EP1097117A2 - Derives d'arylvinylether et leur utilisation comme herbicides - Google Patents

Derives d'arylvinylether et leur utilisation comme herbicides

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Publication number
EP1097117A2
EP1097117A2 EP99940084A EP99940084A EP1097117A2 EP 1097117 A2 EP1097117 A2 EP 1097117A2 EP 99940084 A EP99940084 A EP 99940084A EP 99940084 A EP99940084 A EP 99940084A EP 1097117 A2 EP1097117 A2 EP 1097117A2
Authority
EP
European Patent Office
Prior art keywords
methyl
methoxypropenoate
compound
optionally substituted
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99940084A
Other languages
German (de)
English (en)
Inventor
Nicholas Charles Ray
Catherine Jacqueline White
Michael Gingell
Simon Neil Pettit
Gilles Raphy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Agriculture Ltd
Original Assignee
Aventis Agriculture Ltd
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
Priority claimed from GBGB9815508.8A external-priority patent/GB9815508D0/en
Application filed by Aventis Agriculture Ltd filed Critical Aventis Agriculture Ltd
Publication of EP1097117A2 publication Critical patent/EP1097117A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/58—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/64—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/20—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having nitrogen atoms of amidino groups acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C311/04—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/54—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/02—Thiocyanates
    • C07C331/10—Thiocyanates having sulfur atoms of thiocyanate groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/02—Thiocyanates
    • C07C331/14—Thiocyanates having sulfur atoms of thiocyanate groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D211/78—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/30—Nitrogen atoms non-acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid

Definitions

  • the invention relates to novel aryl vinyl ethers having herbicidal properties, compositions containing them, processes and intermediates for their preparation, a method of controlling weeds by means of such compositions and the safening of aryl vinyl ethers with antidotal or safener compounds.
  • An object of this invention is to provide new aryl vinyl ether derivatives useful as highly effective herbicides, and processes for their preparation.
  • Another object of the instant invention is to provide herbicides which are effective against grasses in addition to broad-leafed weeds. Another object is to provide herbicides which possess selective herbicidal activity.
  • Another object is to provide herbicides effective as low dose herbicides.
  • Another object is to provide herbicides which possess good residual activity.
  • Aryl vinyl ether compounds under certain conditions can produce damage in crop plants, particularly cereal crop plants such as maize and -?-
  • the present invention provides compounds of formula (I):
  • X 2 is O, S, NR 18 or a simple bond (preferably O, S or NR 18 ); X 3 is N or CR 19 ;
  • R 17 and R 18 independently represent a hydrogen atom or an optionally substituted group R , R , R or R , wherein; R 20 represents a lower alkyl radical; R 21 represents a lower alkenyl radical; R 22 represents a lower alkynyl radical; R 23 represents a -(CH 2 )m-phenyl radical; m represents zero or one; R 16 is R 24 or OR 25 or SR 25 , NR 25 R 26 or alkyl substituted by alkoxycarbonyl;
  • R 24 , R 2 and R independently have one of the meanings given for R 18 ;
  • R 19 has one of the meanings given for R 16 ;
  • R 10 represents a radical selected from
  • R represents an optionally substituted N-linked imidazole or triazole ring optionally fused to a benzene ring;
  • R 30a and R 3 la together with the N atom to which they are attached form a 5 or 6 -membered saturated heterocyclic ring optionally containing an additional O, S or NR a group in the ring;
  • R 27 , R 28 and R 281 represent the same or different halogen atoms;
  • R 29 and R 291 represent OR 37 or SR 37 or,
  • R 29 and R 291 together form a divalent radical with which the carbon atom to which they are attached forms a 5 or 6 membered cyclic acetal or thioacetal ring, the ring system of which is optionally substituted by one or more lower alkyl groups;
  • R 30 , R 31 and R 32 independently represent hydrogen, lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted -(CH 2 )m-phenyl;
  • R 33 and R 34 represent R 32 with the exclusion of the hydrogen atom
  • R 35 and R 36 represent a hydrogen atom or a radical which may be any of the following ; alkyl, alkoxy or optionally substituted phenyl;
  • R 37 represents lower alkyl, lower haloalkyl, lower alkenyl or lower haloalkenyl ;
  • R 1 'and R 13 each independently represent hydrogen or alkyl, or
  • R u and R 13 may be together a simple bond creating a double bond with the carbon atom to which they are attached, or
  • R u and R 13 may be a single divalent radical comprising one to six atoms on the main chain, this main chain optionally containing one to three nitrogen atoms, one oxygen atom or one sulphur atom; this divalent radical forming with the two carbon atoms to which they are attached, a saturated or non-saturated carbocyclic or heterocyclic ring (for example phenyl or pyridyl) or a bicyclic ring, these rings being optionally substituted by from one to four R radicals, each ring containing at most eight ring members, preferably at most six, wherein R 15 represents a halogen atom, hydroxy, cyano, lower alkoxycarbonyl, lower alkyl, lower alkenyl, lower alkynyl, optionally substituted cycloalkyl, lower alkoxy, lower alkylthio, lower alkylsulfinyl, lower alkylsulfonyl, lower haloalkoxycarbonyl, lower
  • R b and R c together with the C atoms to which they are attached form a 5 or 6 -membered cyclic acetal group
  • R 1 , 0 ⁇ Rr represents a group (A), (B), (C), (D) or (E):
  • R d , R c , R f , R g and R h represent H, lower alkyl, halogen or OH, and n represents the values 0, 1, 2 or 3;
  • R 1 ' represents R or a hydrogen atom
  • R 12 and R 14 each independently represent hydrogen or alkyl or may form a simple bond, creating a double bond together where R 1 1 and R 13 are together a single divalent radical; preferably with the following provisos; i) when R 10 R ⁇ R 12 C-C(R I3 )(R 14 )- represents a phenyl ring optionally substituted by R 15 ; R 10 represents -CO 2 R 32 , CONR 30 R 31 , CHR 27 R 28 or CR 27 R 28 R 281 , wherein R 32 represents alkyl or haloalkyl; R 30 and R 31 represent H or alkyl, and R 27 , R 28 and R 281 are as defined above; p is zero; X.
