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WO1992010501A1 - Ethers herbicides - Google Patents

Ethers herbicides Download PDF

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Publication number
WO1992010501A1
WO1992010501A1 PCT/US1991/009059 US9109059W WO9210501A1 WO 1992010501 A1 WO1992010501 A1 WO 1992010501A1 US 9109059 W US9109059 W US 9109059W WO 9210501 A1 WO9210501 A1 WO 9210501A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
compound
growth
effective amount
controlling
Prior art date
Application number
PCT/US1991/009059
Other languages
English (en)
Inventor
Onorato Campopiano
Original Assignee
E.I. Du Pont De Nemours And Company
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
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1992010501A1 publication Critical patent/WO1992010501A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • 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
    • A01N43/04—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 one hetero atom
    • A01N43/14—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 one hetero atom six-membered rings
    • A01N43/16—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 one hetero atom six-membered rings with oxygen as the ring hetero atom
    • 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

Definitions

  • This invention relates to certain herbicidal ethers, agriculturally suitable compositions thereof, and a method for their use as broad spectrum preemergent or postemergent herbicides.
  • New compounds effective for controlling the growth of undesired vegetation are in constant demand.
  • such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few.
  • Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer.
  • herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial storage areas.
  • R 3 is hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms; a cyano group; an alkyl group substituted by: a hydroxy group, a cyano group, an alkoxy group containing from 1 to 6 carbon atoms, a C 1-6 alkylsulfonyl group, a C 6-10 arylsulfonyl group, a C 7-11 aralkysulfonyl group, an azido group, a C 1-6 alkoxycarbonyl group, a hydroxycarbonyl group, a dialkoxyphosphonge[sic] group or an amine oxide, carbamoyl or
  • R 3 is an alkenyl or alkynyl group containing 2 to 4 carbon atoms; an aryl or aralkyl group, each containing from 6 to 11 carbon atoms including 1 to 4 carbon atoms in the alkyl portion and optionally ring substituted by halogen or by an alkyl or alkoxy group containing from 1 to 2 carbon atoms, each optionally substituted by one or more halogen atoms, or R 3 is a group-CO 2 R 8 ; -CON(R 8 ) 2 , or -CSNH 2 in which R 3 is a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms; or R 3 is an acyl group containing 1 to 6 carbon atoms or an oxime or an acetal derivative of said acyl group.
  • This invention comprises compounds of Formulas I, II, III, IV and V including stereoisomers, agriculturally suitable compositions containing them, and their
  • X 1 is OR 9 , CO 2 R 11 , C(O)R 11 , CHO, C(O)NR 12 R 13 , SH,
  • Y is OR 18 , CO 2 R 19 , C(O)R 19 , CHO, C(O)NR 20 R 21 , SH,
  • R 1 is H or a straight chain C 1 -C 3 alkyl
  • R 2 and R 4 are independently H, C 1 -C 3 alkyl
  • R 3 and R 5 are independently H or C 1 -C 3 alkyl
  • R 2 and R 3 may be taken together to form a 3- to
  • R 4 and R 5 may be taken together to form a 3- to
  • R 6 is H or C 1 -C 4 alkyl
  • R 7 and R 8 are independently H, C 1 -C 4 alkyl
  • R 9 and R 18 are independently H, C 1 -C 6 alkyl
  • R 10 is C 1 -C 4 alkyl optionally substituted with
  • R 11 and R 19 are independently C 1 -C 4 alkyl optionally substituted with C1-C2 alkoxy, C 1 -C 2 alkylthio, halogen or NR 12 R 13 ; C 3 -C 4 alkenyl; C 3 -C 4 alkynyl; CH 2 -cyclopropyl; or cyclobutyl;
  • R 12 and R 13 are independently H, C 1 -C 3 alkyl or may be taken together to form a 4- to 6-mem-bered ring;
