EP0469061A1 - Oxazolidinones fongicides - Google Patents

Oxazolidinones fongicides

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Publication number
EP0469061A1
EP0469061A1 EP90907560A EP90907560A EP0469061A1 EP 0469061 A1 EP0469061 A1 EP 0469061A1 EP 90907560 A EP90907560 A EP 90907560A EP 90907560 A EP90907560 A EP 90907560A EP 0469061 A1 EP0469061 A1 EP 0469061A1
Authority
EP
European Patent Office
Prior art keywords
substituted
phenyl
alkyl
ring
methyl
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.)
Pending
Application number
EP90907560A
Other languages
German (de)
English (en)
Inventor
John Benjamin Adams, Jr.
Detlef Geffken
Dennis Raymond Rayner
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26992641&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0469061(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US07/341,741 external-priority patent/US4957933A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0469061A1 publication Critical patent/EP0469061A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/44—Two oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/46—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems

Definitions

  • This invention pertains to a novel method-of- use of compounds of Structure I as fungicides for protecting plants from disease.
  • This invention comprises a method of
  • controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I,
  • A is O or NR 4 ;
  • W is O or S
  • R 1 is H; C 1 to C 6 alkyl; C 1 to C 6 haloalkyl; C 3 to C 6 cycloalkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; C 2 to C 6 alk ⁇ xyalkyl; C 1 to C 3 alkyl substituted with C 3 to C 6 cycloalkyl, Phenyl or benzyl, wherein said phenyl or benzyl ring is substituted on the ring with R 6 , and the benzylic carbon is substituted with R 7 ;
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 6 phenoxy substituted with R 6 , or pbenylthio substituted with R 6 ; C 1 to C 2 alkyl substituted with phenoxy or phenylthio, said phen ⁇ xy or phenylthio being substituted on the ring with R 6 ;
  • R 1 and R 2 can be taken together, along with the carbon to which they are attached, to form a carbocyclic or heterocyclic ring (containing
  • the carbocyclic ring can be fused with 1 or 2 R 5 -substituted benzene rings or with an R 6 -substituted thiophene ring;
  • R 3 is phenyl substituted with R 10 ; benzyl
  • R 3 can be thienyl substituted with R 10 , furyl substituted with R 10 , pyridyl substituted with R 10 , pyrimidyl substituted with R 10 , or pyridazyl substituted with R 10 ; or R 3 can be C 2 to C 10 alkyl or C 5 to C 7 cycloalkyl;
  • R 4 is hydrogen; formyl; C 2 to C 4 alkylcarbonyl;
  • alkoxyalkylcarbonyl C 2 to C 4 alkoxy- carbonyl; C 2 to C5 alkylaminocarbonyl; C 1 to C 4 alkylsulfo ⁇ yl; C 1 to C 4 alkyl; C 4 to C 6 cycloalkyl; phenylaminocarbonyl where said phenyl is substituted with R 10 ; and R 4 can be C 3 to C 4 alkenyl or C 3 to C 4 alkynyl; or R 3 and R 4 can be taken together, along with the nitrogen atom to which they are attached, to form a pyrrolidino, piperidino or pyrrolo rin tituted with R 10 , which rings can be to an R 10 -substituted benzene ring; R 5 is en; halogen; C 1 to C 12 alkyl; C 1 to C 12 haloalkyl; C 1 to C 12 alkoxy; C 3 to C 12 alkenyl; C 3 to C
  • alkynyloxy C 2 to C 12 alkoxyalkyl; C 2 to C 12 alkoxyalkoxy; phen ⁇ xymethyl substituted on the phenyl ring with R 6 ; benzyloxy
  • R 6 is hydrogen; 1 to 2 halogen; C 1 to C 4 alkyl; trifluoromethyl; C 1 to C 4 alkoxy;
