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WO2000003975A2 - Aryl vinyl ether derivatives and their use as herbicides - Google Patents

Aryl vinyl ether derivatives and their use as herbicides Download PDF

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Publication number
WO2000003975A2
WO2000003975A2 PCT/EP1999/005470 EP9905470W WO0003975A2 WO 2000003975 A2 WO2000003975 A2 WO 2000003975A2 EP 9905470 W EP9905470 W EP 9905470W WO 0003975 A2 WO0003975 A2 WO 0003975A2
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WIPO (PCT)
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.)
Ceased
Application number
PCT/EP1999/005470
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French (fr)
Other versions
WO2000003975A3 (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
Rhone Poulenc Agriculture Ltd
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Filing date
Publication date
Priority claimed from GBGB9815508.8A external-priority patent/GB9815508D0/en
Application filed by Aventis Agriculture Ltd, Rhone Poulenc Agriculture Ltd filed Critical Aventis Agriculture Ltd
Priority to JP2000560084A priority Critical patent/JP2002520384A/en
Priority to AU54158/99A priority patent/AU5415899A/en
Priority to EP99940084A priority patent/EP1097117A2/en
Publication of WO2000003975A2 publication Critical patent/WO2000003975A2/en
Publication of WO2000003975A3 publication Critical patent/WO2000003975A3/en
Anticipated expiration legal-status Critical
Ceased 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
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    • 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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    • 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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    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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 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 10 represents a radical selected from
  • 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 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 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;
  • 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.
  • 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 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 .
  • 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.
  • 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.
  • 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).
  • 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
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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
  • 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.
  • 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).

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Abstract

The invention relates to aryl vinyl ether derivatives of general formula (I), wherein the substituents are as defined in the description; compositions containing them, processes and intermediates for their preparation and a method of controlling weeds by means of such compositions.

Description

ARYL VINYL ETHER DERIVATIVES AND THEIR USE AS HERBICIDES
Background of the invention
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.
It is known that many herbicides may injure crop plants at herbicide application rates needed to control weed growth. This renders many herbicides unsuitable for controlling weeds in the presence of certain crops. Where weed growth in crops is uncontrolled however, this results in lower crop yield and reduced crop quality, as weeds will compete with crops for nutrients, light and water. Reduction in herbicidal injury to crops without an unacceptable reduction in the herbicidal action can be accomplished by use of crop protectants known as " antidotes ", also sometimes referred to as " safeners " or "antagonists".
Aryl vinyl ether compounds under certain conditions can produce damage in crop plants, particularly cereal crop plants such as maize and -?-
wheat, and it is therefore a further object of the present invention to provide a method for reducing the damage caused to crop plants by aryl vinyl ether compounds.
These and other objects of the instant invention can be achieved in whole or in part by means of the compounds of the invention.
Description of the Invention
The present invention provides compounds of formula (I):
Figure imgf000004_0001
(D wherein: p is O or 1, X' is O. NH or S;
X2 is O, S, NR18 or a simple bond (preferably O, S or NR18); X3 is N or CR19;
R17 and R18 independently represent a hydrogen atom or an optionally substituted group R , R , R or R , wherein; R20 represents a lower alkyl radical; R21 represents a lower alkenyl radical; R22 represents a lower alkynyl radical; R23 represents a -(CH2)m-phenyl radical; m represents zero or one; R16 is R24 or OR25 or SR25, NR25R26 or alkyl substituted by alkoxycarbonyl;
R24, R2 and R independently have one of the meanings given for R18; R19 has one of the meanings given for R16;
R10 represents a radical selected from;
-CH2NO2, -CHR27R28,-CR27R28R281, -CR30R29R291, -CO-NR30R31, -CH2NR30R31, -CH=CR31R32, -CH2N(R30)S(O)qR33, -C(O)SR32, -CH2 C(O)SR32, -(CH2)zCO2R32, -CO2R32, -CH=CHC(O)OR32, -C(R32)=N- NR30R31, -C(R32)=N-NH-C(O)Iower alkyl, -COR32, -C(O)OC(O)R32, -