  • the invention also embraces any stereoisomer, enantiomer, geometric isomer of formula (I) or mixture thereof.
  • the aryl vinyl ether derivatives of the present invention have two possible stereoisomers, (Z) and (E) isomers, as defined in the Cahn- Ingold-Prelog rules at a double bond. It will be understood that the present invention embraces both the pure isomers and mixtures which may be more or less enriched mixtures thereof. Furthermore it is understood that the compounds of formula (I) wherein R 10 , R 11 , R 12 , R 13 , R 14 and R 17 are as defined above, X 3 is CR 19 and in which R 16 is OR 25 wherein R is hydrogen, may exist in a tautomeric form and acetal forms thereof.
  • Suitable salts with bases include alkali metal (e.g. sodium and potassium), alkaline earth metal (e.g. calcium and magnesium), ammonium and amine (e.g. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts.
  • alkali metal e.g. sodium and potassium
  • alkaline earth metal e.g. calcium and magnesium
  • ammonium and amine e.g. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine
  • compounds of formula I containing an amino group include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids for example acetic acid.
  • Formyl groups may exist as their hydrates i.e. as the dihydroxymethyl form.
  • all of the optionally substituted groups may have as the optional substituent one or more halogen atoms, among other possible substituents.
  • cycloalkyl radicals the following may be selected; lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl and halogen.
  • phenyl radicals the following may be selected; phenoxy, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, cyano, lower alkoxycarbonyl, lower haloalkoxycarbonyl, lower alkoxy, lower haloalkoxy, lower alkylthio, lower haloalkylthio, lower alkylsulfonyl, lower haloalkylsulfonyl, lower alkylsulfinyl, lower haloalkylsulfinyl, nitro, lower alkylcarbonyl, lower alkylamino, lower dialkylamino, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkylcarbonylamino and phenyl optionally substituted by halogen, alkyl, alkoxy or benzyloxy.
  • halogen atom means fluorine, chlorine, bromine or iodine
  • alkyl, alkenyl and alkynyl radicals may be straight- or branched- chain groups
  • cycloalkyl groups have from three to six carbon atoms in the ring
  • lower for a radical means that the said radical may have up to 8 carbon atoms (preferably up to 6), which are straight or branched chain.
  • preferred groups of the compounds include those compounds of general formula (I) in which;
  • R ⁇ and R 13 form a non-saturated carbocyclic ring (preferably phenyl) substituted by a halogen atom (preferably chlorine or fluorine); or R 11 and R 13 represent a pyridine ring; or R 1 1 and R 13 represent a phenyl ring which is fused at the o- and m- positions (relative to the R group) to a saturated or unsaturated 5 or 6-membered carbocyclic ring; X 3 is CR 19 wherein R 19 represents a hydrogen atom; X 2 is an oxygen atom;
  • Xi is an oxygen or sulphur atom (preferably an oxygen atom);
  • R 16 is a hydrogen atom or lower alkyl group (preferably methyl) or OR 25 wherein R 25 represents a lower alkyl group or a hydrogen atom
  • R 16 is methoxy
  • R 17 is a hydrogen atom or lower alkyl group (preferably methyl).
  • a preferred class of compounds of formula (I) are those in which: R n and R 13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups; X 3 is CR 19 wherein R 19 represents a hydrogen atom; Xi and X each represent an oxygen atom; R 16 and R I7 each represent a methyl group; and R 10 is -CO 2 R 32 .