  • R 7 is hydrogen; or C 1 to C 4 alkyl
  • R 8 is H; or C 1 to C 4 alkyl
  • R 9 is H; phenyl substituted with H; 1-2 halogen;
  • CF 3 C 1 to C 2 alkyl; or C 1 to C 2 alkoxy; and R 10 is 0-2 groups selected from H; CF 3 ; CF 3 O; NO 2 ; CO 2 Me; halogen; C 1 to C 5 alkyl; C 1 to C 5 alkoxy; or CN; provided that when the phenyl ring is disubstituted, one of the alkyl or alkoxy groups is no larger than C 1 ; provided that, when A is oxygen, R 3 is phenyl
  • A is NR 4 ;
  • R 1 is C 1 to C 4 alkyl; C 1 to C 3 haloalkyl; vinyl; ethynyl; or methoxymethyl;
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 4 is H; C 1 to C 3 alkyl; or C 1 to C 3
  • R 1 is C 1 to C 4 alkyl or vinyl
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 3 is phenyl substituted with 1-2 halogen, methyl or methoxy;
  • R 4 is hydrogen or methyl
  • R 5 is hydrogen; halogen; C 1 to C 4 alkyl; C 1 to C 4 haloalkyl; C 1 to C 6 alkoxy;
  • haloalkoxy phenoxy substituted with R 6 ; provided that if R 5 is not H or F, then it is para to the point of attachment to the ring; R 6 is hydrogen, 1 to 2 F of C1; methyl; or methoxy; and
  • R 7 is hydrogen
  • R 1 is CH 3 ;
  • R 4 is hydrogen or methyl
  • R 5 is H; F; C1; CH 3 ; C 1 to C 6 alkoxy; or
  • R 6 is H or F
  • R 10 is F; H or CH 3 .
  • This invention also comprises novel
  • A is O or NR 4 ;
  • W is O or S
  • R 1 is H; C 1 to C 6 alkyl; C 1 to C 6 haloalkyl; C 3 to C 6 cycloalkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; C 2 to C 6 alkoxyalkyl; C 1 to C 3 alkyl substituted with C 3 to C 6 cycloalkyl, phenyl or benzyl, wherein said phenyl or benzyl ring is substituted on the ring with R 6 , and the benzylic carbon is substituted with R 7 ;
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 6 phenoxy substituted with R 6 , or phenylthio substituted with R 6 ;
  • R 1 and R 2 can be taken together, along with the carbon to which they are attached, to form a carbocyclic or heterocyclic ring (containing
  • the carbocyclic ring can be fused with 1 or 2 R 5 -substituted benzene rings or with an R ⁇ -substituted thiophene ring;
  • R 3 is phenyl substituted with R 10 ; benzyl
  • R 3 can be thienyl substituted with R 10 , furyl substituted with R 10 , pyridyl substituted with R 10 , pyrimidyl substituted with R 10 , or pyridazyl substituted with R 10 ; or R 3 can be C 2 to C 10 alkyl or C 5 to C 7 cycloalkyl;
  • R 4 is hydrogen; formyl; C 2 to C 4 alkylcarbonyl;
  • R 4 can be C 3 to C 4 alkenyl or C 3 to C 4 alkynyl; or R 3 and R 4 can be taken together, along with the nitrogen atom to which they are attached, to form a pyrrolidino, piperidino or pyrrolo ring substituted with R 10 , which rings can be fused to an R 10 -substituted benzene ring;
  • R 5 is hydrogen; halogen; C 1 to C 12 alkyl; C 1 to C 12 haloalkyl; C 1 to C 12 alkoxy; C 3 to C 12 alkenyl; C 3 to C 12 halo
  • alkynyloxy C 2 to C 12 alkoxyalkyl; C 2 to C 12 alkoxyalkoxy; phenoxymethyl substituted on the phenyl ring with R 6 ; benzyloxy
  • R 6 is hydrogen; 1 to 2 halogen; C 1 to C 4 alkyl; trifluoromethyl; C 1 to C 4 alkoxy;
  • R 7 is hydrogen; or C 1 to C 4 alkyl
  • R 8 is H; or C 1 to C 4 alkyl
  • R 9 is H; phenyl substituted with H; 1-2 halogen;
  • CF 3 C 1 to C 2 alkyl; or C 1 to C 2 alkoxy; and R 10 is 0-2 groups selected from H; CF 3 ; CF 3 O;
  • R 1 is not hydrogen, methyl or benzyl
  • R 2 is not methyl, isopropyl or cyclohexyl
  • R 1 and R 2 do not join to form -(CH 2 ) 5 -.
