Classifications

• • 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
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D319/20—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring with substituents attached to the hetero ring

Definitions

• This invention relates to novel fungicidal benzodioxane amine derivatives used for controlling fungal diseases, particularly powdery mildews, in plants.
• X is CH 2 and Y is O;
• X is O and Y is CH 2 or CHOH.
• Z is H or C 1 -C 4 alkyl
• n O or 1.
• Z is C(O), CR 3 R 4 or CR 3 OR 4 ;
• n O or 1.
• Ph is optionally substituted 1,2-phenylene.
• X is NHR, NHR 1 ,
• 53:16137c discloses 7-substituted -2-aminomethyl-1,4-benzodioxan derivatives with sedative action.
• R 1 is H or lower alkyl
• R 2 and R 3 are each H or lower alkyl
• R 2 and R 3 may be taken together as a 5- to
• R 4 is H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or halogen.
• This invention comprises a method for controlling fungal diseases in plants comprising applying to the locus of the plant a compound of formula I
• R 1 and R 2 are independently H, halogen, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 5 alkyl substituted with 1-3 F, Cl or Br or C 2 -C 4 alkoxyalkyl, Si(CH 3 ) 3 , thioalkyl, or phenyl substituted with one or two of the following: halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
• R 3 , R 4 and R 5 are independently H, CH 3 , CF 3 or
• R 6 and R 7 are independently C 1 -C 8 alkyl; or R 6 and R 7 can be taken together as piperidino, morpholino, pyrrolidino, hexamethyleneimino, heptamethyleneimino, wherein these groups are optionally substituted by 1 or 2 of the following: C 1 -C 4 alkyl groups or phenyl rings substituted by hydrogen or 1 or 2 halogen, C 1 -C 4 alkyl, or C 1 or C 4 alkoxy groups.
• X is O or S
• Y is O or S
• Z is C 1 -C 4 unbranched alkylene optionally substituted by 1-2 CH 3 , CF 3 or CH 2 CH 3 groups; m is 0 or 1; and
• alkyl used either alone or in compound words such as “alkoxy-alkyl”, denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.
• Alkoxy denotes e.g., methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy isomers.
• Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 1- ⁇ ropenyl, 2-propenyl,
• Alkynyl denotes straight chain or branched alkynes, e.g., ethynyl, 1-propynyl, 2- ⁇ ropynyl and the different butynyl isomers.
• the total number of carbon atoms in a substituent group is indicated by the C i -C j prefix where i and j are numbers from 1 to 8.
• C 3 -C 4 alkenyl would designate propenyl through butenyl.
• R 1 and R 2 are located at the 6 and 7 positions of the benzene ring
• R 3 , R 4 and R5 are independently H or CH 3 .
• R 1 is H
• R 2 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy
• Rg and Ry are taken together as piperidino, morpholino or pyrrolidino optionally substituted by phenyl or 1-2 C 1 -C 2 alkyl groups.
• Z is C 1 -C 3 unbranched alkylene optionally
• R 6 and R 7 are taken together as piperidino, morpholino, pyrrolidino, 2,6-dimethyl- morpholino, 3,5-dimethylpiperidino and 4-phenylpiperidino;
• R 2 is C 2 -C 4 alkyl or C 2 -C 4 alkoxyalkyl
• X and Y are O.
• the compound of Formula I is selected from the group consisting of:
• This invention also comprises compounds of formula II and agriculturally suitable compositions containing them
• R 1 and R 2 are independently H; halogen; C 1 -C 8
• alkyl C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 1 -C 8 alkoxy; C 1 -C 5 alkyl substituted with 1-3 F, Cl or Br or C 2 -C 4 alkoxyalkyl; Si(CH 3 ) 3 ; thioalkyl; or phenyl substituted with one or two of the following: halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
• R 3 , R 4 and R 5 are independently H, CH 3 , CF 3 or
• R 6 and R 7 are independently C 1 -C 8 alkyl; or R 6 and R 7 can be taken together as piperidino, morpholino, pyrrolidino, hexamethyleneimino, heptamethyleneimino, wherein these groups are optionally substituted by 1 or 2 are of the following: C 1 -C 4 alkyl, or phenyl rings substituted by hydrogen or 1 or 2 halogen, C 1 -C 4 alkyl, or C 1 or C 4 alkoxy groups.
• X is O or S;
• Y is O or S
• Z is C 1 -C 4 unbranched alkylene optionally
• R 6 and R 7 are taken together as piperidino substituted at the 2, 3, 5 or 6 positions, or as substituted morpholine;
• R 1 and R 2 are both H, then R 6 and R 7 are taken together as substituted piperidino or morpholino.
• R 1 and R 2 are located at the 6 and 7 positions of the benzene ring
• R 3 , R 4 and R 5 are independently H or CH 3 .
• R 1 is H
• R 2 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxyalkyl or halogen
• R 6 and R 7 are taken together as piperidino, morpholino or pyrrolidino optionally substituted by phenyl or 1-2 C 1 -C 2 alkyl groups. 3. The method of Preferred 2 wherein
• Z is C 1 -C 3 unbranched alkylene optionally substituted by a CH 3 group. 4. The method of Preferred 3 wherein
• R 6 and R 7 are taken together as piperidino, morpholino, pyrrolidino, 2,6-dimethylmorpholino, 3,5-dimethylpiperidino and
• R 2 is C 2 -C 4 alkyl or C 2 -C 4 alkoxyalkyl
• Typical leaving groups include halides and sulfonates.
• the reaction is run neat with one to three equivalents of the amine with or without an additional base such as potassium carbonate at temperatures between 25 and 150°C.
• a solvent such as DMF may also be used.
• the compounds Ila where X-Z, R 1 -R 7 are as defined above and L is a sulfonate can be prepared from an alcohol IV and sulfonyl chloride (e.g., toluene sulfonyl chloride) in a solvent such as pyridine at temperatures between 0 and 25°C.
• sulfonyl chloride e.g., toluene sulfonyl chloride
• Compounds lib where L is a halogen can be prepared from an alcohol IV and thionyl chloride using the standard conditions known to one familiar with the art.
• the iodide can be prepared from the chloride using sodium iodide/acetone.
• An aqueous base such as potassium or sodium hydroxide at pressures between atmospheric and 100 psi as taught in U.S. 2,056,046.
• a mixture of regioisomers IVa is obtained using this method.
• epoxides VIII Oxidation with a peracid such as m-chloroperoxybenzoic acid (m-CPBA) in a halogenated solvent or ethyl acetate at temperatures between 25 and 100°C forms the esters IX. Subsequent aqueous base hydrolysis provides the alcohols as taught by R.
