WO1997018196A1 - Composes herbicides a base de pyrazole substitue - Google Patents

Composes herbicides a base de pyrazole substitue Download PDF

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Publication number
WO1997018196A1
WO1997018196A1 PCT/GB1996/002783 GB9602783W WO9718196A1 WO 1997018196 A1 WO1997018196 A1 WO 1997018196A1 GB 9602783 W GB9602783 W GB 9602783W WO 9718196 A1 WO9718196 A1 WO 9718196A1
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WIPO (PCT)
Prior art keywords
optionally substituted
alkyl
hydrogen
haloalkyl
alkoxy
Prior art date
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PCT/GB1996/002783
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English (en)
Inventor
Christopher John Mathews
Don Robert Baker
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Zeneca Limited
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Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to EP96938339A priority Critical patent/EP0863879A1/fr
Priority to AU75796/96A priority patent/AU7579696A/en
Priority to JP9518671A priority patent/JP2000500448A/ja
Publication of WO1997018196A1 publication Critical patent/WO1997018196A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl

Definitions

  • this invention relates to novel substituted pyrazole compounds and de ⁇ vatives thereof which exhibit unexpectedly desirable herbicidal activity
  • this invention relates to herbicidal compositions containing a substituted pyrazole compound or derivative thereof and an agriculturally acceptable earner and to a method of controlling undesirable vegetation by applying to an area where control is desired an herbicidally effective amount of a substituted pyrazole compound or derivative thereof
  • this invention is directed to compounds of formula (I)
  • R 1 is optionally substituted C C 6 alkyl or d-C 6 haloalkyl
  • R 2 is optionally substituted d- ⁇ alkyl, C ⁇ -C 6 haloalkyl or d-C 6 cycloalkyl,
  • R ' is hydrogen, halogen, Ci-C ⁇ alkyl or C ⁇ -C ⁇ haloalkyl
  • R 4 is optionally substituted Ci-C ⁇ alkyl, C ⁇ -C 6 haloalkyl, optionally substituted C ⁇ -C 6 alkoxy, optionally substituted d-C 6 cycloalkyl, optionally substituted (C ⁇ -C6)alkoxy(d- C6)alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, or an optionally substituted five or six membered heterocvclic ring containing one or more heteroatoms selected from O, N or S,
  • R 5 is hydrogen, optionally substituted Ci-C ⁇ alkyl or (C ⁇ -C 6 )alkoxy-(C ⁇ -C6)alkyl,
  • R°, R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, optionally substituted C ⁇ -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C ⁇ alkynyl, optionally substituted C ⁇ -C 6 alkoxy, (C ⁇ -C 6 )alkoxy-(C ⁇ -C6)alkyl, C C 6 haloalkyl, Ci-C ⁇ haloalkoxy, cyano, nitro, -S(O) p -R wherein p is 0, 1 or 2 and R 10 is C C 3 alkyl or d-C haloalkyl, -OSO 2 R ⁇ wherein R 11 i 12 IS C,-C, alkyl, -CO 2 H, -COR 12 , -COOR 12 or -NHCOR 1 wherein R 12 is C C 6 alkyl, C ⁇ -C 6 haloalkyl, optionally substituted C ⁇ -C 6
  • Y is O or S
  • this invention is directed to an herbicidal composition containing (A) a compound of formula (la)
  • this invention is directed to a method for controlling undesirable vegetation by applying to an area where such vegetation control is desired an herbicidally effective amount of a compound of formula (la) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A, Y and Z have the same meanings as above, or an agnculturally acceptable salt thereof
  • novel herbicidal compounds of this invention are of the formula (I)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A, Y and X have the same meanings as above, and agriculturally acceptable salts thereof
  • R 1 is Ci-d, alkyl or Ci-C haloalkyl
  • R 2 is C1-C3 alkyl or C 1 -C3 haloalkyl
  • R J is hydrogen
  • R 5 is hydrogen
  • Particularly preferred compounds include N-[4-Methyl-2-[l-methyl-3- (t ⁇ fluoromethyl)-l H-pyrazol-5-yl]oxyphenyl]cyclopropane carboxamide, N-[4-Methyl-2- [ l-methyl-3-(trifluoromethyl)-lH-pyrazol-5-yl]oxyphenyl]isopropane carboxamide and N- [4-Methyl-2-[ l -methyl-3-(trifluoromethyl)-lH-pyrazol-5-yl]oxyphenyl]ethane carboxamide
  • this invention is directed to a herbicidal composition containing (A) a compound of formula (la) wherein R 1 , R 2 , R R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A, Y and Z have the same meanings as above, or an agriculturally acceptable salt thereof; and
  • this invention is directed to a method for controlling undesirable vegetation by applying to an area where such vegetation control is desired an herbicidally effective amount of a compound of formula (la).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A, Y and Z have the same meanings as above, or an agriculturally acceptable salt thereof
  • substituted is intended to mean that the " substituted" group has one or more of the following substituents: halogen (i.e., fluorine, chlorine, bromine and iodine), C1-C4 alkyl, C 1 -C4 alkylthio, C1-C4 alkoxy; (C ⁇ -C 4 )alkoxy- (C ⁇ -C»)alkyl, (Ci-d alkoxyCO-, C ⁇ -C 4 alkyl-S(O) p -, nitro, nit ⁇ le, cyano, carboxy and salts, amides and esters thereof, alkanoyl of 2 to 4 carbon atoms, amino optionally substituted with one or two C1-C4 alkyl, phenyl optionally substituted with one or more C 1 -C 4 alkyl, C1-C4 alkoxy, C ⁇ -C 4 alkyl-S(O) p -, nitro, halogen (i.e., fluorine,