  • A is NR 4 ;
  • R 1 is C 1 to C 4 alkyl; C 1 to C 3 haloalkyl; vinyl; ethynyl; or methoxymethyl;
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 1 is not methyl.
  • R 1 is C 1 to C 4 alkyl or vinyl
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 3 is phenyl substituted with 1-2 halogen, methyl or methoxy;
  • R 4 is hydrogen or methyl;
  • R 5 is hydrogen; halogen; C 1 to C 4 alkyl; C 1 to C 4 haloalkyl; C 1 to C 6 alkoxy;
  • haloalkoxy phenoxy substituted with R 6 ; provided that if R 5 is not H or F, then it is para to the point of attachment to the ring;
  • R 6 is hydrogen, 1 to 2 F or Cl; methyl; or methoxy
  • R 7 is hydrogen
  • R 1 is not methyl.
  • R 1 is CH 3 ;
  • R 4 is hydrogen or methyl
  • R 5 is H; F; C1; C H3 ; C 1 to C 6 alkoxy; or phenoxy substituted with halogen, CH 3 , CH 3 O or NO 2 ;
  • R 6 is H or F
  • R 10 is F; H or CH 3 ;
  • R 2 is not unsubstituted phenyl.
  • the compounds of this invention may be prepared by the route outlined below to 5-methyl-5-phenyl- 3-(phenylamino)-2-thioxo-4-oxazolidinone:
  • enantiomers Although one enantiomer may have superior fungicidal activity for a given compound of Formula I, the other enantiomer is not devoid of activity nor does it interfere with the activity of the more potent enantiomer.
  • compounds of Formula I can be prepared by treating heterocycles of type II with an appropriate amine III.
  • Equation 2 Compounds described by Formula I wherein w is S can be prepared as illustrated in Equation 2. Equation 2
  • the thioxodioxazinones Ila are prepared according to the method outlined in Equation 3.
  • Triethylamine is commonly used as an added base and 1,3-dicyclohexylcarbodiiraide (DCC) is used as the dehydrating agent. Equation 4
  • 2-Hydroxycarboxylic acids can be purchased from commercial sources, or generally prepared from ketones or aldehydes by formation of cyanohydrins, then hydrolysis, as is known in the art.
  • Esters can be prepared from the
  • aryl ⁇ -hydroxycarboxylic acid esters can also be prepared by treating pyruvate esters with nucleophilic organometallic reagents such as phenyl magnesium bromide or phenyl lithium as described in the literature (Salomon, R. G., Pardo, S. N., Ghosh, S., J. org. Chem., 1982, 47, 4692).
  • nucleophilic organometallic reagents such as phenyl magnesium bromide or phenyl lithium as described in the literature (Salomon, R. G., Pardo, S. N., Ghosh, S., J. org. Chem., 1982, 47, 4692).
  • ⁇ -hydroxyhydroxamic acids IV can also be synthesized by treating ⁇ -keto- hydroxamic acids VII with an excess of a Grignard reagent. [Geffken, D.; Burchardt, A.; Arch. Pharm., 1988, 321, 311] The reactions are conducted in refluxing ether for 2 to 6 hours.
  • the ⁇ -ketohydroxamic acids VII can be prepared by condensing the glyoxylic acid chlorides VIII, derived from the corresponding carboxylic acids,
  • Equation 6 Equation 6
  • the starting hydroxamic acids IX are prepared by treating ethyl oxalyl chloride X with
  • X-imidazole or oxalyl chloride
  • hydroxamic acids of type XI produces dioxotetrahydrooxazoles Ic.