  • a most preferred class of compounds of formula (I) are those in which:
  • R 11 and R 13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups;
  • X is CR 19 wherein R 19 represents a hydrogen atom; Xi and X 2 each represent an oxygen atom; R and R each represent a methyl group; and R is -CO 2 R in which R 32 is lower alkyl or hydrogen.
  • CH 3 CH2NO2 means CH 2 NO 2) etc.
  • R 10 represents CO 2 R 32 , wherein R 32 is as hereinbefore defined and in which R 15 , R 25 and R 17 have the meanings indicated hereinbelow.
  • Identification Group I recites individual species in which R 32 represents, hydrogen, Na, Me, Et, n-Pr, i-Pr, c-Pr-methyl, n- Bu, 2-Bu, Pen, c-Pen, c-Hex, Bn, 2-heptyl, octyl, 2-octyl, 2,2,2- trifluoroethyl, 3-chloroprop-l-yl, propargyl, methoxyethyl, ethoxyethyl, allyl.
  • the R 15 group is located according to the numbering system in (I- 2) and (1-7) and when more than one R 15 substituent is present, the various meanings have been placed in the same column.
  • the meanings of R 29 , R 291 ,R 30 and R 31 are as defined hereinabove.
  • R 10 , R 15 , R 25 and R 17 have the meanings shown.
  • the R 15 group is located according to the numbering system in the formulae, and when more than one R 15 substituent is present then the various meanings have been placed in the same column.
  • R 10 , R , 15 and X have the meanings indicated hereinbelow.
  • the R 1 group is located according to the numbering system in (1-14).
  • the reaction is generally carried out in the presence of an organic solvent, preferably the alcohol R 33 OH, optionally in the presence of an acid or base catalyst, preferably an acid catalyst such as sulphuric acid.
  • an organic solvent preferably the alcohol R 33 OH
  • an acid or base catalyst preferably an acid catalyst such as sulphuric acid.
  • compounds of formula (I) wherein the various symbols are as defined above and in which R 10 represents -CO 2 H may be prepared from the corresponding compound wherein R represents -CO 2 R 3 and R 33 represents t-butyl, using an acid such as trifluoroacetic acid in a solvent such as dichloromethane at a temperature of from 0-50°C.
  • compounds of formula (I) wherein the various symbols are as defined above and in which R 10 represents -CONR 30 R 31 may be prepared from the corresponding compound of formula (I) wherein R 10 represents -CO 2 H by successive treatment with a halogenating agent to give the acyl halide, followed by an amine of formula (III):
  • the halogenating agent is generally an oxalyl halide or a sulfonyl halide, the halide; is preferably chloride.
  • the halogenation can be performed in the presence or absence of solvent, preferably in an halogenated hydrocarbon such as dichloromethane at a temperature between 0 °C and 40 °C, optionally in the presence of a dialkylformamide as catalyst, usually dimethylformamide.
  • the reaction of the thus formed acyl halide with an amine of formula (III) is generally performed in an inert solvent such as dichloromethane, optionally in the presence of a base, generally a tertiary amine base such as triethylamine, at a temperature between 0 °C and 40 °C.
  • an inert solvent such as dichloromethane
  • a base generally a tertiary amine base such as triethylamine
  • compounds of formula (I) wherein the various symbols are as defined above, in which R 10 is -CH 2 NO 2 , -CH 2 SCN, -CH 2 CN or -CH 2 N 3 may be prepared from the corresponding compound of formula (I) wherein R 10 is -CH ⁇ -L, where L is a leaving group, generally a sulfonate ester such as a para toluenesulfonate or a mesylate, or wherein R 10 is replaced by -CH 2 -L', where L 1 is a leaving group, generally a halogen, by treatment with the metal salt of the appropriate nitro, thiocyano, cyano or azido anion respectively, especially a group la or lb metal salt, such as sodium, potassium or silver, in an organic solvent such as dimethylformamide or dimethylsulfoxide, at a temperature between 0 °C and 150 °C, preferably 0° to 60 °C
  • reaction optionally in the presence of an organic solvent, such as toluene, acetic acid or an alcohol such as methanol or ethanol, optionally in the presence of an acid, such as para-toluene sulfonic acid or a base, such as sodium acetate, as catalyst.
  • organic solvent such as toluene, acetic acid or an alcohol such as methanol or ethanol
  • an acid such as para-toluene sulfonic acid or a base, such as sodium acetate
  • a base such as sodium acetate
  • the halogen is preferably bromine or iodine.
  • the reaction can be conducted in the absence or presence of solvent, which may be organic or aqueous, generally a polar aprotic solvent such as ⁇ , ⁇ - dimethylformamide or a polyether such as glyme.
  • solvent which may be organic or aqueous, generally a polar aprotic solvent such as ⁇ , ⁇ - dimethylformamide or a polyether such as glyme.
