+

WO1992016511A1 - Herbicides - Google Patents

Herbicides Download PDF

Info

Publication number
WO1992016511A1
WO1992016511A1 PCT/GB1992/000376 GB9200376W WO9216511A1 WO 1992016511 A1 WO1992016511 A1 WO 1992016511A1 GB 9200376 W GB9200376 W GB 9200376W WO 9216511 A1 WO9216511 A1 WO 9216511A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
aryl
alkenyl
cycloalkyl
Prior art date
Application number
PCT/GB1992/000376
Other languages
English (en)
Inventor
Christoph Harde
Gerhard Johann
Gabriele KRÜGER
Richard Rees
Gerhard Tarara
Peter Stuart Gates
Original Assignee
Schering Agrochemicals Limited
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 Schering Agrochemicals Limited filed Critical Schering Agrochemicals Limited
Priority to CS931655A priority Critical patent/CZ165593A3/cs
Priority to JP4505555A priority patent/JPH06505723A/ja
Priority to BR9205763A priority patent/BR9205763A/pt
Priority to AU14102/92A priority patent/AU656178B2/en
Priority to PL92301208A priority patent/PL301208A1/xx
Publication of WO1992016511A1 publication Critical patent/WO1992016511A1/fr
Priority to FI933970A priority patent/FI933970A7/fi