  • the cyclizations can be conducted in an inert solvent, for example benzene or methylene chloride, at temperatures ranging from 0°C to 80°C.
  • the intermediate N-aminocarbamates XII may or may not be isolated. For cases in which ring closure is not spontaneous under the reaction
  • the dioxazinediones IIb are readily prepared from the corresponding ⁇ -hydroxyhydroxamic acid by treatment with 1,1'-carbonyldiimidazole (Equation 11).
  • the cyclization is performed in an inert solvent such as methylene chloride and is complete in less than one minute at 25°C. [Geffken, D.; Arch. Pharm., 1982, 315, 802; Geffken, D., Synthesis, 1981, 38] Equation 11
  • oxazolidinediones described by Formula I wherein W is O can be prepared by desulfurization of thioxooxazolidinones as shown in Equation 12.
  • thioxooxazolidinone (lb) is dissolved in a water-miscible organic solvent such as methanol, acetone, acetonitrile, dimethylformamide, dioxane, tetrahydrofuran, etc. Methanol and acetone are preferred.
  • a water-miscible organic solvent such as methanol, acetone, acetonitrile, dimethylformamide, dioxane, tetrahydrofuran, etc. Methanol and acetone are preferred.
  • Methanol and acetone are preferred.
  • desulfurizing agent such as aqueous OXONE® (KHSO 5 ), aqueous silver nitrate, bleach (NaOC1), various peroxides and peracids or other reagents known by those skillefd in the art to oxidize sulfur.
  • Aqueous OXONE® and aqueous silver nitrate are preferred.
  • the reaction mixture is stirred at temperatures ranging from about -20°C to about 100°C until the reaction is complete.
  • the product can be isolated by evaporation ofthe solvent, and purified by washing with water in a water-immiscible solvent such as methylene chloride of ether. Drying, evaporation of the solvent, followed by further purification by recrystallization or chromatography affords pure oxazolidinediones. Id.
  • a novel process for preparing thioxooxazolidinones lb expeditiously and in good yield is also disclosed herein.
  • the process comprises four sequential reactions:
  • the ester group can be alkyl (C 1 -C 12 ), alkenyl (C 3 -C 4 ), cycloalkyl
  • esters in which Z is C 1 -C 4 alkyl.
  • Thioxooxazolidinones lb prepared by this method preferred for reasons of ease of synthesis, lower expense or greater utility, are compounds wherein:
  • R 1 is methyl
  • R 2 is phenyl substituted with R 5 and R 6 ;
  • R 3 is phenyl substituted with R 10 ;
  • R 4 is hydrogen
  • solvent (s) can be selected, e.g., so that reaction ingredients have a substantial
  • Usable bases are those capable of deprotonation of the hydroxy group without unacceptable side reactions. Included are the alkali metal tertiary alkoxides, hydrides, and hydroxides. Preferred among these in the interest of higher solubility, reactivity, ease or safety of use, higher yields, or economy are the potassium tertiary
  • alkoxides such as potassium tert.-butoxide and
  • potassium tert.-amylate Especially preferred is potassium tert.-butoxide.
  • Usable solvents are the 2-hydroxycarboxylic acid ester itself and generally the non-hydroxylic solvents, including ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane), esters (e.g. methyl and ethyl acetate), amides (e.g. N,N-dimethylformamide, N,N-dimethylacetamide,
  • acetonitrile and the like, and mixtures containing one or more of these solvents.
  • Preferred among these solvents are those in which the reactants have substantial solubility.
  • the temperature can vary from about -80°C to about +100°C with about -20°C to +80°C preferred, and with about -5°C to +50°C more preferred.
  • Ambient temperature is a convenient temperature at which to conduct the reaction.