  • the reaction is usually carried out in the presence of a transition metal compound as catalyst, usually of palladium, such as palladium acetate, optionally in the presence of a base, for example triethylamine and other catalysts such as trialkyl or triaryl phosphines, generally triphenylphosphine.
  • the reactions are performed at temperatures from 0°C to 150 °C, generally
  • compounds of formula (I) wherein the various symbols are as defined above and in which R 10 represents -CHR 27 R 28 or -CR 27 R 28 R 281 and R 27 , R 28 and R 281 are as defined above, may be prepared by the halogenation of the corresponding compound in which one or more of R 27 , R 28 and R 281 are replaced by hydrogen atoms.
  • the reaction is generally performed using a N-halosuccinimide such as N-bromosuccinimide, in a solvent such as carbon tetrachloride, optionally with a radical initiator such as azobisisobutyronitrile, and optionally in the presence of irradiation with light, at a temperature of from 20°C to the reflux temperature of the solvent.
  • a N-halosuccinimide such as N-bromosuccinimide
  • a solvent such as carbon tetrachloride
  • a radical initiator such as azobisisobutyronitrile
  • an alkylating agent to introduce a group R 251 which is alkyl
  • a dialkysulfate such as dimethylsulfate
  • an alkyl halide preferably an alkyl iodide such as methyl iodide.
  • the reaction may be performed in the absence or presence of an organic solvent, such as an ether such as diethyl ether, or a dialkylformamide, such as dimethylformamide, at a temperature between 0° and 40 °C, optionally in the presence of a base which may be organic, such as a tertiary amine, or inorganic, such as a metal carbonate or a metal bicarbonate, such as potassium carbonate.
  • compounds of formula (VIII) wherein R 10 , R 11 , R 12 , R 13 , R 14 , R 17 , X 1 ? X 2 are as hereinbefore defined and X 3 represents CR wherein R represents R may be prepared from the reaction of a compound of formula (IX);
  • the aminomethylating agent is generally a dialkylaminodialkylacetal, such as dimethylformamide dimethyl acetal, or an alkoxybis(dialkylamino)methane, specifically t- butoxybis(dimethylamino)methane (Bredereck's reagent).
  • the reaction is conducted in the absence or in the presence of an organic solvent such as toluene at a temperature between 20°C and 150°C, preferably between 80°C and 130°C.
  • Hydrolysis is accomplished with an acid, generally a mineral acid, such as hydrochloric acid in the presence of an organic solvent, which may or may not be miscible with water, such as tetrahydrofuran.
  • compounds of formula (I) wherein the various symbols are as defined above and in which R 10 represents -COCH 2 COR 33 wherein R 33 is as defined above may be prepared from the corresponding compound in which R 10 is replaced by a group COCH(CO 2 tBu)COR 33 .
  • the reaction is generally performed using an acid such as 4-toluenesulphonic acid in a solvent such as dichloromethane at a temperature of from 0-50°C.
  • compounds of formula (I) wherein R 10 represents -COF may be prepared from the corresponding compound in which R 10 represents CO 2 H, by reaction with a fluorinating agent such as cyanunic fluoride in the presence of a base such as pyridine in an inert solvent such as dichloromethane at 0- 50°C.
  • a fluorinating agent such as cyanunic fluoride
  • a base such as pyridine
  • an inert solvent such as dichloromethane at 0- 50°C.
  • R 10 represents -CO 2 R 33 and R 33 represents t- butyl
  • a solvent such as dichloromethane.
  • the reaction is performed in the presence of an acid such as sulphuric acid and preferably a dehydrating agent such as anhydrous magnesium sulphate at a temperature of from 0-50°C.
  • compounds of formula (IX) may be prepared by the reaction of a compound of formula (X),
  • L is a leaving group, generally a sulfonate, such as a triflate or tosylate, or a halide, generally a chloride, bromide or iodide radical, with a compound of formula (XI),
  • methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3- hydroxypropenoate was mixed with 336mg of K 2 CO 3 , (CH 3 ) 2 SO (0.16ml) and dimethylformamide (8.2ml). The mixture was stirred for 12 hours at 20°C and extracted with ether (following the addition of Na 2 CO 3 ). The organic layer was washed with water and brine and dried so as to give, methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3- methoxypropenoate (compound 1), M.S. analysis showed m/z 343 (M+H).
  • Example 5 lOOmg of methyl 2-(2-bromomethyl-4-chlorophenoxy)-3- methoxyacrylate were mixed with 70mg of N-methylmorpholine N- oxide monohydrate and stirred in acetonitrile at 20°C for 12 hours in the presence of sieves as a drying agent. The mixture was filtered, washed with water and dried so as to give 56mg of methyl 2-(2-formyl-4- chlorophenoxy)-3-methoxypropenoate (compound 5), M.S. m/z 271 (M+H).