• a peracid such as m-chloroperoxybenzoic acid (m-CPBA) in a halogenated solvent or ethyl acetate at temperatures between 25 and 100°C
• the esters X are prepared from substituted catechols or thiocatechols of formula V and a (un) substituted ethyl bromocrotonate in acetone or acetonitrile with a base such as potassium carbonate as taught by G. Cerioni, J. Heterocyclic Chem.. 23, 18-15 (1886). This method provides a mixture of regioisomers.
• Chain extended esters X can also be obtained from aqueous acid hydrolysis of the corresponding nitriles XI. This reaction is conveniently carried out in aqueous methanolic hydrochloric acid at reflux.
• the nitriles XI are prepared from
• these same nitriles XI can be obtained from the corresponding chlorides Ila and a metal cyanide, e.g., sodium cyanide in an alcoholic solvent such as ethanol or methanol.
• a metal cyanide e.g., sodium cyanide in an alcoholic solvent such as ethanol or methanol.
• compounds of Formula I can be prepared by reduction of the corresponding amide XII using a reducing reagent such as lithium aluminum hydride in a convenient solvent, for example,
• the amides XII are prepared from the
• the acid chlorides XIII are prepared from the corresponding acids X using standard reaction
• the N-oxides of Formula I can be prepared from the amines by oxidation using standard reaction conditions known to those skilled in the art.
• the acid salts of formula I can be prepared by treatment of the free base with the corresponding acid (e.g., hydrogen chloride) in an organic solvent such as diethyl ether.
• the method of this invention can be any method of this invention.
• formulation by absorption on a carrier.
• Possible formulation types include dusts granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of the these may be applied directly. Sprayable
• formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength
• compositions are primarily used as intermediates for further formualtion.
• the formulations broadly, contain about 0.1% to 99% by weight of active
• ingredient(s) and at least one of (a) about 0.1% to 2% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following
• Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.
• surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, micro- biological growth, etc.
• 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. Water dispersible granules may be produced by agglomerating a fine powder composition (see, for example B. Cross and H. Scher, "Pesticide Formulations", ACS Symposium Series 371, American Chemical Society, Washington, DC, 1988, pp.
• Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084).
• 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. December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
• the active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the
• the material is warmed to evaporate the solvent.
• the material is allowed to cool and then packaged.
• the active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
• the active ingredient is blended with
• ground concentrate is then blended with powdered pyrophyllite until homogeneous.
• the compounds of this invention are useful as plant disease control agents. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental,
• Cinerea Cercpsporidium personatum, Podosphaera leucotricha, Cercospora beticola, and Uncinula necatur. They also control seed pathogens. 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, or to the media (soil or sand) in which the plants to be protected are growing. 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 5000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.06 to about 3 grams per kilogram of seed.
• the compounds of this invention can be mixed with fungicides, bactericides, acaricides,
• Fungicides nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well known to those skilled in the art. Some are listed below: Fungicides:
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat
• plants were inoculated with a spore suspension of Puccinia recondita. the causal agent of wheat leaf rust, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 20°C for 7 days, when disease ratings were made.
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on broad bean or cucumber seedlings. The following day plants were inoculated with a spore suspension of Botrytis
• cinerea the causal agent of grey mold, and incubated in a saturated humidity chamber at 20°C for 48 hours and then in a growth chamber at 20°C for 4 days, when disease ratings were made.
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant
• TREM 014 polyhydric alcohol esters
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250p ⁇ m of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250p ⁇ m of the surfactant
• TREM 014 polyhydric alcohol esters
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on sugarbeet seedlings. The following day plants were inoculated with a spore suspension of Cercospora beticola, the causal agent of sugarbeet leaf spot, and incubated in a saturated humidity chamber at 22°C for 24 hours and then in a high humidity growth chamber at 22°C for 7 days, when disease ratings were made.
• TREM 014 polyhydric alcohol esters
• test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of from 1000 to 2 ppm in purified water containing 250ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape

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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)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Plural Heterocyclic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 1989
  • 1989-08-15 EP EP89910036A patent/EP0429535A1/en not_active Withdrawn
  • 1989-08-15 KR KR1019900700770A patent/KR900701774A/ko not_active Application Discontinuation
  • 1989-08-15 AU AU42025/89A patent/AU4202589A/en not_active Abandoned
  • 1989-08-15 EP EP89308246A patent/EP0359400A1/en not_active Withdrawn
  • 1989-08-15 WO PCT/US1989/003436 patent/WO1990002122A1/en not_active Application Discontinuation
  • 1989-08-15 JP JP1509540A patent/JPH04500075A/ja active Pending
  • 1989-08-16 CN CN89106494A patent/CN1040371A/zh active Pending
  • 1989-08-16 ZA ZA896254A patent/ZA896254B/xx unknown

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