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon 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
    • C07D413/06—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 carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • This invention concerns new haloacetic acid derivatives having herbicidal activity, processes for their preparation and herbicidal compositions containing them.
  • this invention provides the compounds of the formula:
  • X is halo;
  • R 1 and R 2 which may be the same or different, each represent alkyl, alkoxy, haloalkyl, haloalkoxy, halo, alkylamino or dialkylamino;
  • R 4 is H, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl group;
  • R 6 is H, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or heteroaryl grou ;
  • R 7 is a group as defined for R 6 or is -S0 2 R 8 , -OH, -CN, -OR 10 , -NH 2 , or -NHR 10 ; or R 6 and R 7 together form a ring;
  • R 8 is -N ⁇ R* or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl or heteroaryl group;
  • R 9 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or acyl group;
  • R 12 is a group as defined for R 6 , or is a substituted or unsubstituted acyl group
  • R 6 * and R* which may be the same or different, are each a group as defined for R 6 ; with the proviso that, when R 4 is ortho-substituted phenyl or naphthyl, any ortho-substituent thereon is halogen, -N0 2 , -OH, -OR 10 , -SH, -SR 8 , -SOR 8 , -S0 2 R 8 , -NH 2 , - NR ⁇ 10 , aryl or heteroaryl.
  • Any alkyl group present in the molecule is preferably of 1 to 8 carbon atoms, especially of 1 to 6 carbon atoms, and particularly of 1 to 4 carbon atoms.
  • Specific preferred unsubstituted alkyl or alkyl-containing groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, ethoxy, ethoxy and n-propoxy.
  • alkyl group in the molecule when any alkyl group in the molecule is substituted, this may for example be by one or more halogen atoms (eg fluorine, chlorine or bromine) , alkoxy groups of 1 to 4 carbon atoms (eg methoxy or ethoxy) , hydroxy, nitro, mercapto, amino, substituted amino, cyano, acyl, aryl or heteroaryl groups, or groups of the formula -SR 8 or -SOR 8 .
  • Specific preferred substituted alkyl-containing groups include chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, difluoromethoxy, methoxyethyl and ethoxyethyl.
  • Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, for example allyl, vinyl or propargyl. Any such alkenyl or alkynyl group is preferably unsubstituted, though it may if desired be substituted for example by halogen.
  • Any cycloalkyl group present in the molecule is preferably of 3 to 7 carbon atoms, especially cyclopentyl or cyclohexyl. It is preferably unsubstituted.
  • Any halogen atom present in the molecule is preferably fluorine, chlorine or bromine.
  • the term 'aryl' is used herein to mean aromatic carbocycles, which may be mononuclear, eg phenyl, or polynuclear, eg naphthyl.
  • Any aryl group present in the molecule is preferably a substituted or unsubstituted phenyl group.
  • any aralkyl group present in the molecule is preferably a substituted or unsubstituted benzyl group.
  • Any aryl group present in the molecule, when substituted, is preferably substituted by one or more halogen atoms (eg fluorine, chlorine or bromine) , alkyl or alkoxy groups of 1 to 4 carbon atoms (eg methyl, ethyl, methoxy or ethoxy) , hydroxy, nitro, mercapto, amino, substituted amino (eg alkyla ino, dialkylamino or acylamino groups, especially where the alkyl moieties have from 1 to 4 carbon atoms) , cyano, acyl, aryl or heteroaryl groups, or groups of the formula -SR 8 or -SOR 8 .
  • halogen atoms eg fluorine, chlorine or bromine
  • alkyl or alkoxy groups of 1 to 4 carbon atoms eg methyl, ethyl, methoxy or ethoxy
  • hydroxy, nitro, mercapto amino
  • substituted amino eg
  • heteroaryl*' is used herein to mean aromatic heterocyclic groups, which may be mononuclear or polynuclear.
  • Mononuclear heterocyclic groups are preferably of 5 or 6 ring atoms and contain at least one atom of nitrogen, oxygen or sulfur, eg furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, pyridinyl, pyrazinyl or thiadiazolyl.
  • Polynuclear heterocyclic groups are preferably benzoheterocyclic groups, eg indolyl, benzofuranyl, benzimidazolyl or quinolinyl.
  • Such mononuclear or polynuclear heterocyclic groups may, if desired, be substituted eg by one or more halogen atoms, eg chlorine, fluorine or bromine atoms, nitro groups, substituted or unsubstituted amino groups (eg alkylamino, dialkylamino or acylamino groups, especially where the alkyl moieties have from 1 to 4 carbon atoms) , cyano groups, or alkyl or alkoxy groups of 1 to 4 carbon atoms, eg methyl, ethyl, methoxy or ethoxy.
  • halogen atoms eg chlorine, fluorine or bromine atoms
  • nitro groups substituted or unsubstituted amino groups (eg alkylamino, dialkylamino or acylamino groups, especially where the alkyl moieties have from 1 to 4 carbon atoms)
  • cyano groups or alkyl or alkoxy groups of 1 to 4
  • acyl' * is used herein to mean the residue of carboxylic, sulfonic or phosphorus-containing acids, for example alkanoyl, alkenoyl, alkynoyl, cycloalkanoyl, aralkanoyl, aroyl, carbamoyl, thiocarbamoyl, alkoxycarbonyl, sulfonyl, sulfamoyl and phosphonyl groups, in which any alkyl, alkenyl, alkynyl or aryl group may be substituted or unsubstituted.
  • the salts of the compounds of formula I are preferably those formed with alkali-metals (eg lithium, sodium or potassium) , ammonium salts, or those formed with organic amines such as cyclohexylamine or piperidine.
  • X preferably represents chlorine, fluorine or bromine, especially fluorine.
  • R 1 is preferably chloro, methyl, methoxy, difluoromethoxy or ethoxy, especially methoxy.
  • R 2 is preferably methyl, methoxy or difluoromethoxy, especially methoxy.
  • R 3 is preferably a group -COOR 5 where R 5 is optionally- substituted alkyl of 1 to 4 carbon atoms, especially methyl, ethyl or tetrahydrof rylmethyl.
  • R 4 is preferably an unsubstituted alkyl group, especially isopropyl, sec-butyl or an aryl group, especially phenyl.
  • A, R 1 and R 2 are as defined hereinbefore, and Z is an anionic leaving group, for example halo or a group of formula -S0 2 Z' where Z' is alkyl of 1 to 4 carbon atoms or aryl, is reacted in the presence of a base with a compound of the formula XCH 2 COOR 5 (where R 5 is as defined hereinbefore but is other than hydrogen, and X is halogen) to give the desired compound.
  • the base employed is preferably lithium diisopropylamide, and the reaction is desirably effected in a suitable solvent medium, eg tetrahyd ofuran, and with cooling, eg to about -78°C.