  • R 20 and R 21 are independently H, C 1 -C 3 alkyl or may be taken together to form a 4- to 6-mem-bered ring;
  • R 14 and R 25 are independently H, C 1 -C 3 alkyl or
  • R 15 and R 22 are independently C 1 -C 4 alkyl; R 16 , R 17 , R 24 and R 29 are independently C 1 -C 3 alkyl; R 23 is C 1 -C 3 alkyl, C(O)(C 1 -C 2 alkyl), SO 2 ⁇ C 1 -C 2
  • R 26 is H, halogen, C 1 -C 3 alkyl, OR 27 , SR 27 or CN; R 27 is C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
  • Z is CH 2 , NR 28 , O, S or may be CH and taken to form a double bond with an adjacent carbon;
  • R 28 is H or C 1 -C 3 alkyl
  • q 0, 1 or 2;
  • r 0, 1 or 2;
  • W is phenyl optionally substituted with 1-3
  • W is 5-, 6- or 7-membered heterocyclic ring containing one or more
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.
  • Alkoxy includes methoxy, ethoxy,
  • Alkenyl includes straight chain or branched alkenes, e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers.
  • Alkylthio, etc. are used analogously to the above examples.
  • halogen either alone or in compound words such as "haloalkyl”, means 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.
  • haloalkyl examples include CH 2 CH 2 F, CF 2 CF 3 and
  • heterocycles includes but is not limited to pyrrole, furan, thiophene, tetrahydrofuran, tetrahydropyran, isoxazole, oxazole, pyrazole, imidazole, thiazole,
  • W is phenyl, tetrahydropyran, tetrahydrofuran,
  • thiophene isoxazole, pyridine or pyrazine, each ring optionally substituted with 1-2 substituents selected from halogen, CH 3 and OCH 3 ;
  • X 1 is OR 9 , CO 2 R 11 , C(O)R 11 , CHO, C(O)NR 12 R 13 , SH,
  • R 9 is H, C 1 -C 3 alkyl, allyl, propargyl or SO2CH3;
  • R 11 is C 1 -C 3 alkyl or allyl;
  • R 12 is H or CH 3 ;
  • R 13 is CH 3 ;
  • R 18 is H, C 1 -C 3 alkyl, allyl, propargyl or SO 2 (C 1 -C 3 alkyl);
  • R 22 is C 1 -C 2 alkyl
  • R 29 is CH 3 ;
  • R 1 is C 1 -C 2 alkyl
  • R 2 and R 4 are independently H, F, Cl, C 1 -C 2 alkyl or
  • R 3 and R 5 are independently H or C 1 -C 2 alkyl
  • R 6 is H or C 1 -C 2 alkyl
  • R 7 and R 8 are independently H or C 1 -C 2 alkyl.
  • W is phenyl optionally substituted by 1-2
  • X 1 and X 2 are independently CO 2 (C 1 -C 3 alkyl),
  • Y is O(C 1 -C 2 alkyl), OSO 2 CH 3 or O-propargyl;
  • R 2 and R 4 are indepedently H, Cl or CH3;
  • X 1 is OR 9 or CR 4 R 5 Y;
  • R 9 is allyl, propargyl or SO 2 CH 3 ;
  • R 18 is allyl, propargyl or SO 2 (C 1 -C 3 alkyl);
  • R 19 is C 1 -C 4 alkyl substituted with C 1 -C 2 alkoxy, C 1 -C 2 alkylthio, halogen or NR 12 R 13 ; C 3 -C 4 alkenyl; C 3 -C 4 alkynyl; CH2 ⁇ cyclopropyl; or cyclobutyl;
  • R 22 is C 1 -C 2 alkyl
  • R 29 is CH 3 ;
  • R 1 is C 1 -C 2 alkyl
  • R 2 and R 4 are independently H, Cl, C 1 -C 2 alkyl or OCH 3 ;
  • R 3 and R 5 are independently H or C 1 -C 2 alkyl
  • R 6 is H or C 1 -C 2 alkyl
  • R 7 and R 8 are independently H or C 1 -C 3 alkyl.
  • W is phenyl optionally substituted by 1-2
  • X 1 and X 2 are CR 4 R 5 Y;
  • Y is OR 18 ;
  • R 2 and R 4 are indepedently H, Cl or CH 3 ;
  • R 3 and R 5 are independently H or CH 3 ;
  • R 18 is propargyl or SO 2 CH 3 .
  • compositions of the invention are also suitable for controlling the growth of undesired vegetation.
  • Such compositions comprise an effective amount of any of the compounds disclosed herein and at least one of the following: surfactant, solid, or liquid diluent.
  • Methods for controlling the growth of undesired vegetation by using the compounds of compositions of the invention are similarly considered to be within the scope of the invention. These methods comprise applying to the locus to be protected an effective amount of any of the compounds disclosed herein. Of particular importance is the method wherein the locus to be protected is rice.
  • the compounds of the invention are prepared by treating the appropriately substituted oxabicycloalkanol (Ia-Va or I-V wherein Q is H) with a compound of the formula WCH 2 X in which X is a halogen atom or a mesyloxy, tosyloxy group or the like.