  • Example 13 42 mg of methyl 2-(2-carboxy-4-chlorophenoxy)-3- methoxypropenoate dissolved in a mixture of diethyl ether (0.8 ml) and tetrahydrofuran (0.4 ml) were added to 7.5 mg of a 60% dispersion of sodium hydride in mineral oil. The mixture was stirred at ambient temperature for 4 hours to give a white precipitate that was filtered, washed with ether and dried to give methyl 2-(2-carboxy-4- chlorophenoxy)-3-methoxypropenoate, sodium salt (compound 43), mp 230-234 °C (decomposed).
  • methyl 2-(2-carboxy-4-iodophenoxy)-3-methoxypropenoate sodium salt (compound 116, mp 234-235°C) was prepared.
  • Example 14 50 mg of methyl 2-(2-bromo-4-chlorophenoxy)-3- methoxypropenoate, 30 ⁇ l of triethylamine, 3.4 mg of triphenylphosphine, 40 ⁇ l of methyl acrylate, 1.4 mg of palladium acetate and DMF (2 ml) were stirred at 100 °C for 24 hours. The reaction mixture was worked up with 2N HCI, extracted into ethyl acetate, dried and concentrated. Column chromatography gave methyl 2-(4-chloro-2-
  • Methyl magnesium iodide (0.112ml of a 3M solution) was added dropwise to a stirred solution of methyl 2-(4-chloro-2-formylphenoxy)- 3-methoxypropenoate (0. lg) in toluene. After 1 hour the solvent was evaporated and the residue partitioned between hydrochloric acid (2M) and ethyl acetate.
  • Oxalyl chloride (0.4ml) and N,N-dimethylformamide were added to a solution of methyl 2-(2-carboxy-4-chlorophenoxy)-3- methoxypropenoate (l.Og) in dichloromethane and stirred at reflux for 2 hours and evaporated.
  • a solution of the residue in tetrahydrofuran was added dropwise to a solution of trimethylsilyldiazomethane (2.2ml of a 2M solution in hexane) and triethylamine (0.6ml) in tetrahydrofuran at 0°C. The mixture was kept at 0°C overnight, evaporated and partitioned between sodium bicarbonate solution and ethyl acetate.
  • Cyanuric fluoride (39.6mg) and pyridine (1 1.6mg) were added to a solution of methyl 2-(2-carboxy-4-chlorophenoxy)-3- methoxypropenoate (42mg) in dichloromethane, and stirred at 20°C under nitrogen for 4 hours.
  • methyl 2-(4-chloro-2- methyIphenoxy)-3-methoxypropenoate was prepared from methyl 2-(4- chloro-2-methylphenoxy)-3-hydroxy ⁇ ropenoate, M.S. m/z 257 (M+H); and methyl 2-(2-bromo-4-chlorophenoxy)3-methoxypropenoate, M.S. m/z 321 (M+H), from methyl 2-(2-bromo-4-chlorophenoxy)-3- hydroxypropenoate.
  • Methyl 2-(4-chloro-2-methylphenoxy)-3-hydroxypropenoate, M.S. m/z 241 (M-H) was similarly prepared starting from methyl (4-chloro-2- methylphenoxy)acetate.
  • H 2 SO 1.54(ml) was added to a stirred suspension of anhydrous MgSO 4 in CH 2 C1 2 . After 15 minutes 5g of 5-chlorosalicylic acid was added, followed by t-butanol (13.66ml). The mixture was stoppered and stirred for 43 hours at ambient temperature. To the suspension was added saturated aqueous NaHCO 3 (220ml) and the mixture stirred for 20 minutes.
  • Oxalyl chloride (0.4ml) was added to a solution of methyl 2-(2- carboxy-4-chlorophenoxy)-3-methoxypropenoate (l.Og) in dichloromethane containing N,N-dimethylformamide (1 drop) and stirred at reflux for 2 hours. After evaporation, the residue was dissolved in toluene, and a solution of t-butyl-3-cyclopropyl-3- oxopropanoate magnesium methoxide enolate (1.05g) in toluene added, and the mixture stirred overnight. Hydrochloric acid (2M) was added and stirrred for 5 minutes. The organic phase was washed (water), dried
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • a herbicidally effective amount of at least one aryl vinyl ether derivative of formula (I) or an agriculturally acceptable salt or metal complex thereof comprises applying to the locus a herbicidally effective amount of at least one aryl vinyl ether derivative of formula (I) or an agriculturally acceptable salt or metal complex thereof.
  • the aryl vinyl ether derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
  • the compounds of formula (I) show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (e.g. grass) weeds by pre- and/or post-emergence application.
  • pre-emergence application is meant application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil.