C(=N-OH)R32, -C≡CCOOR32, -CH2SCN, -CH2NCO, -CH2NCS, - CH2N3, -CH2CN, -CH2OSCN, -CH2OCN, -CH2N(R30)CO2R33, - CH2OSO2R33, -CH2SO2OR33, -CH2OCO2R33, -CH=CHNR33R34, - C(O)ONR33R34, -C(=NR35)R32, -CH2P(O)R35 R36 , -CH2 OP(O)R35R36, -CH2OC(O)NR30R36, -CH2OCH2C(O) (optionally substituted phenyl),
-CO2N=C (optionally substituted phenyl)2, N-succinimidomethyl, N- phthalimidomethyl, a tetrazolyl group (especially l-tetrazolyl), - CONHNHR30, -CO2CH2CO (optionally substituted phenyl, or a saturated or unsaturated 5-7 membered heterocyclic ring containing from 1-3 hetero atoms selected from O, N and S), -CO2CH2 (saturated or unsaturated 5-7 membered heterocyclic ring containing from 1-3 hetero atoms selected from O, N and S), CO2 R32a, COCH2COR33, COCHN2, CONH (lower alkyl substituted by hydroxy), - CH(OH)(lower alkyl), C(R32)=N-NH-C(S)NRa, C(R32)=N-NH (optionally substituted unsaturated 5-7 membered heterocyclic ring containing from 1-3 atoms selected from O, N and S), C(R32)=N- NR30aR31a, C(R3 )=N-NHSO2 R33 and C(O)F; z represents one, two, three or four; q represents zero or two; Ra represents H or lower alkyl;
R represents an optionally substituted N-linked imidazole or triazole ring optionally fused to a benzene ring; R30a and R3 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 NRa group in the ring;
R27, R28 and R281 represent the same or different halogen atoms; R29 and R291 represent OR37 or SR37 or,
R29 and R291 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; R30, R31 and R32 independently represent hydrogen, lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted -(CH2)m-phenyl;
R33 and R34 represent R32 with the exclusion of the hydrogen atom;
R35 and R36 represent a hydrogen atom or a radical which may be any of the following ; alkyl, alkoxy or optionally substituted phenyl;
R37represents lower alkyl, lower haloalkyl, lower alkenyl or lower haloalkenyl ; R1 'and R13 each independently represent hydrogen or alkyl, or
Ru and R13 may be together a simple bond creating a double bond with the carbon atom to which they are attached, or
Ru and R13 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 R15 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 haloalkyl, lower haloalkenyl, lower haloalkynyl, halocycioalkyl, lower haloalkoxy, lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkylsulfonyl, nitro, amino, lower alkylamino, lower dialkylamino, optionally substituted phenoxy, lower alkylcarbonylamino, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, -CH2SCN, SF5, -CR30=N-R3\ -CR30=NOR31, -CR30=NNR30 R3 , ) -CR30R29R291, alkoxyalkyl, CRbRcRa, CORa, optionally substituted phenyl or naphthyl; or alkenyloxy substituted by alkoxycarbonyl or CO2H;
Rb and Rc together with the C atoms to which they are attached form a 5 or 6 -membered cyclic acetal group;
or R 1,0υRr
Figure imgf000008_0001
represents a group (A), (B), (C), (D) or (E):
Figure imgf000008_0002
(A) (B)
Figure imgf000008_0003
(C) (D)
Figure imgf000008_0004
(E)
wherein Rd, Rc, Rf, Rg and Rh represent H, lower alkyl, halogen or OH, and n represents the values 0, 1, 2 or 3;
R1 ' represents R or a hydrogen atom; R12 and R14 each independently represent hydrogen or alkyl or may form a simple bond, creating a double bond together where R1 1 and R13 are together a single divalent radical; preferably with the following provisos; i) when R10RπR12C-C(RI3)(R14)- represents a phenyl ring optionally substituted by R15; R10 represents -CO2 R32, CONR30R31, CHR27R28 or CR27 R28 R281, wherein R32 represents alkyl or haloalkyl; R30 and R31 represent H or alkyl, and R27, R28 and R281 are as defined above; p is zero; X. is O; X2 is O; X3 is CH; R16 is OR25; then R15 is not a monohalomethyl group; ii) when R10RUR,2C-C(R13)(R14)- represents a group EtO2C-CH=CH-; p is 1 ; Xj is S; X2 is a bond; Rl7represents phenyl; X3 is CH; then R16 is not NH or NMe2; iii) when Ru, R12, R13, R14 each represent H; p is 1; Xj is S, X2 is O; R17 represents Et; X3 is N; R16 represents -NH(4- nitrophenyl); R10 is not CO2H or CONHPh; iv) when R , R , R , R each represent H; p is zero; X] is S, X2 is O; R17 represents Et; X3 is N; R16 represents -NH(4- nitrophenyl); R10 is not CO2H or CONH2; v) when p represents zero; X] is O; X2 is a bond; R17 represents H; X3 is CH; R16 represents NMe2; R10RUR12C-C(R13)(R14)- represents a 5-methyl-2-R -substituted-thien-3-yl group; R10 is not CO2H or CO2Me; vi) when R , R , R and R each represent H; p is zero; Xi is S; X2 is O, R17 represents H; X3 is N; R16 represents -NH(4- nitrophenyl); R10 is not CO2H; vii) when R10 represents CO2Et; R11, R12, R13 and R14 each represent H; p is zero; Xi is S; X2 is NH, R17 represents phenyl; X3 is CMe; R16 is not NH2 or NHMe; and viii) when p is zero; Xi. is O; X2 is O; R17 represents Me; X3 is CH; R16 represents OMe; R, 0R"R12C-C(R13)(R14)- represents a l,3-dimethyl-4- R10-substituted-pyrazol-5-yl group; R10 is not 4- chlorobenzoyl; and agriculturally acceptable salts and metal complexes thereof which have valuable herbicidal properties. It will be understood that while compounds of formula (I) listed in the provisos i) to viii) above are not considered per se part of the invention, their use as herbicides, and compositions containing them does form part of the invention.