  • This reaction is carried out, as shown in Scheme 1, in the presence of a strong base, such as an alkali metal hydride or an alkali metal alkoxide, in an inert solvent, such as ethers, aromatic hydrocarbons, dimethylformamide and the like.
  • a strong base such as an alkali metal hydride or an alkali metal alkoxide
  • an inert solvent such as ethers, aromatic hydrocarbons, dimethylformamide and the like.
  • Suitable temperatures for the reaction are preferably from -10°C to 100°C.
  • the product ethers are recovered and isolated by conventional techniques.
  • the alcohols, WCH 2 OH are generally known in the art and are most conveniently prepared through metal hydride (e.g., sodium borohydride) reduction of the corresponding ketones which can be derived by Friedel-Crafts type cyclization of derivatives of phenylalkyl-carboxylic acid, phenoxyalkylcarboxylic acids,
  • metal hydride e.g., sodium borohydride
  • the compounds of Formulas I-V may be prepared by the coupling procedure described in Scheme 2, which is used in cases where the standard Williamson ether synthesis proves problematic.
  • This procedure uses a Lewis acidic metal oxide wherein the metal can remove the halide ion by forming an insoluble precipitate.
  • silver (I) oxide can be used and the silver halide is the co-product.
  • Alternative metal oxides that may be used are HgO, CaO, MgO. N,N-Dimethylformamide and ethereal solvents, such as diethyl ether,
  • tetrahydrofuran, dioxane, or 1,2-dimethoxyethane are the preferred solvents.
  • Other solvents likely to provide good yields include dipolar aprotic solvents such as dimethyl sulfoxide, acetone and N,N'-dimethylpropylene- urea.
  • the oxabicycloalkanols (Ia-Va) can be obtained generally by epoxidation-cyclization of unsaturated cyclic alcohols, with or without isolation of the epoxy alcohol intermediates.
  • the compounds of Formula la are synthesized through the sequence shown in Scheme 3, which begins with the Birch reduction of the appropriate aromatic substrate which provides the non-conjugated ketone (1) after mild acidic hydrolysis (see H. L. Dryden et al., J. Org.
  • ⁇ 1 SO 2 NR 12 R 13 or SO 2 N(OCH 3 )(CH 3 ), etc.) could be possible to finally generate the desired product of Formula I in subsequent steps.
  • aldoxime or ketoxime may be synthesized from the aldehyde or ketone respectively using a variety of standard oximation procedures .
  • the alkyl metal reagent thus generated may be quenched with a wide variety of electrophiles according to well known
  • oxabicyclic alcohols of Formula Ila can be synthesized via the synthetic sequence shown beginning with Scheme 4. Diels-Alder cycloaddition of a
  • This epoxide is opened with aqueous acid followed by a selective protection of the primary alcohol with a group such as trialkylsilyl (in the example below) or an ester group (see Greene, T., Protective Groups in Organic
  • the olefin is then oxidized to the epoxide with a peracid such as peracetic or m-chloroperoxybenzoic acid (L. A. Paquette, Org. Syn., (1969), Vol. 49, 62).
  • a peracid such as peracetic or m-chloroperoxybenzoic acid (L. A. Paquette, Org. Syn., (1969), Vol. 49, 62).
  • the epoxide may be isolated or it may be allowed to react further so that the closed ring system II is formed.
  • one route to this end is to oxidize Ila (anti) to the ketone (5a) by a variety of methods such as that of Swern (Swern, D., Synthesis, (1981), 165) or Jones (see Bruce, W. F., Org. Synthesis, Coll. Vol. II, 139) followed by selective reduction with a reducing agent such as sodium
  • (3b) may be elaborated through identical steps to compounds of Formula IV.
  • oxabicyclic alcohols of Formula IIIa can be synthesized via the synthetic sequence shown beginning with Scheme 5. Diels-Alder cycloaddition of acrylic acid with the appropriate diene gives a mixture of 2