  • post- emergence application is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
  • the compounds of formula (I) may be used to control the growth of: broad-leafed weeds, for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa. Chenopodium album. Galium aparine, Ipomoea spp. e.g. Ipomoea pu ⁇ urea, Sesbania exaltata, Sinapis arvensis, Solanum nigrum and Xanthium strumarium, and grass weeds, for example Alopecurus myosuroides. A vena fatua, Digitaria sanguinalis, Echinochloa crus-galli. Eleusine indica and Setaria spp, e.g. Setaria faberii or Setaria viridis. and sedges, for example, Cvperus esculentus.
  • broad-leafed weeds for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa. Chenopodium album. Gal
  • the amounts of compounds of formula (I) applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops.
  • the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop.
  • application rates between lg and lOOOg of active material per hectare give good results. However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
  • the compounds of formula (I) may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g. by directional or non- directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g. wheat, barley, oats, maize and rice, soybean, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence of the crop.
  • cereals e.g. wheat, barley, oats, maize and rice, soybean, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar bee
  • the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, by pre- or post- emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations.
  • plantations e.g. sugar cane, oil palm and rubber plantations.
  • they may be applied in a directional or non- directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at application rates between 50g and 5000g, and preferably between 50g and 2000g, most preferably between lOOg and lOOOg of active material per hectare.
  • the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
  • non-crop-growing areas examples include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks.
  • the active compounds When used for such pu ⁇ oses in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
  • the compounds of formula (I) may be inco ⁇ orated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula (I) are used to control the growth of weeds by post-emergence application, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of formula (I) will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
  • compositions suitable for herbicidal use comprising one or more of the aryl vinyl ethers of formula (I) or an agriculturally acceptable salt or metal complex thereof, in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)].
  • the term "homogeneously dispersed” is used to include compositions in which the compounds of formula ⁇ !) are dissolved in other components.
  • herbicidal compositions is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
  • the compositions contain from 0.05 to 90% by weight of one or more compounds of formula (I).
  • the herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
  • Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
  • the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g.
  • herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% by weight in liquid emulsifiable suspension concentrates and up to 25% by weight in liquid water soluble concentrates.
  • suitable solid diluents or carriers are aluminium silicate, microfine silicon dioxide, talc, chalk, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite.
  • suitable solid diluents or carriers are aluminium silicate, microfine silicon dioxide, talc, chalk, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite.
  • Granular formulations may be prepared by absorbing the compounds of formula (I) (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by granulating compositions in powder form obtained as described above.
  • Solid herbicidal compositions, particularly wettable powders and granules may contain wetting or dispersing agents (for example of the types described above), which may also, when solid, serve as diluents or carriers.
  • Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may inco ⁇ orate a surface-active agent.
  • Suitable liquid diluents for inco ⁇ oration in the liquid compositions include water, glycols, glycol ethers, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, N-alkyl pyrrolidones, toluene, xylene, mineral, animal and vegetable oils, esterified vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents).
  • Surface-active agents, which may be present in the liquid compositions may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers.
  • Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
  • suitable diluents for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
  • liquid compositions of the compound of formula (I) may be used in the form of self-emulsifying concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of such concentrates to water producing compositions ready for use.
  • Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
  • Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, spreading agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents.
  • Preferred herbicidal compositions according to the present invention areaqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula (I), from 2 to 10% of surface-active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water; wettable powders which comprise from 10 to 90% of one or more compounds of formula (I), from 2 to 10% of surface-active agent and from 8 to 88% of solid diluent or carrier; water soluble or water dispersible powders which comprise from 10 to 90% of one or more compounds of formula (I), from 2 to 40% of sodium carbonate and from 0 to 88% of solid diluent; liquid water soluble concentrates which comprise from 5 to 50%, e.g.
  • liquid emulsifiable suspension concentrates which comprise from 10 to 70% of one or more compounds of formula (I), from 5 to 15% of surface-active agent, from 0.1 to 5% of thickener and from 10 to 84.9% of organic solvent, e.g. mineral oil; water dispersible granules which comprise from 1 to 90%, e.g. 25 to 75% of one or more compounds of formula (I), from 1 to 15%, e.g.
  • emulsifiable concentrates which comprise 0.05 to 90%, and preferably from 1 to 60% of one or more compounds of formula (I), from 0.01 to 10%, and preferably from 1 to 10%, of surface-active agent and from 9.99 to 99.94%, and preferably from 39 to 98.99%, of organic solvent.