  • R 3 represents a group -CN, -COOR 5 or -CONR 6 R 7 may also be prepared by a process in which a compound of the formula:
  • R 1 , R 2 and R 4 are as defined hereinbefore, and R 3 * is -CN, -COOR 5 or -CONR 6 R 7 (where R 5 , R 6 and R 7 are as defined hereinbefore) is halogenated to give the desired compound.
  • the halogenation may be effected by conventional techniques depending on the nature of the halogen involved.
  • bromination may be effected by means of N-bromosuccinimide.
  • Fluorination may be effected by first subjecting the compound of formula III to the action of a strong base, eg sodium hydride or lithium diisopropylamid , and reacting the formed anion with a fluorinating agent, eg N-fluoro-N-propyl-p- toluenesulfonamide or N-fluoro-N'-chloromethyl- triethylenediamine salts.
  • a strong base eg sodium hydride or lithium diisopropylamid
  • a fluorinating agent eg N-fluoro-N-propyl-p- toluenesulfonamide or N-fluoro-N'-chloromethyl- triethylenediamine salts.
  • R 3 represents a group -CN, -COOR 5 , -CHO or -CH 2 0H, and R 1 and R 2 each represent alkyl, alkoxy, amino or alkylamino, may also be prepared by a process in which a compound of the formula:
  • R 1 , R 2 , R 4 , X and A are as defined hereinbefore is subjected to the action of a suitable electrophile in the presence of a strong base, to give the desired compound.
  • the strong base employed may, for example, be butyllithium or lithium diisopropylamide, and the reaction is desirably effected at reduced temperature, eg at -78°C, and in a suitable solvent medium, eg tetrahydrofuran.
  • Suitable electrophiles include cyanates (eg phenyl cyanate) , chloroformates (eg alkyl chloroformates) , aldehydes (eg formaldehyde) and formamides (eg formdimethylamide) .
  • cyanates eg phenyl cyanate
  • chloroformates eg alkyl chloroformates
  • aldehydes eg formaldehyde
  • formamides eg formdimethylamide
  • the compounds of formula IV where R 1 and R 2 are alkyl may be made by standard methods.
  • the compounds of formula I where R 3 is carboxy can of course be prepared from the corresponding esters by hydrolysis, and many further conversions of the acid or ester function can be effected in known ways.
  • the compounds of formula I where R 3 is a group -COOR 5 may be reduced, eg by means of diisobutylaluminium hydride, to the corresponding compounds where R 3 is a group -CHO (using one molar proportion of the hydride) or -CH 2 OH (using two molar proportions of the hydride) .
  • the reductions are conveniently effected in a suitable solvent medium, eg tetrahydrofuran, and with cooling, eg to 5°C.
  • the compounds of formula I where R 3 is -CHO can be converted by known techniques to the corresponding hydrazones (eg by reaction with a compound of formula H ⁇ -N ⁇ 12 in a suitable solvent medium, eg an alcohol) , oximes (eg by reaction with a compound of formula H 2 NOR 6 in a suitable solvent medium, eg an alcohol), ketals, 1,3- dioxolanes, 1,3-dithiolanes, 1,3-dioxanes, 1,3-dithianes or imidazolidines (eg by heating in the presence of an acid catalyst with a compound of formula RQH or HQ-(CH 2 ) 2 . 3 -QH where Q is 0, S or NH) .
  • a suitable solvent medium eg an alcohol
  • oximes eg by reaction with a compound of formula H 2 NOR 6 in a suitable solvent medium, eg an alcohol
  • ketals 1,3- dioxolanes, 1,3-di
  • the compounds of formula I where R 3 is carboxy may be converted to the corresponding compounds in which R 3 is a group -CONHS0 2 R 8 by a two-stage process in which the acid is first reacted with thionyl chloride to give the corresponding acyl chloride, and this is then reacted with a compound of the formula NaNHS0 2 R 8 to give the desired compound.
  • the salts of the compounds of formula I may be prepared by reaction of the corresponding unsalified compound of formula I with an appropriate salt-forming base by methods known per se.
  • the compounds of formula I where R 3 is -CN can be converted by known techniques into the corresponding thioamides where R 3 is -CSNH 2 (eg by reaction with hydrogen sulfide in a suitable base such as pyridine) .
  • the compounds of formula I where R 3 is a heterocycle may be prepared by ring closure procedures well known per se carried out on the corresponding compounds of formula I where R 3 is -CN, -CSNH 2 or -CONR 6 R 7 .
  • ring closure reactions may be performed on the compounds of formula I where R 3 represents -CSNH 2 for example by reaction thereof with dibromoethane, or on the compounds of formula I where R 3 is -CONR 6 R 7 for example by reaction thereof with an acid chloride or anhydride.
  • the compounds of formula I and the salts thereof are herbicidally-active against a wide range of broadleaf and grass weeds, but are comparatively safe to certain crop species. They may thus be of use as herbicides, and especially as selective herbicides, particularly in cereals, eg maize, wheat or rice, in beet crops, eg sugar beet, in soybeans or in cotton.
  • this invention provides a herbicidal composition which comprises one or more compounds of formula I or salts thereof in association with a suitable carrier and/or surface active agent.
  • compositions of the invention usually contain from 0.01 to 99% by weight of the present compounds, and are normally produced initially as concentrates containing from 0.5 to 99%, preferably from 0.5 to 85%, and especially from 10 to 50% by weight thereof. Such concentrates are diluted if necessary before application to the locus to be treated such that the active ingredient comprises from 0.01 to 5% by weight of the formulation applied.
  • the carrier may be water, in which case an organic solvent may also be present, though this is not usually employed.
  • a flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent,e.g. xanthan gum.
  • the carrier may alternatively be a water immiscible organic solvent, e.g. a hydrocarbon which boils within the range 130-270°C, e.g. xylene, in which the compound is dissolved or suspended.
  • a water immiscible organic solvent e.g. a hydrocarbon which boils within the range 130-270°C, e.g. xylene, in which the compound is dissolved or suspended.
  • An emulsifiable concentrate containing a water immiscible solvent may be formed with a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water.
  • the carrier may alternatively be a water-miscible organic solvent e.g. 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.
  • a water-miscible organic solvent e.g. 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or dimethylformamide.