  • (6a) is useful to generate compounds of Formula III, while (6b) is useful for similar elaboration to form compounds of Formula V.
  • the acid (6a) is esterified and then treated at low temperature with lithium diisopropylamide followed by addition with an aldehyde or ketone to form an unsaturated aldol.
  • the olefin is then oxidized to the epoxide with a peracid such as peracetic or m-chloroperoxybenzoic acid (Paquette, L.A., Org. Syn., (1969), Vol. 49, 62).
  • the epoxide may be isolated or it may be allowed to react further so that the closed ring system IIIa is formed.
  • This ester may then be reduced and capped with a variety of capping reagents to provide III
  • (6b) may be elaborated through identical steps to compounds of Formula V as shown in Scheme 6.
  • thermometer sidearm was fitted with a coldfinger
  • thermometer thermometer
  • Claisen adapter The whole apparatus was dried under a nitrogen stream while heating with a heat gun. The apparatus was allowed to cool under a nitrogen stream. Once at room temperature, a nitrogen line connected to a bubbler was connected to the bent neck of the Claisen head, the remaining straight neck being topped by a stopper. The apparatus was lowered into a -35°C bath (isopropanol precooled with dry ice) and maintained at that temperature either by periodic addition of dry ice to the bath or by use of a Cryocool cooling unit set at that temperature. The cold finger condenser was then charged with dry ice acetone and the NH3 (200 mL) was condensed into the flask to a preset mark. The stopper on the Claisen head was then replaced with an addition funnel charged with 30.0 g of
  • the mixture was filtered and the filtrate was poured into a separatory funnel, the lower aqueous layer was drawn off and washed once with ether.
  • the combined organic phases were concentrated to about 500 mL. At this point a solution of 3.3 g oxalic acid dihydrate in 75 mL of water was added and the mixture was stirred overnight (alternatively one may use 20 mL of 1N HCl with a stirring time of 6 hours).
  • the mixture was poured into a separatory funnel and then separated; the aqueous layer was washed once with ether.
  • thermometer sidearm and magnetic stir bar A 1-L one-neck flask with thermometer sidearm and magnetic stir bar was heated with a heat gun and allowed to cool, all under a nitrogen stream. A thermometer was fitted into the sidearm, and the neck was topped with a septum. A needle connected to a nitrogen bubbler was punched through the septum as a vent. The flask was charged with 330 mL of dry THF, followed by 14.7 mL of diisopropylamine. The flask was cooled to -10°C
  • Ethylenediaminetetraacetic acid EDTA
  • saturated aqueous NaCl saturated aqueous NaCl.
  • the combined organic layers were dried over anhydrous Na2S ⁇ 4, filtered, concentrated, and
  • Methyl exo-4-ethyl- ⁇ , ⁇ -dimethyl-3-hydroxy-7-oxabicyclo[2.2.1]heptane-l-acetate (1.0 g) and 2-fluorobenzyl bromide were dissolved in 4 mL THF and 4 mL dimethylacetamide. A magnetic stirring bar was added and the mixture was cooled under nitrogen to -10°C.
  • IR (neat) 2970, 2860, 1455, 1380, 1350, 1110, 1060,
  • Exo-1-ethyl-4-(2-hydroxy-1,1-dimethylethyl)-2- (phenylmethoxy)-7-oxabicyclo[2.2.1]heptane (0.1 g) was dissolved in 1.5 mL of dichloromethane under nitrogen. The solution was cooled to 0°C. Triethylamine (0.07 mL) was added followed by methanesulfonyl chloride (0.03 mL). The mixture was stirred for 1 hour at 0°C. Then ice was added and the mixture was extracted with ether. The layers were separated, the aqueous was washed again with ether. The combined organic layers were dried over
  • Methyl exo-4-ethyl- ⁇ -methyl-3- hydroxy-7-oxabicyclo[2.2.1]heptane-1-acetate Methyl 4-ethyl- ⁇ -methyl-1-hydroxy-cyclohex-3-ene-1- acetate (5.15g) was dissolved in 100 mL dry CH 2 CI 2 under N 2 . Vanadylacetylacetonate (320 mg) was added and stirred 10 minutes. The solution was cooled to -10°C. To this stirred solution was added dropwise a solution made by dissolving 3.23 mL of 90% t-butyl hydroperoxide into 15 mL of CH 2 CI 2 and drying the solution over 3 ⁇ molecular sieves.
