue. Flash column chromatography on silica gel (n-butyl chloride) afforded 0.16 g of the title compound, m.p. 117-120°C; E NMR (CDC13) : δ 10.63 (d, 1H)Γ 7.75 (dd, IH) , 7.57 (d, IH) , 4.43 (t, 2H) , 3.07 (t, 2H) , 1.84 (q, 2H) , 1.68 (q, 2H) , 0.95-1.15 (m, 6H) .
Using the procedures outlined in Schemes 1-4, the compounds of Tables 1-7 can be prepared.
Ih Ii
I Ik
II The following abbreviations are used in the tables which follow.
t - is tertiary OMe - is ethoxy s - is secondary SEt - is ethylthio n - is normal CN - is cyano i - is iso TMS - is trimethylsilyl Me - is methyl S(0)Me - is methylsulfinyl Et - is ethyl S(0) Me - is methylsulfonyl Ph - is phenyl
TABLE 1
Compounds of Formula Ih R3=R5=H; W=Q
___ .si
Me Me
Et n-propyl
-i-propyl Me
2-propenyl Me
2-propenyl 2-propenyl
2-propenyl Λ-propyl n-propyl 2-propenyl
2-propenyl Λ-propyl
2-propenyl 2-propenyl
2-propenyl π-butyl
Et n-propyl
Et Et Et 2-propenyl R1 Me n-propyl Me 2-propenyl
-•--hexyl Me n-butyl Et i-propyl n-propyl Me n-propyl n-propyl i-propyl 2-propenyl 2-propenyl n-propyl Me 2-propenyl n-propyl Me ιι-heptyl Et -π-dodecyl Me Et n-propyl 2-propenyl 2-propenyl 2-propenyl 2-propenyl n-propyl 2-butenyl 2-propenyl -5-butyl Me ά-pentyl 2-propenyl n-dodecyl n-hexyl 2-propenyl 2-propenyl n-propyl 2-propenyl 2-propenyl 2-propenyl n-propyl Et 2-butenyl 2-propenyl n-propyl (CH2)17Me 2-propenyl 2-propenyl 2-pentenyl n-propyl 2-hexenyl 2-butenyl 2-propenyl 2-propenyl n-propyl Me n-oσtyl n-heptyl Me (CH2> llMe n-propyl s-butyl
-- i Rp
Me F Me CH2CH2SEt
F F Me cyclohexylmethyl
Br Et Et cyclooctyl
I H Me phenethyl
Cl H Et CH2CH2CN
Cl H Me CH2CH2N02
Cl H 2-propenyl cyclopropylmethyl
Cl Cl Et benzyl
Br Me n-propyl phenyl
Cl H Et 4-chlorophenyl
Cl H n-propoxy n-butyl
CF** H ethoxy 2-propenyl
Br H methoxy (CH2)17Me Cl H n-propyl CH2CH=CHC1 Cl H 0CH2CH2C1 2-butenyl 3 H CH2C(C1)=CH2 n-butyl
Br Me CH2CH=CHC1 CH2CH=CMe2 t-butyl H CH2CH=CMe2 OCH2CF3
CH=CHMe H Me cyclohexyl
C≡CMe H Me n-butyl
OCH2C≡CH H Et 2-c clohexenyl
S(0)Me H Et CH2C≡CCF3
CH2S(O)Me H Me Et
CN H .n-propyl 2-propenyl
C02Me H Et .n-propyl
C02Et H Et 2-butenyl
Cl cyclohexyl Et Et
Cl CH=CHMe Et Et
Cl C-≡CEt Me n-pentyl
Cl CH2Br Me 2-butynyl
Me CF3 2-propenyl 2-propenyl
Cl CH=CHCF3 n-butyl Me
Cl C---CCF3 n-propyl n-propyl
Br 0CH2C≡CH n-propyl CH2CH2C1
. i .si _s±
Cl H Et 4-methylbenzyl Cl H Et 4-CF -benzyl Cl H Et 3-CF3-phenethyl Cl H Et 4-methoxybenzyl Cl H Me 4-methoxyphenethyl
.si
CH=CHCF3 CH2CH=CHC1 n-propyl Et n-butyl Me
2-dodecenyl CH2CH2OEt
Me n-propyl
2-propenyl 2-propenyl
2-propenyl n-propyl
Et 2-propenyl
2-butenyl n-propyl n-propyl n-butyl n-hexyl i-propyl
Et i-butyl
Me s-pentyl
2-propenyl Me
2-hexenyl Et
2-butynyl n-butyl
CH2CH2OMe 2-propenyl
CH2SCHMe2 2-pentenyl
1-butenyl phenyl Me 4-chlorophenyl
R3=R5=H o4 ϋ. -Si JSi
Cl H S (0) n-propyl n-propyl Br H S (0) 2 n-pentyl Et
∞3 Me S (0) 2 i-propyl n-propyl
--si --si --Si --Q. J- --Si ___
H Cl Me O NH n-propyl phenyl
H OCH2CHMe2 H O NMe n-butyl Me H Br H 0 NH 2-propenyl phenyl H Br H O NH CH2CH2OMe 4-chlorophenyl H Cl H S NEt n-hexyl n-butyl H Cl H O NH Et benzyl
Me Me H O O i-pentyl Et
H I H O 0 CH2OCH2CH=CH2 n-propyl H Cl H S O CH2SCH2CH2Me Et H CF3 H O S 2-butenyl Me H CF3 H O S Me phenyl H Cl H O O CH2C(C1)=CH2 n-propyl H Me Cl 0 0 n-propyl 2-pentenyl
TABLE 7 compounds of Formula I
_Q .Si s o o 2-propenyl n-propyl s o 0 2-propenyl 2-propenyl s o o n-butyl n-hexyl s o 0 s-butyl 2-butenyl s o o Et 2-pentenyl s o o n-propyl 2-propenyl s o o 2-propenyl n-propyl s o o 2-butenyl Et s o o Me n-propyl s o o CH2CH20Me Et s o 0 CH2CH2C1 2-hexenyl s o o 2-propenyl 2-propenyl s o o 2-butenyl n-propyl s o 0 CH=CHMe n-heptyl s o s n-butyl Et s s o 2-propenyl 2-butenyl s o o 2-butynyl 2-pentenyl