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 R10, R11, R12, R13, R14 and R17 are as defined above, X3 is CR19 and in which R16 is OR25 wherein R is hydrogen, may exist in a tautomeric form and acetal forms thereof. By the term "agriculturally acceptable salts" is meant salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. 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. Suitable acid addition salts, e.g. formed by 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. In the above definitions used in formula (I) all of the optionally substituted groups may have as the optional substituent one or more halogen atoms, among other possible substituents.
Among the optional substituents for cycloalkyl radicals, the following may be selected; lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl and halogen.
Among the optional substituents for 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.
In the present patent specification, including the accompanying claims, certain atoms and groups have the following meanings: halogen atom means fluorine, chlorine, bromine or iodine; the 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.
Among the compounds represented by general formula (I) described above, preferred groups of the compounds include those compounds of general formula (I) in which;
Rπ and R13 form a non-saturated carbocyclic ring (preferably phenyl) substituted by a halogen atom (preferably chlorine or fluorine); or R11 and R13 represent a pyridine ring; or R1 1 and R13 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; X3 is CR19 wherein R19 represents a hydrogen atom; X2 is an oxygen atom;
Xi is an oxygen or sulphur atom (preferably an oxygen atom); R16 is a hydrogen atom or lower alkyl group (preferably methyl) or OR25 wherein R25 represents a lower alkyl group or a hydrogen atom
(most preferably R16 is methoxy);
R17 is a hydrogen atom or lower alkyl group (preferably methyl). Compounds in which R10 is -CHR27R28 (in which R27 and R28 are preferably bromine), or -COR32 or -CO2R32 (in which R32 is preferably lower alkyl or hydrogen), or -CH2OSO2R33 (preferably R33 represents substituted phenyl), or -CH2NO2, or -CH2OCH2C(O)Ph, or -CH2OTs, or -C(R32)=N-NHSO2R33 (in which R32 is hydrogen and R33 is lower alkyl), or -C(R32)=N-NH-C(S)NRa (in which R32 is hydrogen and Ra is lower alkyl), or -C(R32)=N-NR30R3I(in which R32 and R30 are hydrogen and R31 is optionally substituted -(CH2)m-phenyl), or
-C(R32)=N-N30aR31a (in which R32 is hydrogen, and R30a and R3 Ia together with the N atom to which they are attached form a 6 membered saturated heterocyclic ring containing an additional O and NRa group in the ring), or -C(R )=N-NH(optionally substituted unsaturated 6 membered heterocyclic ring containing a nitrogen atom) (in which R32 is hydrogen), or -C(O)F, or -CO2CH2CO(optionally substituted phenyl), or -CO R32a (in which R32a is an optionally substituted N-linked triazole ring fused to a benzene ring), or -CO-NR30R3I(in which R30 is hydrogen and R31 is lower alkyl), or -CONHNHR30 (in which R30 is optionally substituted -(CH2)m-phenyI), or -C(R32)=NNH-C(O)lower alkyl (in which R32 is hydrogen), or -C(O)SR32 (in which R32 is lower alkyl) or -CH(OH)lower alkyl, or -COCHN2, or -CR30R29R291 (in which R30 is hydrogen, and R and R together form a divalent radical with which the carbon atom to which they are attached forms a 5 membered optionally substituted thioacetal ring), or -C(=N-OH)R32 (in which R32 is lower alkyl), or -(CH2)zCO2R (in which R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxyalkyl, optionally substituted -(CH2)m-phenyl); or R10RUR12C-C(R13)(R14)- represents a group A in which Rd and Rc represent hydrogen or halogen; and R is -COR\ or halogen, or lower alkyl, or lower alkoxy, or lower haloalkoxy, or lower alkoxycarbonyl, or CRbRcRa (in which Rb and Rc form a 5 membered cyclic acetal group and in which Ra represents hydrogen) are also preferred.
A preferred class of compounds of formula (I) are those in which: Rn and R13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups; X3 is CR19 wherein R19 represents a hydrogen atom; Xi and X each represent an oxygen atom; R16 and RI7 each represent a methyl group; and R10 is -CO2R32.