  • Methyl exo-4-ethyl- ⁇ -methyl-3-hydroxy-7-oxabicyclo[2.2.1]heptane-1-acetate (1.1 g) was dissolved in 5 mL CH 2 CI 2 and 15 mL hexane. Added a small scoop of 3A molecular sieves. Added 2.7 g of benzyl 2,2,2- trichloroacetimidate. A stock solution of BF 3 ⁇ Et 2 O in CH 2 CI 2 was made by dissolving 0.09 mL of BF 3 ⁇ Et 2 O in 0.91 mL of CH 2 CI 2 . Ten drops of this solution were added every hour for 5 hrs.
  • Exo-1-ethyl-4-(2-hydroxy-1,1-dimethylbutyl)-2- (phenylmethpxy)-7-oxabicyclo[2.2.1]heptane Exo-4-ethyl- ⁇ - ⁇ -dimethyl-3-(phenylmethoxy)-7- oxabicyclo[2.2.1]heptane-1-al was dissolved in 4.5 diethylether under N 2 . This was cooled to -10°C.
  • Exo-1-ethyl-4-(2-hydroxy-lyl-dimethylbutyl)-2- (phenylmethoxy)-7-oxabicyclo[2.2.1]heptane 150 mg was dissolved in a mixture of 0.5 mL each of THF and
  • Methyl exo-4-ethyl- ⁇ - ⁇ -dimethyl-3-hydroxy-7-oxabicyclo[2.2.1]heptane-1-acetate (500 mg) was dissolved in 10 mL n-propanol. 160 mg of sodium hydride (60% dispersion in oil) was added and the contents were heated at reflux for 4 hrs. Reaction was allowed to cool and then stirred overnight. Added saturated aqueous NH 4 CI, extracted with ether, dried organics over Na 2 SO 4 ,
  • IR (neat, cm -1 ): 2900, 1720, 1450, 1280, 1150-1110-1060, 750.
  • Methyl-exo-4-ethyl- ⁇ - ⁇ -dimethyl-3-hydroxy-7- oxabicyclo[2.2.1]heptane-1-acetate 500 mg was dissolved in 5 mL of allyl alcohol. To this was added sodium hydride (160 mg of a 60% dispersion in oil). The
  • reaction was heated at reflux under N 2 for 1 hr, then allowed to cool down to room temperature. Quenched with saturated aqueous NH 4 CI (about 2 mL). Removed some of the allyl alcohol. Diluted with water and extracted mixture twice with ether. Combined organics were washed with saturated NaCl, dried over Na 2 SO 4 , filtered, concentrated, chromatographed on SiO 2 to get 240 mg of desired alcohol as an oil.
  • Methyl-exo-4-ethyl- ⁇ - ⁇ -dimethyl-3-hydroxy-7-oxabicyclo[2.2.1]heptane-1-acetate (1.5 g) was dissolved in 15 mL ethanol. Contents were cooled to about 10°C.
  • Exo-1-ethyl-4-(2-hydroxy-1,1-dimethyl)-2-(2-fluorophenylmethoxy)-7-oxabicyclo[2.2.1]heptane 150 mg was dissolved in 0.5 mL each of THF and dimethylacetamide.
  • Methyl exo-4-ethyl- ⁇ -chloro- ⁇ -methyl-3-hydroxy-7-oxabicyclo[2.2.1]heptane-1-acetate (700 mg) was dissolved in 2.66 mL each of THF and dimethylacetamide. 2-Fluoro- benzylbromide (0.64 mL) was added and the reaction was cooled to. Potassium t-butoxide (600 mg) was added and the reaction was slowly allowed to warm to room
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of 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
  • 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 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • solution concentrates are preferably stable against phase separation at 0°C.
  • 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
  • Example B The active ingredient is first sprayed onto the amorphous silica, then the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
  • Example B The active ingredient is first sprayed onto the amorphous silica, then the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
  • Example D A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules aredried and packaged.
  • Example D A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules aredried and packaged.
  • Atlox 3403F and 3404F are blends of anionic and ionic
  • 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 solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
  • Example G The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packagedfor use.
  • Example G Example G