  • the carrier may alternatively be a solid, which may be finely divided or granular.
  • suitable solids are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers.
  • the carrier can be natural or synthetic or can be modified natural material.
  • Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the particulate carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture.
  • An aerosol composition may be formed by admixing the compound with a propellant, e.g. a polyhalogenated alkane such as dichlorofluoro ethane, and suitably also with a solvent.
  • a propellant e.g. a polyhalogenated alkane such as dichlorofluoro ethane, and suitably also with a solvent.
  • 'surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.
  • the surface active agents used may comprise anionic surface active agents, for example mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulfates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl tau
  • the surface active agents may also comprise non-ionic agents, for example condensation products or fatty acid esters, fatty alcohols, fatty acid amides or alkyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide e.g. polyoxyethylene sorbitan fatty acid esters, block copolymer ⁇ of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5- decyn-4,7-diol, or ethoxylated acetylenic glycols.
  • non-ionic agents for example condensation products or fatty acid esters, fatty alcohols, fatty acid amides or alkyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers e.g. sorbitan fatty acid esters, condensation products of
  • the surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl trimethyl- ammonium bromide, or ethoxylated tertiary fatty amines.
  • cationic agents for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl trimethyl- ammonium bromide, or ethoxylated tertiary fatty amines.
  • Preferred surface active agent-s include ethoxylated fatty alcohol sulfates, lignin sulfonates, alkyl-aryl sulfonates,salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, sodium oleoyl N-methyltauride, dialkyl sulfosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.
  • the present active compounds may be admixed with another pesticide, eg a herbicide, fungicide or insecticide, or a plant growth regulator, particularly another herbicide.
  • Suitable further herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluometuron, oxyfluorfen, fomesafen, bentazone, prometryne, norflurazon, chlomazone, EPTC, imazaquin, and especially isoproturon, methabenzthiazuron, trifluralin, ioxynil, bromoxynil, benazolin, ecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin, pendimethalin, ethofumesate, benfuresate, phenmedipham, benzophenap, butachlor, chlomethoxyfen, dim
  • Butyllithium (21ml of a 1.6M solution in hexane) was added to di-isopropylamine (4.94ml) in dry tetrahydrofuran (100ml) under nitrogen at a temperature of -78°C, and the mixture was stirred for 30 minutes.
  • Hexamethylphosphoric triamide (5.12ml) was added, and the mixture was stirred for a further 10 minutes.
  • Butyllithium (12.8ml of a 1.6M solution in hexane) was added to di-isopropylamine (3.05ml) in dry tetrahydrofuran (120ml) under nitrogen at a temperature of -78°C, and the mixture was stirred for 30 minutes.
  • the product of Example 1 (3.4g) in dry tetrahydrofuran (20ml) was then added at a temperature of -65°C, and the mixture was stirred for 1 hour, during which the temperature rose to -30°C. After cooling to -60°C, 3.18g of hexamethylphosphoric triamide were added, and the mixture was stirred for 15 minutes.
  • Ethyl 2-fluoro-3-meth l-2-(4,6-dimethoxy-l,3,5- triazin-2-yl)butanoate (1.5g) (see Example 11 below) was dissolved in tetrahydrofuran (40ml) , and the solution was cooled to 5°C under nitrogen.
  • Di-isobutyl aluminium hydride (ll l of 1.0M in hexane) was added, and the mixture was stirred for 24 hours at room temperature, after which it was treated dropwise with water (5ml) .
  • the solution was stirred for a further 30 minutes, and silica (10g) was added.
  • the suspension was filtered, and the solution was dried and evaporated.
  • Example 5 The product of Example 5 (0.60g) was dissolved in dry ether (40ml) with triethylamine (0.35ml) at 5°C, and acetyl chloride (0.18ml) in dry ether (10ml) was added dropwise. The solution was left to stand at room temperature for 2 days, after which it was filtered, and the organic layer was washed with water and dried. The residue was purified by chromatography, giving 0.35g of the desired product as a clear oil.
  • Example 7 The product of Example 5 (0.60g) was dissolved in dry ether (40ml) with triethylamine (0.35ml) at 5°C, and acetyl chloride (0.18ml) in dry ether (10ml) was added dropwise. The solution was left to stand at room temperature for 2 days, after which it was filtered, and the organic layer was washed with water and dried. The residue was purified by chromatography, giving 0.35g of the desired product as a clear oil.
  • Methyl 2-fluoro-3-methyl-2-(4,6-dimethoxypyrimidin-2- yl)butanoate (l.Og) (see Example 9 below) was dissolved in methanol (7ml) , and was treated with 5N sodium hydroxide solution (1.5ml) at 5-10°C. The methanol was evaporated off, and the residue was treated with water, then made acid with 5N hydrochloric acid, saturated with sodium chloride, and extracted with ether. The ethereal solution was washed with saturated sodium chloride solution and dried over magnesium sulfate. The product obtained by evaporation of the ether was triturated with pentane, yielding the desired product (0.87g). Examples 8-48
  • Seeds of the test species listed below were each sown in 8.5cm square pots filled to within 2cm of the top with sterile loam, and were covered with a 2-5mm layer of loam.
  • the pots were watered, and then treated by application to the soil surface in a spray cabinet with the compounds of the Examples listed below formulated as a solution/suspension in 3:1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) monolaurate solution (10 g per litre) .
  • the concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare.
  • the plant species listed below were grown in 8.5cm square pots containing sterile loam in a glasshouse (minimum temperature 16°C for temperate species, 21°C for non-temperate species, 16 hours per day photoperiod), and were treated in a spray cabinet at the 2-3 leaf stage with the compounds of the Examples listed below formulated as a solution/suspension in 3:1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) onolaurate solution (10 g per litre) . The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare.