A most preferred class of compounds of formula (I) are those in which:
R11 and R13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups; X is CR19 wherein R19 represents a hydrogen atom; Xi and X2 each represent an oxygen atom; R and R each represent a methyl group; and R is -CO2R in which R32 is lower alkyl or hydrogen.
The following compounds are particularly preferred:
1. methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3- methoxypropenoate;
2. methyl 2-(2-carboxy-4-chlorophenoxy)-3-methoxypropenoate; 3. methyl 2-(2-carboxy-4-iodophenoxy)-3-methoxypropenoate;
4. methyl 2-(2-dibromomethyl-4-chlorophenoxy)-3- methoxypropenoate;
5. methyl 2-(2-formyl-4-chlorophenoxy)-3-methoxypropenoate;
6. methyl 2-[4-chloro-2-((N-methyI-N- phenylamino)methyl)phenoxy]-3-methoxypropenoate;
7. methyl 2-[4-chloro-2-(N-allylamino)methyl)phenoxy]-3- methoxypropenoate; 8. methyl 2-[4-chloro-2-(N-benzylamino)methyI)phenoxy]-3- methoxypropenoate;
9. methyl 2-[4-chloro-2-(N-cyclopropylamino)methyl)phenoxy]- 3-methoxypropenoate; 10. methyl 2-[4-chloro-2-(azidomethyl)phenoxy]-3- methoxypropenoate;
11. methyl 2-[4-chloro-2-(N-succinimidomethyl)phenoxy]-3- methoxypropenoate;
12. methyl 2-[4-chloro-2-(N-phthalimidomethyl)phenoxy]-3- methoxypropenoate;
13. methyl 2-[4-chloro-2-(N-isopropyl-N- (methanesulfonyl)aminomethyl)phenoxy]-3-methoxypropenoate;
14. methyl 2-[4-chloro-2-(N-methyl-N- (methanesuIfonyl)aminomethyl)phenoxy]-3-methoxypropenoate; 15. methyl 2-[4-chloro-2-(N-(methoxycarbonyl)aminomethyl)- phenoxy]-3-methoxypropenoate;
16. methyl 2-(4-chloro-2-(nitromethyl)phenoxy)-3- methoxypropenoate;
17. methyl 2-(4-chloro-2-(cyanomethyl)phenoxy)-3- methoxypropenoate;
18. methyl 2-(4-chloro-2-(thiocyanomethyl)phenoxy)-3- methoxypropenoate;
19. methyl 2-(4-chloro-2-methoxycarbonylphenoxy)-3- methoxypropenoate; 20. methyl 2-(4-chloro-2-ethoxycarbonylphenoxy)-3- methoxypropenoate;
21. methyl 2-(4-chloro-2-N-(4-trifluoromethoxyphenyl)- aminocarbonyl)phenoxy-3-methoxypropenoate;
22. 2-(4-chloro-2-N-(2-chloro-4-(ethoxycarbonyl)phenyl)- aminocarbonyl)phenoxy-3-methoxypropenoate;
23. 2-(4-chloro-2-N-(3,5-difluorophenyl)aminocarbonyl)phenoxy- 3-methoxypropenoate; 24. 2-(4-chloro-2-N-(3-trifluoromethylphenyl)aminocarbonyI)- phenoxy-3-methoxypropenoate;
25. 2-(4-chloro-2-N-(3,5-dichlorophenyl)aminocarbonyl)phenoxy- 3-methoxypropenoate; 26. 2-(4-chloro-2-N-(2,6-difluorophenyl)aminocarbonyl)phenoxy-
3-methoxypropenoate;
27. 2-(4-chloro-2-N-(4-bromo-3-trifluoromethylphenyl)- aminocarbonyl)phenoxy-3-methoxypropenoate;
28. 2-(4-chloro-2-N-(3-chlorophenyI)aminocarbonyl)phenoxy-3- methoxypropenoate;
29. 2-(4-chloro-2-N-(5-chloro-2-methylphenyl)aminocarbonyl)- phenoxy-3-methoxypropenoate;
30. 2-(4-chloro-2-N-(2,5-difluorophenyl)aminocarbonyl)phenoxy- 3-methoxypropenoate; 31. 2-(4-chloro-2-N-(3-phenoxyphenyl)aminocarbonyl)phenoxy-3- methoxypropenoate;
32. 2-(4-chloro-2-N-(3-bromo-5-trifluoromethylphenyl)- aminocarbonyl)phenoxy-3-methoxypropenoate;
33. 2-(4-chloro-2-N-(3,5-dibromophenyl)aminocarbonyl)phenoxy- 3-methoxypropenoate;
34. 2-(4-chloro-2-N-(5-methoxy-2-methylphenyl)aminocarbonyl)- phenoxy-3-methoxypropenoate;