  • aryl is intended to include aryl groups, such as phenyl, which are unsubstituted or are substituted with one or more of the foregoing substituents
  • heteroaryl is intended to include heteroaryl groups, such as pyndyl, py ⁇ midyl, t ⁇ azmyl, th enyl, furyl and thiazolyl, which are unsubstituted or are substituted with one or more of the substituents listed above
  • salts, amides and esters thereof used above in relation to carboxy substitution includes, for example, salts formed from alkali metals (e g , sodium, potassium and lithium), alkaline earth metais (e g , calcium and magnesium), the ammonium ion and substituted ammonium ions wherein one, two, three or four of the hydrogen atoms have been replaced by optionally substituted C ⁇ -C 6 hydrocarbyl moieties as defined above
  • the carboxy substitution includes esters and amides which mav be formed from the carboxy group and an optionally substituted C ⁇ -C 6 hvdrocarbyl moiety in the case of the ester, or an optionally substituted Ci-d- hydrocarbyl amine in the case of the amide
  • halogen ' includes fluoro, chloro, bro o and lodo groups
  • the halogens may be the same or different
  • the compounds of the present invention have been found to be active herbicides, possessing utility as pre-emergence and post-emergence herbicides These compounds are useful against a wide range of plant species including broadleaf, grassy and perennial species
  • the compounds of this invention have also been found to be pa ⁇ icularly effective in controlling undesirable vegetation typically found in rice crops
  • the terms "herbicide” and “herbicidal” are used herein to denote the inhibitive control or modification of undesired plant growth.
  • Inhibitive control and modification include all deviations from natural development, such as, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing
  • the term "herbicidally effective amount” is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing.
  • plants is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.
  • agriculturally acceptable salt is easily determined by one of ordinary skill in the art and includes hydrohalide, acetic, sulfonic, phosphonic, inorganic and organic acid salts.
  • the compounds of this invention may be prepared by treatment of an amine (II) with an acid chloride, acid anhydride, chlorothio formate, chlorofoimate or similar reagent in the presence of a suitable base and in a suitable solvent, according to the procedures described, for example, in J. March, Advanced Organic Chemistry, third edition, pp.
  • amines (II) are believed to be novel and are to be considered as yet another aspect of the present invention
  • amine (II) may be treated sequentially with phosgene, or a phosgene equivalent, and an appropriate alcohol or thiol to generate (la) wherein R 5 is hydrogen
  • phosgene or a phosgene equivalent
  • la wherein R 5 is hydrogen
  • the amine (II) may be prepared by reduction of the corresponding nitro compound (III), such reductions are widely desc ⁇ bed in the literature Those skilled in the art will know that the reduction may be earned out using a vanety of reducing agents such as hydrogen in the presence of a catalyst, sodium borohyd ⁇ de in the presence of a palladium catalyst, a sulfide or a metal such as iron in the presence of an acid, the particular method of choice will depend on.
  • reducing agents such as hydrogen in the presence of a catalyst, sodium borohyd ⁇ de in the presence of a palladium catalyst, a sulfide or a metal such as iron in the presence of an acid
  • the nitrobenzene of formula (III) may be prepared by reacting a compound of type (IV), where Hal is haiogen such as fluo ⁇ ne or chlo ⁇ ne, with a hydroxypyrazole (V)
  • the reaction is preferably earned out in an organic solvent such as N,N-d ⁇ methylformam ⁇ de, dimethylsuifoxide, acetonitnie, a lower alcohol or a lower alkyl ketone and in the presence of a suitable base such as an alkali metal carbonate, hydroxide or alkoxide Moderate temperatures, for example from 0° to 100°C are suitably employed [SCHEME 3]
  • Hydroxypyrazoles of the type (V) can be made by methods known in the art Hydroxypyrazoies of the type (V), wherein R J is halogen, may be made, for example by reaction of an unsubstituted pyrazole R J is H) with a halogenating agent such as sulfuryl chlo ⁇ de or N-bromosuccinimide in a suitable solvent
  • a halogenating agent such as sulfuryl chlo ⁇ de or N-bromosuccinimide
  • Compounds of the type (V), (R 3 is hydrogen or alkyl) may be prepared by treatment of an approp ⁇ ate ⁇ -ketoester ( VT) with an alkylhydrazine in a suitable solvent, as desc ⁇ bed, for example by DeStevens et al , JACS, 81. 6292, (1959) [SCHEME 4]
  • the compounds of the present invention are useful as herbicides and can be applied in a vanety of ways known to those skilled in the art, at vanous concentrations