Landscapes

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

Abstract

Dérivés herbicides d'acide halocétique correspondant à la formule (I) et sels de ces dérivés. Dans la formule, A représente -N= ou -CH=; X représente halo; R1 et R2, qui peuvent être identiques ou différents, représentent chacun alkyle, alcoxy, haloalkyle, haloalcoxy, halo, alkylamino ou dialkylamino; R3 représente -CN, -COOR?5, -CONR6R7¿, -CSNH¿2?, -CHO, -CH=Z, -CH(OAlkyle)2, -CH2OH, -CH2OR?9¿, ou un groupe hétérocyclique à 5 ou 6 éléments substitué ou non substitué lié par un atome de carbone cyclique qui est situé entre deux hétéroatomes cycliques; R4 représente H ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle ou aralkyle substitué ou non substitué; r5 représente H, -N=CR6aR6b ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle ou aralkyle substitué ou non substitué; R6 représente H ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle, aralkyle ou hétéroaryle substitué ou non substitué; R7 est un groupe correspondant à la définition de R6 ou représente -SO¿2R?8, -OH, -CN, -OR10, -NH2, ou -NHR?10; ou R6 et R7¿ forment ensemble un cycle; R8 représente -NR6aR6b ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle, aralkyle ou hétéroaryle substitué ou non substitué; R9 est un groupe alkyle, alcényle, alkynyle, cycloalkyle, aralkyle ou acyle substitué ou non substitué; R10 est un groupe correspondant à la définition de R9 ou est un groupe aryle ou hétéroaryle substitué ou non substitué; Z repréente =N-NR6R12 ou =NOR6; R12 est un groupe correspondant à la définition de R6, ou est un groupe acyle substitué ou non substitué; et R?6a et R6b¿, qui peuvent être identiques ou différents, représentent chacun un groupe correspondant à la définition de R6; à condition que, lorsque R4 représente naphtyle ou phényle ortho-substitué, tout ortho-substituant dans ce groupe soit halogène, -NO¿2?, -OH, -OR?10¿, -SH, -SR8, -SO2R8, -NH2, -NR6R10, aryle ou hétéroaryle.
PCT/GB1992/000376 1991-03-13 1992-03-03 Herbicides WO1992016511A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CS931655A CZ165593A3 (en) 1991-03-13 1992-03-03 Herbicides
JP4505555A JPH06505723A (ja) 1991-03-13 1992-03-03 ハロ酢酸誘導体除草剤
BR9205763A BR9205763A (pt) 1991-03-13 1992-03-03 Derivados do ácido haloacético e sais dos mesmos, composição herbicida e processo de combater ervas daninhas
AU14102/92A AU656178B2 (en) 1991-03-13 1992-03-03 Herbicides
PL92301208A PL301208A1 (en) 1991-03-13 1992-03-03 Herbicides
FI933970A FI933970A7 (fi) 1991-03-13 1993-09-10 Herbicider