Compounds of this invention will generally be used in an agriculturally suitable composition. The compositions of this invention comprise an effective amount of a 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 include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. 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 100 weight percent. Weight Percent
Wettable Powders
Oil Suspensions, Emulsions, Solutions, (including Emulsifiable Concentrates)
Dusts
Granules, Baits and Pellets
High Strength Compositions
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 and solvents 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, etc. 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. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4,
1967, pp 147-148, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 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 DE 3,246,493. 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 through 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 worked up in conventional ways. Compound numbers refer to compounds in Index Tables A and B, hereinafter. Example A
Wettable Powder
Compound 3 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B Granule
Compound 3 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C Extruded Pellet Compound 3 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 3 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%. The compounds and compositions of this invention are usef l 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, to the media in which the plant to be protected is growing, or to the plant seed or seedling an effective amount of a compound of Formula I, an N-oxide thereof, an agriculturally suitable salt thereof, or a fungicidal composition containing said compound, N-oxide, or salt. 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. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, 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 fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma and other generea and species closely related to these pathogens. They are particularly effective in the control of Erysiphe graminis, the causal agent of wheat powdery mildew, both preventive and curative.
Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi- component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathioπ-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, 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, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuramΛ dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, . triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difeno- conazole, diniconazole,- fluquinconazole, ipconazole, me conazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; 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 and baculovirus.
In certain instances, combinations with other fungicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the plant or 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. The'following Tests demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection a forded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.
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.
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.
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. 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. 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.
TEST F The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the 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.
Results for Tests A-F are given in Table C. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls) . NT = Not Tested.
TABLE C
*The compound was spray at a concentration of 40 ppm.