  • the compounds are useful in controlling the growth of undesirable vegetation by pre-emergent or post-emergent application to the locus where control is desired
  • the compositions of this invention comp ⁇ se a compound of formula (la) above and a suitable earner, which earners are well known to one of ordinary skill in the art
  • the compounds are applied as formulations containing the vanous adjuvants and carriers known to or used in the industry for facilitating dispersion
  • the choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly
  • the compounds of the invention may thus be formulated as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as microcapsules
  • These formulations may contain as little as about 0 5% to as much as about 95% or more by weight of active ingredient
  • the optimum amount for any given compound will depend upon the nature of plants to be controlled.
  • the rate of application will generally vary from about 0.01 to about 1 1.5 kilograms per hectare, preferably from about 0.02 to about 4.5 kilograms per hectare.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin days, silicas and other readily wettable organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xyiene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or solutions of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surrounds at controlled rates.
  • Encapsulated droplets are typically about 1 to 50 microns in diameter.
  • the enclosed material typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound.
  • Shell of membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xyiene and other organic solvents.
  • Pressurized sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier may also be used.
  • formulations include wetting, dispersing or emulsifying agents.
  • examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.
  • Each of the above formulations can be prepared as a package containing the herbicide together with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc .).
  • the formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
  • the compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provide a higher level of effectiveness in controlling weeds and often provide results unattainable with separate formulations of the individual herbicides.
  • B. hormone herbicides particularly the phenoxyalkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D,2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
  • pyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
  • D. dinitrophenols and their derivatives e.g. acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
  • F. aryiurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron;
  • G. phenyicarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
  • uracil herbicides such as lenacil, bro acil and termacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
  • K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepiperate;
  • M l,2,4-triazin-5-one herbicides such as metamitron and metribuzin
  • N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
  • O. anilide herbicides such as pretilachlor, butachlor, the corresponding aiachlor, the corresponding compound propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor;
  • P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
  • haloalkanoic herbicides such as dalapon, TCA and salts thereof;
  • diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
  • S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
  • T. triketone and cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, suicotrione, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfiiron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazathapyr;
  • W arylanilide herbicides such as flamprop and esters thereof, benzoylprop- ethyl, diflufenican,
  • X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos,
  • Y. organoarsenical herbicides such as MSMA
  • herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac and mefanacet; and
  • CC. contact herbicides examples of which include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat
  • Dust and liquid compositions for example, can be applied by the use of powerdusters, boom and hand sprayers and spray dusters
  • the formulations can also be applied from airplanes as a dust or a spray or by rope wick applications
  • Wettable powders 70% 70 parts active compound 5 parts sodium dibutylnaphthylsulfonate
  • wettable powders are prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
  • Emulsifiable concentrate is a liquid crystal
  • compositions which constitute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled.
  • the rate of application of active ingredients varies from about 0.01 to about 28 kilograms per hectare, preferably about 0.02 to about 1 1 kilograms per hectare with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.
  • Raney Nickel (ca 0 5 g) was added to a solution of the compound prepared in A above