  • reaction Step 2 carbon disulfide (CS 2 ) is contacted with the product of Step 1 at about -20°C to +100°C, preferably -10°C to +50°C, for about 5 seconds to about 24 hrs., preferably for about 5 to 30 min.
  • the reaction is rapid for soluble reactants.
  • Ambient temperature is a convenient temperature at which to conduct the reaction.
  • an acylating agent capable of forming a mixed-anhydride with the product of Reaction Step 2 is contacted with the product of Reaction Step 2.
  • acylating agents include chloroformates, e.g. methyl chloroformate, ethyl chloroformate, propyl chloroformate, butyl
  • acylating agents are methyl and ethyl chloroformate.
  • the reaction is rapid, and is complete in about 5 seconds to an hour with soluble reactants. Most reactions are complete in about 1 to 30 minutes.
  • the temperature can range from.about -20°C to +50°C. The preferred range is from about -10°C to +25°C. Ice to ambient
  • temperatures is a convenient temperature range for conducting this reaction.
  • the substituted hydrazine reactant is contacted with the product of Reaction Step 3.
  • the substituted hydrazine can be used as the free base or as a mixture of its acid salt with an adijed acid scavenger such as a tertiary amine base (e.g. triethylafiine, N,N-diisopropyl-N-ethylamine).
  • adijed acid scavenger such as a tertiary amine base (e.g. triethylafiine, N,N-diisopropyl-N-ethylamine).
  • Reaction times may be 10 seconds to about 1 day, preferably about 1 minute to 8 hrs.
  • Reaction temperatures can range from about -20°C to +100°C. Ice to ambient temperatures is a convenient range at which to conduct the reaction.
  • Step 4 The product of Step 4 can be isolated by
  • the resulting thin slurry was allowed to come to -10°C, then diluted with 200 mL each of water and ether.
  • the aqueous phase was adjusted to pH 7 by addition of IN aqueous HC1, the ether phase was separated, the aqueous phase was extracted with two 100 mL portions of ether, and the combined ether phases were washed with three 100-mL portions of water and 100 mL of brine, dried over magnesium sulfate, and evaporated to leave 5.8 g of a dark brown oil. Chromatography over silica gel, eluting with methylene
  • the pyruvate solution was chilled to -10°C, and the Grignard solution was run in over 15 minutes with good stirring, cooling to maintain an internal temperature of -5 to -10°C.
  • tert.-butoxide (4.76 g, 0.0424 mole) was added. The ice bath was removed, and the mixture was stirred for 10 minutes. This procedure provided a clear, yellow solution at 21°C. Carbon disulfide (2.8 ml, 0.046 mole) was added, and caused the formation of an orange color and a temperature rise to 32°C. The solution was cooled in an ice bath for 10 minutes, causing the temperature to fall to 4°C.
  • Phenylhydrazine (97%, 4.5 ml, 0.044 mole) was added. The temperature rose to 24°C while the
  • the oil was mixed with 1-chlorobutane and water, and the layers were separated.
  • the organic layer was washed with IN HC1, water, and saturated aq. sodium bicarbonate solution.
  • the oil was crystallized from carbon tetrachloride/hexane, and the solid product further purified by boiling with isopropanol (without dissolution of all solid), cooling, and filtering.
  • the product was obtained as3.56 g (27% of theoretical) of analytically-pure white solid, m.p. 187-189°C.
  • phenylhydrazine was added, the resulting slurry was stirred and allowed to come to room temperature, another 20 mL of THF was added, and the mixture was stirred another 15 minutes at room temperature. Most of the solvent was then removed by rotary
  • the compounds of this invention will generally be used in formulation with a liquid or solid diluent or with an organic solvent.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like any of these may be
  • Sprayab formulations can be
  • compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 35% surfactant(s) and b) about 5% to 99%
  • Emulsifiers Annual MC Publishing 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. Preferably, ingredients should be approved by the U.S. Environmental Protection
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent
  • Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.
  • the iiigreidients are combined and stirred to produce a solution, which can be used for low volume applications.