Claims

What is claimed is:
1. A compound of Formula I
wherein:
Q is O or S;
W is O; S; S (O) ; S(O)2; NH; or NR9;
X is CR3 or N;
Y is CR4 or N;
Z is CR5=CR6; CR5=N; N=CR6; S; O; or NR7; having the directionality of the CR5=CR6, CR5=N and N=CR6 linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;
R1 is C1-C18 alkyl; C3-C7 cycloalkyl; C2-C18
alkenyl; C2-C18 alkynyl; C1-C18 haloalkyl;
C2-C18 haloalkenyl; C2-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl; C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C1-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynylthioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl; C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxyalkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl; C4-C18 trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10, cyano, or nitro; C1-C8 alkyl substituted with CO2R8; C1-C18 alkoxy; C1-C18 haloalkoxy; C3-C18 alkynyloxy; C3-C18 alkenyloxy; C1-C18 alkylthio; C3-C18 alkenylthio; or C3-C18 alkynylthio;
R2 is C1-C18 alkyl; C3-C7 cycloalkyl; C3-C18
alkenyl; C3-C18 alkynyl; C1-C18 haloalkyl;
C3-C18 haloalkenyl; C3-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl;
C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynylthioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl;
C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxyalkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl; C4-C18 trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10; C2-C18 cyanoalkyl; C2-C18
nitroalkyl; C1-C8 alkyl substituted with CO2R8; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R13; or R1 and R2 can be taken together along with the
C=C-W fragment to which they are attached to form a 5-7 membered ring in which the R1-R2 bridge is a saturated, all-carbon chain
optionally substituted with C1-C12 alkyl;
R3 and R5 are each independently hydrogen; halogen;
C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; or
C1-C4 haloalkoxy;
R4 and R6 are each independently hydrogen; halogen;
C1-C8 alkyl; C3-C8 cycloalkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C3-C8
haloalkenyl; C3-C8 haloalkynyl; C1-C8 alkoxy;
C1-C8 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkynyloxy; C1-C8 alkylthio; C3-C8 alkenylthio; C3-C8 alkynylthio; C1-C8 alkylsulfinyl; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkylthioalkyl; C2-C8 alkylsulfinylalkyl; C2-C8 alkylsulfonylalkyl; C4-C8 cycloalkylalkyl;
C3-C8 trialkylsilyl; cyano; nitro; CO2Me;
CO2Et; or NR11R12;
R7 is C1-C4 alkyl or C1-C4 haloalkyl;
R8 and R9 are each independently C1-C4 alkyl;
R10 and R11 are each independently H or C1-C4 alkyl; R12 is C1-C8 alkyl;
R8 and R10, or the groups R11 and R12, can be taken together to form -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2-, or -CH2CH(Me)OCH(Me)CH2-; and
R13 is halogen; C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 haloalkyl;
provided that:
i) when Z is CR5=CR6, then at least one substituent selected from the group consisting of R3, R4, R5 and R6, is hydrogen; and
ii) the total number of carbons in R3, R4, R5 and R6 is equal to or less than 16; iϋ) the total number of nitrogen atoms
incorporated into the bicyclic
framework is less than or equal to four;
iv) R3 and R4 are not both hydrogen; and v) X and Y are not both nitrogen.
N-oxides and agriculturally suitable salts thereof.
2. A compound of Claim 1 wherein:
W is O; S; ΝH; or ΝR9;
X is CR3;
Y is CR4; R1 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C2-C8 haloalkenyl; C2-C8 alkoxyalkyl; C2-C8 alkylthioalkyl; C4-C8 cycloalkylalkyl; C2-C8 cyanoalkyl; C1-C8 alkoxy; C1-C18 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkenylthio; or C4-C8 alkenyloxyalkyl; R2 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8
alkynyl; C1-C8 haloalkyl; C2-C8 haloalkenyl; C2-C8 alkoxyalkyl; C2-C8 alkylthioalkyl; C4-C8 cycloalkylalkyl; C2-C8 cyanoalkyl; C4-C8 alkenyloxyalkyl; or phenyl optionally substituted with R13; and
R4 and R6 are each independently hydrogen; halogen; C1-C8 alkyl; C3-C8 cycloalkyl; C1-C8 haloalkyl; C1-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylthio; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkylthioalkyl; C4-C8 cycloalkylalkyl;
C3-C8 trialkylsilyl; or cyano.