35. methyl 2-(4-chloro-2-acetylaminoiminomethylenephenoxy)-3- propenoate; 36. methyl 2-(4-chloro-2-hydroxyiminomethylenephenoxy)-3- propenoate;
37. methyl 2-(4-chloro-2-methoxyiminomethylenephenoxy)-3- propenoate;
38. methyl 2-(4-chloro-2-ethoxyiminomethylenephenoxy)-3- propenoate;
39. methyl 2-(4-chloro-2-aIlyloxyirninomethylenephenoxy)-3- propenoate; 40. methyl 2-(4-chloro-2-t-butyIoxyiminomethylcnephenoxy)-3- propenoate;
41. methyl 2-(4-chloro-2-benzyIoxyiminomethylenephenoxy)-3- propenoate; 42. methyl 2-(4-chloro-2-phenoxyiminomethylenephenoxy)-3- propenoate;
43. methyl 2-(2-carboxy-4-chlorophenoxy)-3 -methoxypropenoate, sodium salt;
44. methyl 2-(4-chloro-2-(2-methoxycarbonylethenyl)phenoxy)-3- methoxypropenoate;
45. methyl 2-(2-carboxy-4-medιylphenoxy)-3- methoxypropenoate;
46. methyl 2-[2-carboxy-3-(2-methoxy-l- methoxycarbonyl viny loxy)phenoxy] -3 -methoxypropenoate; 47. 2,4-dichlorophenyl 2-(2-carboxy-4-chlorophenoxy)-(3- methoxy)thiopropenoate;
48. methyl 2-(2-carboxy-4-chlorophenoxy)-3-(l-ethoxy carbonyl)ethoxypropenoate;
49. methyl 2-(2-carboxy-4-chlorophenoxy)-3-prop-2-yn yloxypropenoate;
50. methyI 2-{4-chloro-2-[N'-(2- chlorophenyl)hydrazinocarbonyl]phenoxy}-3-methoxypropenoate;
51. methyl 2-[4-chloro-2-(prop-2-ynyloxycarbonyl)phenoxy]-3- methoxypropenoate; 52. methyl 2-[2-(benzyloxycarbonyl)-4-chlorophenoxy]-3- methoxypropenoate;
53. methyl 2-[4-chloro-2-(propyloxycarbonyl)phenoxy]-3- methoxypropenoate;
54. methyl 2-[2-(butyloxycarbonyl)-4-chlorophenoxy]-3- methoxypropenoate;
55. methyl 2-[4-chloro-2-(prop-2-yloxycarbonyl)phenoxy]-3- mcthoxypropenoate; 56. methyl 2-[4-chloro-2-(3-chloropropyloxycarbonyl) phenoxy]- 3-methoxypropenoate;
57. methyl 2-[4-chloro-2-(but-2-yIoxycarbonyl)phenoxy]-3- methoxypropenoate; 58. methyl 2-[4-chloro-2-(3-pentyloxycarbonyl)phenoxy]-3- methoxypropenoate;
59. methyl 2-[4-chloro-2-(hept-2-yIoxycarbonyl)phenoxy]-3- methoxypropenoate;
60. methyl 2-[4-chloro-2-(octyloxycarbonyl)phenoxy]-3- methoxypropenoate;
61. methyl 2-[4-chloro-2-(cyclopentyloxycarbonyl)phenoxy]-3- methoxypropenoate;
62. methyl 2-[4-chloro-2-(2-methoxyethoxycarbonyl) phenoxy]-3- methoxypropenoate; 63. methyl 2-[4-chloro-2-(2-ethoxyethoxycarbonyl)phenoxy]-3- methoxypropenoate;
64. methyl 2-[4-chloro-2-(cyclopropylmethoxycarbonyl) phenoxy]-3-methoxypropenoate;
65. methyl 2-(4-methoxy-2-methoxycarbonylphenoxy)-3- methoxypropenoate;
66. methyl 2-[2-(benztriazol-l-yloxycarbonyI)-4-chlorophenoxy]- 3-methoxypropenoate;
67. methyl 2-[4-chloro-2-(4-nitrophenoxycarbonyl)phenoxy]-3- methoxypropenoate; 68. methyl 2-[4-chloro-
2-(2,4,5-trichlorophenoxycarbonyl)phenoxy]-3-methoxypropenoate;
69. methyl 2-[4-chloro-2-(2,3,4,5,6- pentachlorophenoxycarbonyl)phenoxy]-3-methoxypropenoate;
70. methyl 2-[4-chloro-2-(ethyIcarbamoyl)phenoxy]-3- methoxypropenoate;
71. methyl 2-[4-chloro-2-(ethylthiocarbonyl)phenoxy]-3- methoxypropenoate ; 72. methyl 2-(2-carboxy-4-methoxyphenoxy)-3- methoxypropenoate;
73. butyl 2-(2-carboxy-4-chlorophenoxy)-3-methoxypropenoate;
74. methyl 2-(2-carboxy-3-fluorophenoxy)-3-methoxypropenoate; 75. methyl 2-(2-carboxy-3-chlorophenoxy)-3-methoxypropenoate;
76. methyl 2-(2-carboxy-3-methylphenoxy)-3- methoxypropenoate;