  • non-ionic surfactants 6% Acetophenone 79%
  • the compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of plant pathogens in the basidiomycete, and ascomycete classes and particularly against fungi in the
  • oomycete class are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops, such as Plasmopara viticola,
  • the compounds of this invention can be mixed with fungicides, bactericides, acaricides,
  • Suitable agents of this type are nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material. Suitable agents of this type are
  • chloroneb 1,4-dichloro-2,5-dimethoxybenzene
  • chloroneb methyl 1-(butylearbamoyl)-2-benzimidazolecarbamate (benomyl)
  • combinations with other fungicides having a similar spectrum of disease control but a different mode of action will be particularly advantageous for resistance management and/or improved properties such as curative activity for established infections.
  • a particularly effective combination in both regards is one involving a compound of Formula I and cynoxanil.
  • Disease control is ordinarily accomplished by applying an effective amount of the compound 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.
  • the compound may also be applied to the seed from which the plants to be protected are to be grown. 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 10,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 1 to 10 grams per kilogram of seed.
  • test compounds were 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). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaegualis (the causal agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.
  • a spore suspension of Venturia inaegualis the causal agent of apple scab
  • test compounds were 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). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosporidium personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22°C for 24 hr, a high humidity atmosphere at 22 to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made.
  • a spore suspension of Cercosporidium personatum the causal agent of peanut late leafspot
  • test compounds were 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). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Pu ⁇ cinia recondita (the causal agent of wheat leaf rust) and incubated in a
  • test compounds were 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). This 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 hr, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Trem 014 polyhydric alcohol esters
  • test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 40 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters).
  • the suspension was sprayed to the point of run-off on grape seedlings.
  • 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 hours, moved to a gfowth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 hours, after which the disease ratings were made.
  • test compounds were dissolved in acetone in an aiftount equal to 3% of the final volume and then suspended a f 200 ppm in purified water conta he surfactant Trem 014 (polyhydric .alcohol esters). This suspension was sprayed to the point of run-off on cucumber
  • 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 hr, 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
  • test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 40 ppm in purified water containing 250 ppm of the surfactant Trem 014
  • test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 40 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). The suspension was sprayed to the point of run-off on cucumber
  • Pseudoperonospora cubensis the causal agent of cucumber downy mildew
  • incubated in a saturated atmosphere at 20°C for 24 hours moved to a growth chamber at 20°C for 6 days, and the incubated in a saturated atmosphere at 20°C for 24 hours, after which the disease ratings were made.
  • test compounds were 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).
  • Trem 014 polyhydric alcohol esters
  • the suspension was sprayed to the point of run-off on wheat seedlings.
  • the following day the seedlings were inoculated with spores of Ervsiohe oraminis (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 compounds were 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 suspension was sprayed to the point of run-off on rice seedlings.
  • the seedlings were inoculated with a spore suspension of Rhizoctonia solani (the causal agent of rice sheath blight) and incubated in a saturated atmosphere at 27°C for 48 hours, moved to a growth chamber at 29°C for 48 hours after which the disease ratings were made.
  • test compounds were 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 suspension was sprayed to the point of run-off on rice seedlings.
  • Trem 014 polyhydric alcohol esters
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls).
  • a "-" indicates that no test was performed at the indicated concentration on that disease.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

L'invention concerne un procédé permettant de combattre des maladies affectant des plantes par l'utilisation de thioxo-oxazolidinones, d'oxazolidinediones et d'hétérocycles apparentés, dont certains sont nouveaux, et des compositions appropriées à un usage agricole qui contiennent ces composés.