3. A compound of Claim 2 wherein:
Q is O;
W is O; S; NH; or NMe;
Z is CR5=CR6; CR5=N; S; or O;
R1 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8
alkynyl; C1-C8 haloalkyl; C2-C8 haloalkenyl; C1-C8 alkoxy; C2-C8 alkoxyalkyl; or C3-C8 alkenyloxy;
R2 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8
alkynyl; C1-C8 haloalkyl; C2-C8 haloalkenyl; C2-C8 alkoxyalkyl; or phenyl optionally substituted with R13; and R4 and R6 are each independently hydrogen; halogen; C1-C8 alkyl; C1-C8 haloalkyl; C1-C8 alkoxy; C1-C8 haloalkoxy; C3-C8 trialkylsilyl; or cyano.
4. A compound of Claim 3 wherein:
Z is CR5=CR6 or S;
R1 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8
alkynyl; C1-C8 haloalkyl; or C2-C8 haloalkenyl;
R2 is C1-C8 alkyl; C2-C8 alkenyl; C2-C8
alkynyl; C1-C8 haloalkyl; C2-C8
haloalkenyl; or phenyl optionally
substituted with R13; and
R4 and R6 are each independently hydrogen; halogen; C1-C8 alkyl; C1-C8 haloalkyl; C1-C8 alkoxy; or C1-C8 haloalkoxy.
5. A compound of Claim 4 which is
7-bromo-3-(n-propyl)-1-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one;
7,9-dibromo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one; or
7-iodo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one.
6. A fungicidal composition comprising an effective amount of a compound of Formula I
wherein:
Q is O or S;
W is O; S; S (O); S(O)2; NH; or NR9;
X is CR3 or N;
Y is CR4 or N; Z is CR5=CR6; CR5=N; N=CR6; S; O; or NR7; having the directionality of the CR5=CR6, CR5=N and N=CR6 linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;
R1 is C1-C18 alkyl; C3-C7 cycloalkyl; C2-C18
alkenyl; C2-C18 alkynyl; C1-C18 haloalkyl;
C2-C18 haloalkenyl; C2-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl; C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18
alkynylthioalkyl; C6-C18 cycloalkylthioalkyl;
C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl; C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxyalkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl;
C4-C18 trialkylsilylalkyl; C1-C18 alkyl
substituted with NR8R10, cyano, or nitro; C1-C8 alkyl substituted with CO2R8; C1-C18 alkoxy;
C1-C18 haloalkoxy; C3-C18 alkynyloxy; C3-C18 alkenyloxy; C1-C18 alkylthio; C3-C18 alkenylthio; or C3-C18 alkynylthio;
R2 is C1-C18 alkyl; C3-C7 cycloalkyl; C3-C18
alkenyl; C3-C18 alkynyl; C1-C18 haloalkyl;
C3-C18 haloalkenyl; C3-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl;
C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynylthioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl;
C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxy alkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl; C4-C18 trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10; C2-C18 cyanoalkyl; C2-C18 nitro- alkyl; C1-C8 alkyl substituted with CO2R8; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R13; or R1 and R2 can be taken together along with the
C=C-W fragment to which they are attached to form a 5-7 membered ring in which the R1-R2 bridge is a saturated, all-carbon chain
optionally substituted with C1-C12 alkyl;
R3 and R5 are each independently hydrogen; halogen;
C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; or C1-C4 haloalkoxy;
R4 and R6 are each independently hydrogen; halogen;
C1-C8 alkyl; C3-C8 cycloalkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C3-C8 haloalkenyl; C3-C8 haloalkynyl; C1-C8 alkoxy; C1-C8 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkynyloxy;
C1-C8 alkylthio; C3-C8 alkenylthio; C3-C8 alkynylthio; C1-C8 alkylsulfinyl; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkylthioalkyl; C2-C8 alkylsulfinylalkyl; C2-C8 alkylsulfonylalkyl; C4-C8 cycloalkylalkyl; C3-C8 trialkylsilyl; cyano; nitro; CO2Me; CO2Et; or NR11R12.