  • Herbicidal compositions according to the present invention may also comprise the compounds of formula ⁇ !) in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
  • herbicides for example to increase the range of weed species controlled for example alachlor [2-chloro-2,6'- diethyl-N-(methoxy-methyl)-acetanilide], amidosulfuron, which is 1- (4,6-dimethoxypyrimidin-2-yl)-3-mesyl(methyl)sulfamoylurea, atrazine [2-chloro-4-ethylamino-6-isopropylamino- 1 ,3,5-triazine], bromoxynil [3,5-dibromo-4-hydroxybenzonitrile], chlortoluron [N'-(3-chloro-4- methylphenyl)-N,N-dimethylurea], cinidon-ethyl, which is ethyl (Z)-2- chloro-3-[2-chloro-5-( 1 )
  • synthetic pyrethroids e.g. permethrin and cypermethrin
  • fungicides e.g. carbamates, e.g. methyl N-(l-butyl- carbamoyl- benzimidazol-2-yl)carbamate, and triazoles e.g. l-(4-chloro- phenoxy)-3 ,3- dimethyl- 1 -( 1 ,2,4-triazol- 1 -y I)-butan-2-one.
  • Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids or bases, may, if desired, be utilized in the form of conventional derivatives, for example alkali metal and amine salts and esters.
  • the following Examples illustrate herbicidal compositions according to the present invention. The following trade marks appear in the Examples: Synperonic, Solvesso, Arylan, Arkopon, Sopropon, Tixosil, Soprophor, Attagel, Rhodorsil.
  • the Active Ingredient listed in the following examples refers to compounds of general formula (I).
  • Example Cl An emulsifiable concentrate is formed from:
  • NMP N-Methylpyrrolidinone
  • CaDDBS Calcium dodecylbenzenesulphonate
  • NPEOPO Nonylphenol ethylene oxide propylene oxide condensate
  • Aromatic solvent Solvesso
  • a wettable powder is formed from:
  • a suspension concentrate is formed from: Active Ingredient 50% w/v
  • Attaclay (Attagel) 1.5% w/v
  • a water dispersible granule is formed from: Active Ingredient 50% w/w
  • Microfine silicon dioxide (Tixosil 38) 3% w/w by blending the above ingredients together, grinding the mixture in an air jet mill and granulating by addition of water in a suitable granulation plant (e.g. Fluid bed drier) and drying.
  • a suitable granulation plant e.g. Fluid bed drier
  • the active ingredient may be ground either on its own or admixed with some or all of the other ingredients.
  • Seed of various broad-leaf and grass weed species were sown and herbicide, dissolved in a mixture of acetone and water, was applied at a rate of 62g/ha to the soil surface.
  • the said weeds are Amaranthus retroflexus. Abutilon theophrasti. Galium aparine. Setaria viridis. Alopecurus myosuroides. A vena fatua and Echinochloa crus-galli.
  • a method of reducing phytotoxicity to crop plants caused by compounds of formula (I) which comprises applying generally to the crop plant locus or crop plant seed an antidotally effective amount of an antidote effective to said compound.
  • the crops that may be protected by the method of the invention include cereal crops corn, rice, wheat, soybean, sorghum and cotton.
  • the method of the invention is preferably performed where the crop to be protected is maize or a cereal crop, particularly wheat.
  • the amount of antidote used in the compositions of the invention varies according to a number of parameters including the particular antidote employed, the crop to be protected, the amount and rate of herbicide applied, and the edaphic and climatic conditions prevailing. Also, the selection of the specific antidotes for use in the method of the invention, the manner in which it is to be applied and the determination of the activity which is non-phytotoxic but antidotally effective, can be readily performed in accordance with common practice in the art.
  • non-phytotoxic is meant an amount of the antidote which causes at most minor or no injury to the desired crop species.
  • antidotally effective is meant an antidote used in an amount which is effective as an antidote to decrease the extent of injury caused by the herbicide to the desired crop species.
  • the weight ratio of herbicide (a) to antidote (b) is from about 16: 1 to about 0.25: 1, preferably from about 8: 1 to about 0.5: 1, more preferably from 2: 1 to about 1: 1.
  • antidotes suitable for use in the present invention include the following (in which alkyl, alkenyl, alkynyl and alkoxy groups and moieties thereof are 'lower' as hereinbefore defined; cycloalkyl and phenyl groups are optionally substituted as hereinbefore defined; halogen is as hereinbefore defined; cycloalkenyl groups have from three to six carbon atoms in the ring and are optionally substituted by lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl and halogen; and bicycloalkyl means a saturated fused bicycloalkane one ring of which contains from 5 to 8 carbon atoms and the other ring contains from 3 to 6 carbon atoms and is optionally substituted by lower alkyl or halogen): (i) a compound of the formula (VITI):
  • R and R which may be the same or different, are selected from the group consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; haloalkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino; formyl; haloalkyl-N-alkylamido; haloalkylamido; haloalkylamidoalkyl; haloalkyl-N-alkylamidoalkyl; haloalkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalky
  • Especially preferred antidotes for use in the present invention include: cloquintocet, cloquintocet-mexyl, fenchlorazole, fenchlorazole- ethyl, benoxacor and R29148.