77. methyl 2-(2-carboxy-4-chlorophenoxy)-3- methylthiopropenoate; 78. methyl 2-(2-carboxyphenoxy)-3-methoxypropenoate;
79. methyl 2-(l-carboxynaphth-2-yloxy)-3-methoxypropenoate;
80. methyl 2-(2-carboxy-3,4 difIuorophenoxy)-3- methoxypropenoate;
81. methyl 2-(2-carboxy-3-chloro-4-fluorophenoxy)-3- methoxypropenoate;
82. methyl 2-(2-carboxy-4-chloro-3-fluorophenoxy)-3- methoxypropenoate;
83. methyl 2-(2-carboxy-4-difluoromethylphenoxy-3- methoxypropenoate; 84. methyl 2-(4-bromo-2-carboxyphenoxy)-3- methoxypropenoate;
85. methyl 2-(2-carboxy-4-fluorophenoxy)-3-methoxypropenoate;
86. methyl 2-(3-bromo-2-carboxyphenoxy)-3- methoxypropenoate; 87. methyl 2-(2-carboxy-3-thiocyanatomethylphenoxy)-3- methoxypropenoate;
88. methyl 2-(3-acetoxymethyI-2-carboxyphenoxy)-3- methoxypropenoate;
89. methyl 2-(2-carboxy-3,4-dichlorophenoxy)-3- methoxypropenoate;
90. methyl 2-(2-carboxy-3-dihydroxymethylphenoxy)-3- methoxypropenoate; 91. methyl 2-(3-hydroxyphthalid-7-yloxy)-3-methoxypropenoate;
92. methyl 2-{4-chloro-2-[N'-(2,4-dichlorophenyl)hydrazino carbonyljphenoxy } -3-methoxypropenoate;
93. methyl 2- {4-chloro-2-[N'-(3- trifluoromethylphenyl)hydrazinocarbonyl]phenoxy } -3- methoxypropenoate;
94. methyl 2-[2-(2,2,2-trifluoroethoxycarbonyl)phenoxy]-3- methoxypropenoate;
95. methyl 2-[4-chloro-2-(2,2,2-trichIoroethoxycarbonyl) phenoxy]-3-methoxypropenoate;
96. methyl 2-{4-chloro-2-[(l-hydroxy-2-methylprop-2- yl)carbamoyl]phenoxy}-3-methoxypropenoate;
97. methyl 2-[4-methyl-2-(2,2,2-trifluoroethoxycarbonyl) phenoxy]-3-methoxypropenoate; 98. methyl 2-(3-fluoro-2-hexylthiocarbonylphenoxy)-3- methoxypropenoate;
99. methyl 2-[4-fluoro-2-(2-ethoxyethoxycarbonyl)phenoxy]-3- methoxypropenoate;
100. methyl 2-(4-bromo-2-methoxycarbonylphenoxy)-3- methoxypropenoate;
101. methyl 2-(4-fluoro-2-methoxycarbonyIphenoxy)-3- methoxypropenoate;
102. methyl 2-(2-ethoxycarbonyl-3-fluorophenoxy)-3- methoxypropenoate; 103. methyl 2-[3-fluoro-2-(prop-2-ynyloxycarboπyl)ρhenoxy]-3- methoxypropenoate;
104. methyl 2-(2-benzyloxycarbonyl-3-fluorophenoxy)-3- methoxypropenoate;
105. methyl 2-[3-fluoro-2-(2-methoxyethoxycarbonyl)phenoxy]- 3-methoxypropenoate;
106. methyl 2-[2-(2-ethoxyethoxycarbonyl)-3-fluorophenoxy]-3- methoxypropenoate; 107. methyl 2-[3-fluoro-2-(tetrahydrofuran-2-yImethoxycarbonyl) phenoxy]-3-methoxypropenoate;
108. methyl 2-[2-(3-chloropropyloxycarbonyI)-3-fluorophenoxy]- 3-methoxypropenoate; 109. methyl 2-(2-butyloxycarbonylphenoxy)-3- methoxypropenoate;
110. methyl 2-(2-pentyloxycarbonylphenoxy)-3- methoxypropenoate;
111. methyl 2-(2-octyloxycarbonylphenoxy)-3- methoxypropenoate;
112. methyl 2-[2-(3-chloropropyloxycarbonyl)phenoxy]-3- methoxypropenoate;
113. methyl 2-[2-(prop-2-ynyloxycarbonyl)phenoxy]-3- methoxypropenoate; 114. methyl 2-(2-benzyloxycarbonylphenoxy)-3- methoxypropenoate;
115. methyl 2-(2-carboxy-3,4-difluorophenoxy)-3- methoxypropenoate;
116. methyl 2-(2-carboxy-4-iodophenoxy)-3-methoxypropenoate sodium salt;
1 17. methyl 2-[3-methyl-2-(4- methylbenzyloxycarbonyl)phenoxy]-3-methoxypropenoate;
118. methyl 2-[2-(2-ethoxyethoxycarbonyl)-3,4- difluorophenoxy]-3-methoxypropenoate; 1 19. methyl 2-[3,4-difluoro-2-(4-methylbenzyloxycarbonyl) phenoxy]-3-methoxypropenoate;