  • the active ingredient, solvent and emulsifiers are blended together. This solution is added to a mixture of the ethylene glycol and water with stirring.
  • the compound is added directly to the water with stirring to produce the solution, which may then be packaged for use.
  • Grass and broadleaf weed species controlled include, but are not limited to, barnyardgrass (Echinochloa crus-galli), blackgrass
  • difformis Several compounds in this invention are particularly useful for the control of barnyardgrass and selected broadleaf weeds such as duck salad and umbrella sedge in upland and paddy rice.
  • the aforesaid compounds also have utility for weed control of selected vegetation in specified areas such as around storage tanks, parking lots, highways, and
  • plantation crops such as banana, coffee, oil palm, and rubber.
  • said compounds are useful to modify plant growth.
  • a herbicidally effective amount of the compounds of this invention is determined by a number of factors.
  • herbicidally effective amount of the subject compounds is applied at rates from 0.01 to 20 kg/ha with a preferred rate range of 0.03 to 1 kg/ha. Although a small number of compounds show no herbicidal activity at the rates tested, it is anticipated these compounds are
  • herbicidally active at higher application rates One skilled in the art can easily determine application rates necessary for the herbicidally effective amount that will achieve the desired level of weed control.
  • CDAA 2-chloro-N,N-di-2-propenylacetamide
  • CDEC 2-chloroallyl diethyldithiocarbamate chlomethoxyfen 4-(2,4-dichlorophenoxy)-2-methoxy-1- nitrobenzene
  • paraquat 1,1'-dimethy1-4,4'-dipyridinium ion pebulate S-propyl butylethylcarbamothioate pendimethalin N-(1-ethyIpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine
  • prodiamine 2,4-dinitro-N 3 ,N 3 -dipropyl- 6-(trifluoromethyl)-1,3-benzenediamine
  • prosulfocarb S-benzyldipropylthiocarbamate prynachlor 2-chloro-N-(1-methyl-2-propynyl)- acetanilide
  • Plant response ratings summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
  • Plant species in the preemergence and postemergence tests consisted of barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium
  • pensylvanicum corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Diyitaria san ⁇ minalis), downy brome (Bromus tectorum), duck salad (Heteranthera limosa), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), johnsongrass (Sorghum halepense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweedweed
  • Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test.
  • Plant species in the paddy test consisted of barnyardgrass (Echinochloa crus-galli), rice (Oryza sativa), and umbrella sedge (Cyperus difformis).
  • Plastic pots were partially filled with silt loam soil. The soil was then flooded with water, Japonica rice (Oryza sativa) sprouted seeds and 1.5 leaf transplants were planted in the soil. Seeds of barnyardgrass
  • plantings was raised to 2 cm above the soil surface.
  • Plastic pots were partially filled with silt loam soil. The soil was then saturated with water.
  • Indica and Japonica rice (Qryza sativa) seedlings at the 2.0 to 2.5 leaf stage, seeds selected from barnyardgrass
  • Pots receiving these preemergence treatments were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and untreated controls were maintained in the greenhouse approximately 21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table E, are reported on a 0 to 10 scale where 0 is no effect and 10 is complete control.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne certains éthers herbicides des formules I à V, leurs compositions adaptées à l'agriculture, et leur procédé d'utilisation comme herbicides de pré-émergence ou de post-émergence à large spectre.
PCT/US1991/009059 1990-12-10 1991-12-10 Ethers herbicides WO1992010501A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62513390A 1990-12-10 1990-12-10
US625,133 1990-12-10