R7 is C1-C4 alkyl or C1-C4 haloalkyl;
R8 and R9 are each independently C2-C4 alkyl;
R10 and R11 are each independently H or C1-C4 alkyl; R12 is C1-C8 alkyl;
R8 and R10, or the groups R11 and R12, can be taken together to form -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2-, or -CH2CH(Me)OCH(Me)CH2-; and R13 is halogen; C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 haloalkyl;
provided that :
i) when Z is CR5=CR6, then at least one substituent selected from the group consisting of R3, R4, R5 and R6, is hydrogen; and
ii) the total number of carbons in R3, R4, R5 and R6 is equal to or less than 16; iϋ) the total number of nitrogen atoms
incorporated into the bicyclic
framework is less than or equal to four;
iv) R3 and R4 are not both hydrogen; and v) X and Y are not both nitrogen; and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
7. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a compound of Formula I
wherein:
Q is O or S;
W is O; S; S (O); S(O)2; NH; or NR9;
X is CR3 or N;
Y is CR4 or N; Z is CR5=CR6; CR5=N; N=CR6; S; O; or NR7; having the directionality of the CR5=CR6, CR5=N and N=CR6 linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;
R1 is C1-C18 alkyl; C3-C7 cycloalkyl; C2-C18
alkenyl; C2-C18 alkynyl; C1-C18 haloalkyl;
C2-C18 haloalkenyl; C2-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl; C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynylthioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl; C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxyalkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl; C4-C18
trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10, cyano, or nitro; C1-C8 alkyl substituted with CO2R8; C1-C18 alkoxy; C1-C18 haloalkoxy; C3-C18 alkynyloxy; C3-C18 alkenyloxy; C1-C18 alkylthio; C3-C18 alkenylthio; or C3-C18 alkynylthio;
R2 is C1-C18 alkyl; C3-C7 cycloalkyl; C3-C18
alkenyl; C3-C18 alkynyl; C1-C18 haloalkyl;
C3-C18 haloalkenyl; C3-C18 haloalkynyl; C2-C18 alkoxyalkyl; C2-C18 alkylthioalkyl; C2-C18 alkylsulfinylalkyl; C2-C18 alkylsulfonylalkyl;
C4-C18 cycloalkylalkyl; C4-C18 alkenyloxyalkyl; C4-C18 alkynyloxyalkyl; C4-C18 cycloalkyloxyalkyl; C4-C18 alkenylthioalkyl; C4-C18 alkynylthioalkyl; C6-C18 cycloalkylthioalkyl; C2-C18 haloalkoxyalkyl; C3-C18 haloalkenyloxyalkyl;
C4-C18 haloalkynyloxyalkyl; C4-C18 alkoxy alkenyl; C4-C18 alkoxyalkynyl; C4-C18 alkylthioalkenyl; C4-C18 alkylthioalkynyl; C4-C18 trialkylsilylalkyl; C1-C18 alkyl substituted with NR8R10; C2-C18 cyanoalkyl; C2-C18
nitroalkyl; C1-C8 alkyl substituted with CO2R8; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R13; or R1 and R2 can be taken together along with the
C=C-W fragment to which they are attached to form a 5-7 membered ring in which the R1-R2 bridge is a saturated, all-carbon chain
optionally substituted with C1-C12 alkyl;
R3 and R5 are each independently hydrogen; halogen;
C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; or C1-C4 haloalkoxy;
R4 and R6 are each independently hydrogen; halogen;
C1-C8 alkyl; C3-C8 cycloalkyl; C2-C8 alkenyl; C2-C8 alkynyl; C1-C8 haloalkyl; C3-C8
haloalkenyl; C3-C8 haloalkynyl; C1-C8 alkoxy; C1-C8 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkynyloxy; C1-C8 alkylthio; C3-C8 alkenylthio; C3-C8 alkynylthio; C1-C8 alkylsulfinyl; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkylthioalkyl; C2-C8 alkylsulfinylalkyl; C2-C8 alkylsulfonylalkyl; C4-C8 cycloalkylalkyl;
C3-C8 trialkylsilyl; cyano; nitro; CO2Me;
CO2Et; or NR11R12;
R7 is C1-C4 alkyl or C1-C4 haloalkyl;
R8 and R9 are each independently C1-C4 alkyl;
R10 and R11 are each independently H or C1-C4 alkyl; R12 is C1-C8 alkyl;
R8 and R10, or the groups R11 and R12, can be taken together to form -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2-, or -CH2CH(Me)OCH(Me)CH2-; and R13 is halogen; C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 haloalkyl;
provided that:
i) when Z is CR5=CR6, then at least one substituent selected from the group consisting of R3, R4, R5 and R6, is hydrogen; and
ii) the total number of carbons in R3, R4, R5 and R6 is equal to or less than 16; iϋ) the total number of nitrogen atoms
incorporated into the bicyclic
framework is less than or equal to four;
iv) R3 and R4 are not both hydrogen; and v) X and Y are not both nitrogen; or
N-oxides or agriculturally suitable salts thereof.
8. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a composition of Claim 6.
9. A method for controlling wheat powdery mildew comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a compound of Claim 1.
10. A method for controlling wheat powdery mildew comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a composition of Claim 6.
EP93911028A 1992-05-13 1993-05-10 Substituted pyrido 1,2-a]pyrimidinone derivatives as fungicides Withdrawn EP0640083A1 (en)

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US88221592A 1992-05-13 1992-05-13
US882215 1992-05-13
PCT/US1993/004188 WO1993023398A1 (en) 1992-05-13 1993-05-10 Substituted pyrido[1,2-a]pyrimidinone derivatives as fungicides

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Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
CN103983627A (en) * 2008-06-17 2014-08-13 韩国巴斯德研究所 Pyridopyrimidine compounds as anti-tubercular agents
UA110924C2 (en) * 2009-08-05 2016-03-10 Е. І. Дю Пон Де Немур Енд Компані Mesoionic pesticides
WO2012090514A1 (en) * 2010-12-27 2012-07-05 Sumitomo Chemical Company, Limited Arthropod pest control composition and method for controlling arthropod pests
PE20142364A1 (en) * 2012-02-10 2015-01-10 Hoffmann La Roche COMPOUNDS TO TREAT SPINAL MUSCULAR ATROPHY
KR102099997B1 (en) 2012-03-01 2020-04-13 피티씨 테라퓨틱스, 인크. Compounds for treating spinal muscular atrophy
EA028382B1 (en) 2012-03-23 2017-11-30 ПиТиСи ТЕРАПЬЮТИКС, ИНК. Compounds for treating spinal muscular atrophy
EP3082820B1 (en) 2013-12-19 2022-07-20 PTC Therapeutics, Inc. Methods for modulating the amount of rna transcripts
EP4249472A3 (en) 2015-05-30 2023-12-13 PTC Therapeutics, Inc. Methods for modulating rna splicing
IL281633B (en) 2015-12-10 2022-07-01 Ptc Therapeutics Inc Methods for treating huntington's disease
EP3544435A4 (en) 2016-11-28 2020-11-04 PTC Therapeutics, Inc. Methods for modulating rna splicing
EP3634953B1 (en) 2017-06-05 2024-01-03 PTC Therapeutics, Inc. Compounds for treating huntington's disease
CN111372611A (en) 2017-06-14 2020-07-03 Ptc医疗公司 Methods of modifying RNA splicing
CA3067591A1 (en) 2017-06-28 2019-01-03 Ptc Therapeutics, Inc. Methods for treating huntington's disease
US11395822B2 (en) 2017-06-28 2022-07-26 Ptc Therapeutics, Inc. Methods for treating Huntington's disease
CA3094703A1 (en) 2018-03-27 2019-10-03 Ptc Therapeutics, Inc. Compounds for treating huntington's disease
WO2020005873A1 (en) 2018-06-27 2020-01-02 Ptc Therapeutics, Inc. Heterocyclic and heteroaryl compounds for treating huntington's disease
US11685746B2 (en) 2018-06-27 2023-06-27 Ptc Therapeutics, Inc. Heteroaryl compounds for treating Huntington's disease
CN113214249B (en) * 2021-04-23 2023-09-19 成都大学 Synthesis method of pyrido [1,2-a ] pyrimidine-4-thioketone compound

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB970439A (en) * 1961-09-06 1964-09-23 Cutter Lab Pyridopyrimidinone compounds
US3755582A (en) * 1971-03-04 1973-08-28 Du Pont Quinazolinone fungicides
CA1232904A (en) * 1984-03-26 1988-02-16 Adi M. Treasurywala Substituted pyrimidones with antifungal properties
JPS63112566A (en) * 1986-10-28 1988-05-17 Nissan Chem Ind Ltd Pyrimidinone derivative, production thereof, insecticide, acaricide and fungicide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9323398A1 *

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