120. methyl 2-(2-benzyloxycarbonyl-3,4-difluorophenoxy)-3- methoxypropenoate;
121. methyl 2-[2-(4-methylbenzoylmethoxycarbonyl) phenoxy]-3- methoxypropenoate;
122. methyl 2-[4-fluoro-2-(4-methylbenzoylmethoxycarbonyl) phenoxy]-3-methoxypropenoate; 123. methyl 2-[2-(4-nitrobenzoyImethoxycarbonyI)phenoxy]-3- methoxypropenoate;
124. methyl 2-[2-(3,4- dichlorobenzoylmethoxycarbonyl)phenoxy]-3-methoxypropenoate; 125. methyl 2-[2-(4-cyanobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate;
126. methyl 2-[4-chloro-2-(benzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate;
127. methyl 2-[2-(benzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate;
128. methyl 2-[4-chloro-2-(diphenylmethyIeneimino- oxycarbonyl)phenoxy]-3-methoxypropenoate;
129. methyl 2-[4-chloro-2-(3-cyclopropyI-3- oxopropanoyl)phenoxy]-3-methoxypropenoate; 130. methyl 2-[2-(pyrid-2-yIhydrazonomethylene)phenoxy]-3- methoxypropenoate;
131. methyl 2-[4-chloro-2-(N- methylsulphonylhydrazonomethylene)phenoxy]-3-methoxypropenoate;
132. methyl 2-[4-chloro-2-(2,4,6-trichlorophenylhydrazono methylene)phenoxy]-3-methoxypropenoate;
133. methyl 2- {4-chloro-2-[N-(4- mo hoIinyl)iminomethyIene]phenoxy } -3-methoxypropenoate;
134. methyl 2-[4-chloro- 2-(pyrid-2-ylhydrazonomethylene)phenoxy]-3-methoxypropenoate; 135. methyl 2-[4-chloro-2-(4- fluorophenylhydrazonomethylene)phenoxy]-3-methoxypropenoate;
136. methyl 2-[4-chloro-2-(4-nitrophenylhydrazonomethylene) phenoxy]-3-methoxypropenoate;
137. methyl 2-{4-chloro-2-[N-(dimethylthiocarbamoyl)hydrazonomethylene]phenox y)-3-methoxypropenoate; 138. methyl 2-[4-chloro-2-(l,3-dithiolan-2-yl)phenoxy]-3- methoxypropenoate;
139. methyl 2-[2-methoxycarbonyl-3-(2-methyl-l,3-dioxolan-2- yl) phenoxy]-3-methoxypropenoate; 140. methyl 2-(2-methoxycarbonylbenzyloxy)-3- methoxypropenoate;
141. methyl 2-(3-acetyl-2-methoxycarbonylphenoxy)-3- methoxypropenoate;
142. methyl 2-[4-chIoro-2-(l-hydroxyethyl)phenoxy]-3- methoxypropenoate;
143. methyl 2-[4-chloro-2-(diazoacetyI)phenoxy]-3- methoxypropenoate ;
144. methyl 2-[4-(3-acetamidophenyl)-2-carboxyphenoxy]-3- methoxypropenoate; 145. methyl 2-{2-carboxy-4-[3-fIuoro-4-phenyl]phenylphenoxy}-
3-methoxypropenoate;
146. methyl 2-[2-carboxy-4-(naphth-2-yl)phenoxy]-3- methoxypropenoate;
147. methyl 2-[4-(4-benzyloxyphenyl)-2-carboxyphenoxy]-3- methoxypropenoate;
148. methyl 2-[2~carboxy-4-(benzo-l,3-dioxolan-5-yI)phenoxy]- 3-methoxypropenoate;
149. methyl 2-[4-chloro-2-(methoxymethoxycarbonyl)phenoxy]- 3-methoxypropenoate; 150. methyl 2- {2-[2-
(methoxyethoxy)methoxycarbonyl]phenoxy} -3-methoxypropenoate;
151. methyl 2-[4-chloro-2-(fluorocarbonyl)phenoxy]-3- methoxypropenoate;
152. methyl 2-(3-formyl-2-methoxycarbonylphenoxy)-3- methoxypropenoate;
153. methyl 2-(3-dibromomethyl-2-carboxyphenoxy)-3- methoxypropenoate; 154. methyl 2-(3-bromophthalid-7-yloxy)-3-methoxypropenoate;
155. methyl 2-(phthalid-7-yloxy)-3-methoxypropenoate;
156. methyl 2-[4-chloro-2-(methylcarbamoyI)phenoxy]-3- methoxypropenoate; 157. methyl 2-(2-carboxy-4-chlorophenoxy)-3-ethoxypropenoate;
158. methyl 2-(2-carboxy-4-chlorophenoxy)-3-(2- trifluoromethoxybenzyloxy)propenoate;