Publications (1)

Publication Number Publication Date
WO1992010501A1 true WO1992010501A1 (fr) 1992-06-25

Family

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Application Number Title Priority Date Filing Date
PCT/US1991/009059 WO1992010501A1 (fr) 1990-12-10 1991-12-10 Ethers herbicides

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AU (1) AU9117491A (fr)
WO (1) WO1992010501A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024099118A1 (fr) * 2022-11-09 2024-05-16 青岛清原化合物有限公司 Composés oxabicycloalcane, leur procédé de préparation, composition herbicide et utilisation associée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116634861A (zh) * 2020-09-09 2023-08-22 联邦科学和工业研究组织 秆锈病抗性基因

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0081893A2 (fr) * 1981-12-16 1983-06-22 Shell Internationale Researchmaatschappij B.V. Herbicides oxabicycloalquiniques
EP0308170A1 (fr) * 1987-09-15 1989-03-22 E.I. Du Pont De Nemours And Company Oxabicycloalcanes sélectifs
WO1989011481A1 (fr) * 1988-05-23 1989-11-30 E.I. Du Pont De Nemours And Company Ethers d'oxabicycloalkane herbicides
WO1990010634A1 (fr) * 1989-03-14 1990-09-20 E.I. Du Pont De Nemours And Company Oxabicycloalcanes selectifs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0081893A2 (fr) * 1981-12-16 1983-06-22 Shell Internationale Researchmaatschappij B.V. Herbicides oxabicycloalquiniques
EP0308170A1 (fr) * 1987-09-15 1989-03-22 E.I. Du Pont De Nemours And Company Oxabicycloalcanes sélectifs
WO1989011481A1 (fr) * 1988-05-23 1989-11-30 E.I. Du Pont De Nemours And Company Ethers d'oxabicycloalkane herbicides
WO1990010634A1 (fr) * 1989-03-14 1990-09-20 E.I. Du Pont De Nemours And Company Oxabicycloalcanes selectifs

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024099118A1 (fr) * 2022-11-09 2024-05-16 青岛清原化合物有限公司 Composés oxabicycloalcane, leur procédé de préparation, composition herbicide et utilisation associée

Also Published As

Publication number Publication date
AU9117491A (en) 1992-07-08

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