EP90907560A 1989-04-21 1990-04-10 Oxazolidinones fongicides Pending EP0469061A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US34174289A 1989-04-21 1989-04-21
US341741 1989-04-21
US341742 1989-04-21
US07/341,741 US4957933A (en) 1989-04-21 1989-04-21 Fungicidal oxazolidinones

Publications (1)

Publication Number Publication Date
EP0469061A1 true EP0469061A1 (fr) 1992-02-05

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EP90303859A Expired - Lifetime EP0393911B1 (fr) 1989-04-21 1990-04-10 Oxazolidinones fongicides
EP90907560A Pending EP0469061A1 (fr) 1989-04-21 1990-04-10 Oxazolidinones fongicides

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EP90303859A Expired - Lifetime EP0393911B1 (fr) 1989-04-21 1990-04-10 Oxazolidinones fongicides

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EP (2) EP0393911B1 (fr)
JP (1) JP2963388B2 (fr)
KR (1) KR0148128B1 (fr)
CN (2) CN1028143C (fr)
AT (1) ATE110719T1 (fr)
AU (1) AU638460B2 (fr)
BG (1) BG60677B1 (fr)
BR (1) BR9007309A (fr)
CZ (1) CZ286037B6 (fr)
DE (2) DE69011930T2 (fr)
DK (1) DK0393911T3 (fr)
ES (1) ES2063264T3 (fr)
FI (1) FI914927A0 (fr)
HU (1) HU214551B (fr)
IE (1) IE66407B1 (fr)
IL (1) IL94152A (fr)
NL (1) NL350010I2 (fr)
NO (1) NO914117L (fr)
NZ (1) NZ233374A (fr)
RO (1) RO111765B1 (fr)
RU (1) RU2092051C1 (fr)
UA (1) UA35548C2 (fr)
WO (1) WO1990012791A1 (fr)
YU (1) YU80390A (fr)

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EP0533734A1 (fr) * 1990-06-11 1993-03-31 E.I. Du Pont De Nemours And Company Iminooxazolidinones fongicides
AU1578192A (en) * 1991-03-15 1992-10-21 E.I. Du Pont De Nemours And Company Fungicidal 4-thioxooxazolidin-2-ones and 4-iminooxazolindin-2-ones
US5298516A (en) * 1991-03-27 1994-03-29 Sankyo Company, Limited Thiazolidone compounds and method of using the same as a vasodilator
FR2685328B1 (fr) * 1991-12-20 1995-12-01 Rhone Poulenc Agrochimie Derives de 2-imidazoline-5-ones et 2-imidazoline-5-thiones fongicides.
WO1993018016A1 (fr) * 1992-03-11 1993-09-16 E.I. Du Pont De Nemours And Company Oxazolidinones fongicides
EP0637301A1 (fr) * 1992-04-24 1995-02-08 E.I. Du Pont De Nemours And Company Oxazolidinones fongicides
ES2149815T3 (es) * 1992-05-22 2000-11-16 Du Pont Imidazolinonas fungicidas.
WO1994011359A1 (fr) * 1992-11-13 1994-05-26 E.I. Du Pont De Nemours And Company Procedes de preparation de 2,4-oxazolidinediones
JP3818543B2 (ja) * 1995-03-08 2006-09-06 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 殺菌・殺カビ性混合物
CZ296513B6 (cs) * 1995-07-12 2006-03-15 E. I. Du Pont De Nemours And Company Synergická fungicidní kompozice
GB9607785D0 (en) * 1996-04-15 1996-06-19 Zeneca Ltd Fungicides
GB9607784D0 (en) * 1996-04-15 1996-06-19 Zeneca Ltd Fungicides
US6313121B1 (en) * 1997-03-05 2001-11-06 Syngenta Crop Protection, Inc. Microbicides