  • Raney Nickel (ca 0 08g) was added to a solution of the compound prepared in B above (0 8 g , 2 5 mmol) in methanol (50 ml) and the mixture shaken m a Parr hydrogenator at 50
  • a 5-hydroxy-l-methyl-3-tnfluororornethylpyrazole (30 g, 180 mmol) (Example 1, Part A) was dissolved in toluene (250 mL) Lawesson's reagent (36 5 g, 90 mmol) was added and the mixture was heated to reflux for 8 hours An additional 10 0 g (20 mmol) of Lawesson's reagent was added and the mixture continued at reflux for 2 hours The mixture was allowed to cool, stir ⁇ ng at room temperature for 18 hours The solution was poured into saturated aqueous sodium carbonate solution and partitioned The resulting aqueous phase was acidified to pH 2 with concentrated hydrochlonc acid The mixture was extracted with diethyl ether, dned over magnesium sulfate, filtered and the filtrate evaporated to give the desired product as a yellow oil (26 g)
  • Example 5 above ( 1.25 g, 4 mmol) in ethyl acetate (20 mL) and the mixture was heated at reflux for 1 hour The mixture was cooled to room temperature and the solvent removed by rotary evaporation. The residue was dissolved in isopropanol (20mL) and stirred at room temperature for 1 hour, then the solvent was evaporated. Trituration with hexane gave
  • the grass weeds planted were broadleaf signalgrass (Brachiarta platyphylla) "BRAPP", large crabgrass (Digttana sangiitnalts) “DIGSA", bamyardgrass (Echtnochloa crusga/li) "ECHCG”, rigid ryegrass (Loliu rigtdum) "LOLRI”; fall panicum (Panicum dtchotomi ⁇ orum) "PANDI”; giant foxtail (Setart fahert) "SETFA”, green foxtail (Setana vtndis) "SETVI”; blac grass (Alopecurus myosurotdes) “ALOMY”, wild oat (Avena fatita) "AVEFA” and Johnsongrass (Sorghum halepense) "SORHA”
  • the broadleaf weeds planted were velvetleaf (Abutilon theophrastt) "ABUTH”, redroot pigweed (Amaranihus retroflexus) “AMARE”, common lambsquarters (Chenopodium album) "CHEA ", ivyieaf morningglory (Ipomoea hederacea) "IPOHE”, common purslane ⁇ Portulaca oleracea) “POROL”, common cockleburr (Xanthium strumartum) “XANST”, and catchweed bedstraw (Galtum aparine) “GALAP” Additionally, yellow nutsedge (Cyperus esculentus) "CYPES” nutlets were also sown.
  • Solutions of the test compounds were prepared by weighing out an approp ⁇ ate amount of the test compound to provide an application rate of 0 25 kilograms per hectare ( kg/ha), then dissolving the compound in a 50 50 mixture of deionized water and acetone containing 0 5% v/v Tween 20 ® (polyoxyethylene sorbitan monolaurate emulsifier) as a surfactant Additional solvents, not exceeding 15% of spray volume, were used if needed to dissolve the compound
  • the soil surface was sprayed inside an enclosed linear spray table with the nozzle set above the soil line
  • the spray table was calibrated to deliver 400 L/ha with the application rate being 0 25 kg/ha
  • the flats were placed into a greenhouse and watered as needed
  • the greenhouse environmental systems provided the plants with natural and artificial lighting to attain 14 hours of light per day Day and night temperatures were maintained at 29° and 21°C, respectively
  • the degree of weed control was evaluated and recorded 17-21 days after treatment as a percentage of weed control as compared to the growth of the same species of the same age in an untreated control flat
  • Percent control is the total injury to the plants due to all factors including inhibited emergence, stunting, malformation, chlorosis and other types of plant injury
  • the results of the pre-emergence screening tests are shown in Tables II and III below The control ratings range from 0 to 100 percent, where 0 represents no effect with growth equal to the untreated control and where 100 represents complete kill The symbol "--" indicates that no test was performed at the 0 25 kg/ ha level of application
  • the soil was prepared with the same methodology described for the pre- emergence test The following species were used.
  • Post-emergence flats were placed in the greenhouse under the same environmental conditions as described for the pre-emergence flats and watered as needed Plants were grown for 10 to 12 days (or to the appropriate growth stage) p ⁇ or to compound application Grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage Yellow nutsedge was 5 to 7 cm tall at application
  • Seeds of three weeds species were seeded into 8 9 X 8 9 cm pots.
  • the pots were previously filled with clay soil which contained 2.2% organic matter and had a pH of 5 7
  • the weed species were vomnochloa crus-gallt ("ECHCG”), Cyperus serottnus (“CYPDI”), and Sagittarta pygmaea (“SAGPY”).
  • EHCG Bachnochloa crus-gallt
  • CYPDI Cyperus serottnus
  • SAGPY Sagittarta pygmaea
  • the rice hybrid "Kosihikara” Oryza sattva
  • the pots were placed into a 10 liter plastic tubs, lined with a plastic bag. At an early growth stage, the rice plants were transplanted into an 8 9 cm X 8.9 cm pot, 3 plants per pot at a depth of 2 cm The pots were placed into the tubs with the weed species The tubs were flooded with water to a depth of 2-3 cm