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919105297A GB9105297D0 (en) 1991-03-13 1991-03-13 Herbicides
GB9105297.7 1991-03-13

Publications (1)

Publication Number Publication Date
WO1992016511A1 true WO1992016511A1 (fr) 1992-10-01

Family

ID=10691491

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/000376 WO1992016511A1 (fr) 1991-03-13 1992-03-03 Herbicides

Country Status (13)

Country Link
EP (1) EP0575404A1 (fr)
JP (1) JPH06505723A (fr)
AU (1) AU656178B2 (fr)
BR (1) BR9205763A (fr)
CA (1) CA2106088A1 (fr)
CZ (1) CZ165593A3 (fr)
FI (1) FI933970A7 (fr)
GB (1) GB9105297D0 (fr)
HU (1) HUT64677A (fr)
IE (1) IE920777A1 (fr)
IL (1) IL101202A (fr)
PL (1) PL301208A1 (fr)
WO (1) WO1992016511A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006642A1 (fr) * 1993-09-02 1995-03-09 Bayer Aktiengesellschaft 1,3,5-triazin-diamines substituees par malodinitrile a effet herbicide
US5491172A (en) * 1993-05-14 1996-02-13 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and N-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
US5506192A (en) * 1990-06-07 1996-04-09 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
WO1997000253A1 (fr) * 1995-06-14 1997-01-03 Hoechst Schering Agrevo Gmbh Tetrazoles substitues, leur procede de preparation et leur utilisation comme herbicides et regulateurs de la croissance vegetale
US5633287A (en) * 1993-05-14 1997-05-27 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and n-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
RU2133746C1 (ru) * 1994-03-22 1999-07-27 Кумиай Кемикал Индастри Ко., Лтд. Производные никотиновой кислоты, способ их получения и гербицидная композиция

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353640A2 (fr) * 1988-08-02 1990-02-07 Hoechst Schering AgrEvo GmbH N-acylsulfonamides hétérocycliques, procédé pour leur préparation, agents les contenant et leur utilisation comme herbicides régulateurs de croissance des plantes
EP0410590A1 (fr) * 1989-07-27 1991-01-30 AgrEvo UK Limited Herbicides dérivés de pyrimidines

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7077091A (en) * 1990-01-11 1991-08-05 E.I. Du Pont De Nemours And Company Herbicidal pyrimidines and triazines
HU212435B (en) * 1990-06-07 1996-06-28 Sandoz Ag Herbicidal compositions containing substituted phthalides and heterocyclic phthalides as active ingredient and process for preparation of their active ingredients.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353640A2 (fr) * 1988-08-02 1990-02-07 Hoechst Schering AgrEvo GmbH N-acylsulfonamides hétérocycliques, procédé pour leur préparation, agents les contenant et leur utilisation comme herbicides régulateurs de croissance des plantes
EP0410590A1 (fr) * 1989-07-27 1991-01-30 AgrEvo UK Limited Herbicides dérivés de pyrimidines