FR2771898B1 (fr) * 1997-12-04 2000-01-07 Rhone Poulenc Agrochimie Composition fongicide et/ou bactericide synergique
US6090806A (en) * 1998-08-31 2000-07-18 American Cyanamid Company Fungicidal mixtures
DE10347090A1 (de) 2003-10-10 2005-05-04 Bayer Cropscience Ag Synergistische fungizide Wirkstoffkombinationen
DE10349501A1 (de) 2003-10-23 2005-05-25 Bayer Cropscience Ag Synergistische fungizide Wirkstoffkombinationen
DE102005015677A1 (de) 2005-04-06 2006-10-12 Bayer Cropscience Ag Synergistische fungizide Wirkstoffkombinationen
DE102005026482A1 (de) 2005-06-09 2006-12-14 Bayer Cropscience Ag Wirkstoffkombinationen
US8754009B2 (en) 2005-06-09 2014-06-17 Bayer Cropscience Ag Active compound combinations
DE102007045920B4 (de) 2007-09-26 2018-07-05 Bayer Intellectual Property Gmbh Synergistische Wirkstoffkombinationen
CN101555207B (zh) * 2008-04-10 2012-10-17 上海生农生化制品有限公司 一种对苯氧基苯基乳酸酯化高收率的方法
CN102365018B (zh) 2009-03-25 2014-10-29 拜尔农作物科学股份公司 具有协同作用的活性成分结合物
BR112012001080A2 (pt) 2009-07-16 2015-09-01 Bayer Cropscience Ag Combinações de substâncias ativas sinérgicas contendo feniltriazóis
CN103396410A (zh) * 2013-08-07 2013-11-20 北京金五元科技发展有限责任公司 吡噁唑菌酮的合成及作为农用杀菌剂的应用
CN104472502A (zh) * 2014-11-27 2015-04-01 广东中迅农科股份有限公司 一种含有噁唑菌酮和咯菌腈的杀菌组合物
CN104488888A (zh) * 2014-12-03 2015-04-08 广东中迅农科股份有限公司 一种含有噁唑菌酮和苯锈啶的杀菌组合物
EP2910126A1 (fr) 2015-05-05 2015-08-26 Bayer CropScience AG Combinaisons de composés actifs à propriétés insecticides
CN105541743A (zh) * 2015-12-10 2016-05-04 上海生农生化制品有限公司 一种双联类噁唑菌酮化合物及其合成方法
CN107540626A (zh) * 2016-06-23 2018-01-05 华东理工大学 噁唑菌酮的多晶型及其制备方法

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Publication number Publication date
UA35548C2 (uk) 2001-04-16
CN1096157A (zh) 1994-12-14
DE69011930T2 (de) 1995-01-19
DK0393911T3 (da) 1994-10-03
BG95344A (bg) 1993-12-24
KR0148128B1 (ko) 1998-08-17
IE901410L (en) 1990-10-21
JPH09104677A (ja) 1997-04-22
EP0393911A1 (fr) 1990-10-24
CZ286037B6 (cs) 1999-12-15
HU214551B (hu) 1998-08-28
HUT60255A (en) 1992-08-28
IL94152A (en) 1995-08-31
DE69011930D1 (de) 1994-10-06
BR9007309A (pt) 1992-03-24
DE10199034I2 (de) 2011-07-21
NO914117D0 (no) 1991-10-18
NL350010I1 (nl) 2003-04-01
AU638460B2 (en) 1993-07-01
KR920701179A (ko) 1992-08-11
FI914927A0 (fi) 1991-10-18
IE66407B1 (en) 1995-12-27
JP2963388B2 (ja) 1999-10-18
EP0393911B1 (fr) 1994-08-31
CZ198490A3 (cs) 1999-10-13
CN1058841C (zh) 2000-11-29
CN1047079A (zh) 1990-11-21
BG60677B1 (en) 1995-12-29
CN1028143C (zh) 1995-04-12
RO111765B1 (ro) 1997-01-30
ATE110719T1 (de) 1994-09-15
NZ233374A (en) 1991-02-26
HU904470D0 (en) 1991-12-30
WO1990012791A1 (fr) 1990-11-01
AU5655490A (en) 1990-11-16
ES2063264T3 (es) 1995-01-01
NL350010I2 (nl) 2004-01-05
RU2092051C1 (ru) 1997-10-10
NO914117L (no) 1991-11-29
YU80390A (en) 1991-10-31

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