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne des composés herbicides à base de pyrazole substitué et leurs dérivés. Ces composés sont représentés par la formule générale (Ia). Dans cette formule générale Y est O ou S et Z est une liaison simple carbone-carbone, O, S, C=O ou C=N. L'invention concerne également des procédés mettant en ÷uvre ces composés et dérivés pour lutter contre une végétation non souhaitée. L'invention concerne enfin des composés herbicides dans lesquels Z est une liaison simple carbone-carbone, S, C=O ou C=N.
PCT/GB1996/002783 1995-11-15 1996-11-12 Composes herbicides a base de pyrazole substitue WO1997018196A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96938339A EP0863879A1 (fr) 1995-11-15 1996-11-12 Composes herbicides a base de pyrazole substitue
AU75796/96A AU7579696A (en) 1995-11-15 1996-11-12 Herbicidal substituted pyrazole compounds
JP9518671A JP2000500448A (ja) 1995-11-15 1996-11-12 除草性置換ピラゾール化合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55940495A 1995-11-15 1995-11-15
US08/559,404 1995-11-15

Publications (1)

Publication Number Publication Date
WO1997018196A1 true WO1997018196A1 (fr) 1997-05-22

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Application Number Title Priority Date Filing Date
PCT/GB1996/002783 WO1997018196A1 (fr) 1995-11-15 1996-11-12 Composes herbicides a base de pyrazole substitue

Country Status (6)