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506192A (en) * 1990-06-07 1996-04-09 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
US5627137A (en) * 1990-06-07 1997-05-06 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
US5627138A (en) * 1990-06-07 1997-05-06 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
US5491172A (en) * 1993-05-14 1996-02-13 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and N-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
US5633287A (en) * 1993-05-14 1997-05-27 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and n-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
WO1995006642A1 (fr) * 1993-09-02 1995-03-09 Bayer Aktiengesellschaft 1,3,5-triazin-diamines substituees par malodinitrile a effet herbicide
RU2133746C1 (ru) * 1994-03-22 1999-07-27 Кумиай Кемикал Индастри Ко., Лтд. Производные никотиновой кислоты, способ их получения и гербицидная композиция
WO1997000253A1 (fr) * 1995-06-14 1997-01-03 Hoechst Schering Agrevo Gmbh Tetrazoles substitues, leur procede de preparation et leur utilisation comme herbicides et regulateurs de la croissance vegetale

Also Published As

Publication number Publication date
CA2106088A1 (fr) 1992-09-14
FI933970A0 (fi) 1993-09-10
CZ165593A3 (en) 1994-02-16
BR9205763A (pt) 1994-11-08
IL101202A (en) 1996-01-31
GB9105297D0 (en) 1991-04-24
HU9302573D0 (en) 1993-12-28
FI933970A7 (fi) 1993-09-10
IL101202A0 (en) 1992-11-15
AU1410292A (en) 1992-10-21
PL301208A1 (en) 1994-04-18
JPH06505723A (ja) 1994-06-30
HUT64677A (en) 1994-02-28
IE920777A1 (en) 1992-09-23
EP0575404A1 (fr) 1993-12-29
AU656178B2 (en) 1995-01-27

Similar Documents

Publication Publication Date Title
EP0625970B1 (fr) Herbicides contenant des sulfonamides
EP0410590B1 (fr) Herbicides dérivés de pyrimidines
EP0435170B1 (fr) Dérivés de pyrimidine ou de triazine et composition herbicide les contenant
EP0246749A2 (fr) Triazoles herbicides
EP0244948A2 (fr) Herbicides de triazolopyrimidine
US5317005A (en) Pyrimidinyl and triazinyl herbicides
WO1992016511A1 (fr) Herbicides
US5024693A (en) Herbicides
US5502028A (en) Herbicidal pyrimidinyl or triazinyl haloacetic acid derivatives
WO1993011118A1 (fr) Herbicides et fongicides derives de pyrole
US5604181A (en) Pyrimidine derivatives herbicides
US4956004A (en) Herbicidal triazinediones
JPH05208935A (ja) 新規なハロゲン化シクロアルカンカルボン酸誘導体、それを有効成分とする除草剤およびそのための中間体
US5401710A (en) Herbicides
WO1992010484A1 (fr) Herbicides
JPH04342574A (ja) アリールアルデヒドヒドラゾン誘導体とその製造法及びこれを有効成分とする除草剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR CA CS FI HU JP KR NO PL RO RU SD US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU MC ML MR NL SE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
EX32 Extension under rule 32 effected after completion of technical preparation for international publication
WWE Wipo information: entry into national phase

Ref document number: 1992906289

Country of ref document: EP

LE32 Later election for international application filed prior to expiration of 19th month from priority date or according to rule 32.2 (b)
WWE Wipo information: entry into national phase

Ref document number: PV1993-1655

Country of ref document: CZ

ENP Entry into the national phase

Ref document number: 1993 119048

Country of ref document: US

Date of ref document: 19930910

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 933970

Country of ref document: FI

WWE Wipo information: entry into national phase

Ref document number: 2106088

Country of ref document: CA

LE32 Later election for international application filed prior to expiration of 19th month from priority date or according to rule 32.2 (b)
LE32 Later election for international application filed prior to expiration of 19th month from priority date or according to rule 32.2 (b)
WWP Wipo information: published in national office

Ref document number: 1992906289

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV1993-1655

Country of ref document: CZ

ENP Entry into the national phase

Ref document number: 1994 357526

Country of ref document: US

Date of ref document: 19941216

Kind code of ref document: A

WWR Wipo information: refused in national office

Ref document number: PV1993-1655

Country of ref document: CZ

WWW Wipo information: withdrawn in national office

Ref document number: 1992906289

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载