  • Herbicide, furilazole, benoxacor, dichlormid, cloquintocet, fenchlorazole, naphthalic anhydride and R29148 were applied as technical materials prepared in acetone. Mixtures of the Herbicide and safeners were applied post-emergence. Two weeks after treatment the percent reduction in plant growth, compared to an untreated control (the Herbicide sprayed alone), was assessed.
  • the safeners provided an antidotal effect on maize and wheat by decreasing the extent of injury caused by the Herbicide.
  • EXPERIMENTAL EXAMPLE 4 Representative compounds of formula (I), Compounds 2 and 82 and cloquintocet-mexyl, were applied as technical materials prepared in acetone to a locus comprising a natural population of Galium aparine and wheat (Triticum aestivum).
  • the percent reduction in plant growth, compared to an untreated control was assessed 20 and 33 days after treatment (DAT).
  • a product comprising: (a) an aryl vinyl ether derivative as defined in general formula (I) or an agriculturally acceptable salt or metal complex thereof, and (b) an antidote as hereinbefore described; as a combined preparation for simultaneous, separate or sequential use, for example, in controlling the growth of weeds at a locus, e.g. crop locus.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Furan Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pyridine Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

L'invention concerne des dérivés d'arylvinyléther représentés par la formule générale (I). Pour les besoins de ladite formule, les substituants sont tels que définis dans l'invention. L'invention concerne en outre des compositions renfermant les dérivés considérés, ainsi que des procédés et des intermédiaires utilisés pour leur élaboration. L'invention concerne enfin un procédé permettant d'éliminer les mauvaises herbes en utilisant ce type de composition.
EP99940084A 1998-07-16 1999-07-16 Derives d'arylvinylether et leur utilisation comme herbicides Withdrawn EP1097117A2 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GB9815508 1998-07-16
GBGB9815508.8A GB9815508D0 (en) 1998-07-16 1998-07-16 New herbicidal compositions
GB9816783 1998-07-31
GBGB9816783.6A GB9816783D0 (en) 1998-07-16 1998-07-31 New herbicidal compositions
GBGB9826903.8A GB9826903D0 (en) 1998-07-16 1998-12-07 New herbicidal compositions
GB9826903 1998-12-07
PCT/EP1999/005470 WO2000003975A2 (fr) 1998-07-16 1999-07-16 Derives d'arylvinylether et leur utilisation comme herbicides

Publications (1)

Publication Number Publication Date
EP1097117A2 true EP1097117A2 (fr) 2001-05-09

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Application Number Title Priority Date Filing Date
EP99940084A Withdrawn EP1097117A2 (fr) 1998-07-16 1999-07-16 Derives d'arylvinylether et leur utilisation comme herbicides

Country Status (4)

Country Link
EP (1) EP1097117A2 (fr)
JP (1) JP2002520384A (fr)
AU (1) AU5415899A (fr)
WO (1) WO2000003975A2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9930703D0 (en) * 1999-12-24 2000-02-16 Rhone Poulenc Agrochimie New herbicidal compositions
DE10139465A1 (de) * 2001-08-10 2003-02-20 Bayer Cropscience Ag Selektive Herbizide auf Basis von substituierten, cayclischen Ketoenolen und Safenern
KR20050029209A (ko) 2002-07-15 2005-03-24 미리어드 제네틱스, 인크. 화합물, 조성물 및 이의 사용방법
AP3539A (en) * 2010-08-31 2016-01-13 Meiji Seika Pharma Co Ltd Pest control agent
CN103319421B (zh) * 2013-06-07 2016-06-08 常州大学 一种嘧啶水杨酸类除草剂嘧啶肟草醚的制备方法
WO2020262648A1 (fr) * 2019-06-28 2020-12-30 住友化学株式会社 Dérivé d'ester (méth)acrylique, et application et intermédiaire de production de celui-ci

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
DE3904931A1 (de) * 1989-02-17 1990-08-23 Bayer Ag Pyridyl-substituierte acrylsaeureester
DE4019307A1 (de) * 1990-06-16 1991-12-19 Bayer Ag 2-methoximinocarbonsaeureester
FR2751642B1 (fr) * 1996-07-24 1998-09-11 Hoechst Schering Agrevo Sa Nouveaux derives de l'acide beta-methoxy acrylique, leur procede de preparation et leur application comme pesticides
CN1251575A (zh) * 1997-04-01 2000-04-26 住友化学工业株式会社 肟醚化合物,其用途和制备肟醚化合物的中间体
DE19745376A1 (de) * 1997-10-14 1999-04-15 Bayer Ag Thiomide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0003975A3 *

Also Published As

Publication number Publication date
AU5415899A (en) 2000-02-07
WO2000003975A3 (fr) 2000-08-03
JP2002520384A (ja) 2002-07-09
WO2000003975A2 (fr) 2000-01-27

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