Country Link
EP (1) EP0863879A1 (fr)
JP (1) JP2000500448A (fr)
AR (2) AR006747A1 (fr)
AU (1) AU7579696A (fr)
WO (1) WO1997018196A1 (fr)
ZA (1) ZA969565B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007698A1 (fr) * 1997-08-11 1999-02-18 Bayer Aktiengesellschaft (hetero)aryloxypyrazoles utilises comme herbicides
WO2002036547A1 (fr) * 2000-11-01 2002-05-10 Ajinomoto Co.,Inc. Composes amides d'acide cyclopropanecarboxylique et utilisations medicales
WO2002094792A1 (fr) * 2001-05-21 2002-11-28 Bayer Cropscience Ag Benzoylpyrazoles substitues a action herbicide
US6750222B2 (en) 2001-12-15 2004-06-15 Bayer Cropscience Gmbh Substituted phenyl derivatives

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JP2007031342A (ja) * 2005-07-27 2007-02-08 Ihara Chem Ind Co Ltd ５−ヒドロキシ−１−アルキルピラゾール誘導体の製造方法
EP2128138A1 (fr) * 2007-01-29 2009-12-02 Takeda Pharmaceutical Company Limited Composé de pyrazole
CA2862417C (fr) 2012-01-06 2017-09-05 Abide Therapeutics, Inc. Composes de carbamate et leur preparation et utilisation
CN107660199B (zh) 2015-03-18 2021-11-23 H.隆德贝克有限公司 哌嗪氨基甲酸酯及其制备和使用方法
KR20180004263A (ko) 2015-05-11 2018-01-10 어바이드 테라퓨틱스, 인크. 염증 또는 신경병성 통증의 치료 방법
WO2017143283A1 (fr) 2016-02-19 2017-08-24 Abide Therapeutics, Inc. Sonde de présence de monoacylglycérol lipase radiomarquée
CN109996790B (zh) 2016-09-19 2023-05-16 H.隆德贝克有限公司 哌嗪氨基甲酸酯及其制备和使用方法
JOP20190105A1 (ar) 2016-11-16 2019-05-09 Lundbeck La Jolla Research Center Inc مثبطات أحادي أسيل جليسرول ليباز (magl)
JOP20190106A1 (ar) 2016-11-16 2019-05-09 Lundbeck La Jolla Research Center Inc مثبطات أحادي أسيل جليسرول ليباز (magl)
WO2019222266A1 (fr) 2018-05-15 2019-11-21 Abide Therapeutics, Inc. Inhibiteurs de magl
JP2023523219A (ja) 2020-04-21 2023-06-02 ハー・ルンドベック・アクチエゼルスカベット モノアシルグリセロールリパーゼ阻害剤の合成

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008249A (en) * 1974-03-01 1977-02-15 Basf Aktiengesellschaft Substituted pyrazoles
EP0177710A1 (fr) * 1984-08-25 1986-04-16 Bayer Ag Phénylurées substituées

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008249A (en) * 1974-03-01 1977-02-15 Basf Aktiengesellschaft Substituted pyrazoles
EP0177710A1 (fr) * 1984-08-25 1986-04-16 Bayer Ag Phénylurées substituées

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007698A1 (fr) * 1997-08-11 1999-02-18 Bayer Aktiengesellschaft (hetero)aryloxypyrazoles utilises comme herbicides
WO2002036547A1 (fr) * 2000-11-01 2002-05-10 Ajinomoto Co.,Inc. Composes amides d'acide cyclopropanecarboxylique et utilisations medicales
WO2002094792A1 (fr) * 2001-05-21 2002-11-28 Bayer Cropscience Ag Benzoylpyrazoles substitues a action herbicide
US7635664B2 (en) 2001-05-21 2009-12-22 Bayer Cropscience Ag Herbicidal substituted benzoylpyrazoles
US6750222B2 (en) 2001-12-15 2004-06-15 Bayer Cropscience Gmbh Substituted phenyl derivatives

Also Published As

Publication number Publication date
EP0863879A1 (fr) 1998-09-16
AR008287A1 (es) 1999-12-29
JP2000500448A (ja) 2000-01-18
AR006747A1 (es) 1999-09-29
ZA969565B (en) 1997-08-08
AU7579696A (en) 1997-06-05

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