159. methyl 2-{4-chloro-2-[N'-(4- fluorophenyl)hydrazinocarbonyl]phenoxy } -3-methoxypropenoate; 160. methyl 2-{4-chIoro-2-[N'-(4- methoxyphenyl)hydrazinocarbonyl]phenoxy } -3-methoxypropenoate;
161. methyl 2-[2-(2,2,2-trichloroethoxycarbonyl)phenoxy]-3- methoxypropenoate;
162. methyl 2-[3-fluoro-2-(2,2,2- trifluoroethoxycarbonyl)phenoxy]-3-methoxypropenoate;
163. methyl 2-[4-chloro-2-(2,2,2- trifluoroethoxycarbonyl)phenoxy]-3-methoxypropenoate;
164. methyl 2-[3-fluoro-2-(2,2,2- trichloroethoxycarbonyI)phenoxy]-3-methoxypropenoate; 165. methyl 2-(2-ethylthiocarbonyl-3-fluorophenoxy)-3- methoxypropenoate;
166. methyl 2-[2-(4-fluorobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate;
167. methyl 2-(3-dibromomethyl-2-methoxycarbonylphenoxy)-3- methoxypropenoate.
The numbers 1-167 are assigned to these compounds for reference and identification hereafter.
Specific examples of the compound of general formula (I), provided by the present invention are shown in Tables 1 to 14 hereinbelow, the compounds having the general formula 1-2, 1-3, 1-4, 1-5,
1-6, 1-7, 1-8, 1-9, 1- 10, 1- 1 1, 1-12, 1-13, 1-14 and 1-15. In the Tables, abbreviations used have the following meanings; Me means methyl, Et means ethyl, Pr means n-propyl, i-Pr means iso-propyl, c-Pr means cyclopropyi, Bu means n-butyl, Pen means pentyl, c-Pen means cyclopentyl, c-Hex means cyclohexyl, Bn means benzyl, Ph means phenyl and Ts means tosyl. Also, where numbers appear directly after atoms or groups they are understood to be subscripts, (e.g. CH3 means
CH3) CH2NO2 means CH2NO2) etc.)
Furthermore it is understood that the compounds in the following tables may represent either the Z or E isomers at the double bond of formula (I) which is substituted by R16 wherein R16 represents OR25, or represents a mixture of both isomers.
O 00/03975
-23-
Table 1
Figure imgf000025_0001
In formulae (1-2) and (1-7) below, R10 represents CO2R32, wherein R32 is as hereinbefore defined and in which R15, R25 and R17 have the meanings indicated hereinbelow. It is to be understood that in the following table, Identification Group I recites individual species in which R32 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 R15 group is located according to the numbering system in (I- 2) and (1-7) and when more than one R15 substituent is present, the various meanings have been placed in the same column.
Where R 4 1'5J represents -CR 3J
Figure imgf000025_0002
or - CR30=NN R30 R31, the meanings of R29, R291,R30and R31 are as defined hereinabove.
Figure imgf000025_0003
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0002
Table 2
Figure imgf000028_0001
(1-3)
In formulae (1-3 to 1-6 and 1-8 to 1-11), R10, R15, R25 and R17 have the meanings shown. The R15 group is located according to the numbering system in the formulae, and when more than one R15 substituent is present then the various meanings have been placed in the same column.
Where R15 represents -CR30=NOR31, -CR30R29R291 or CR30=NN R30 R31, the meanings of R29, R291,R30and R31 are as defined hereinabove.
Figure imgf000028_0003
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0002
Table 3
Figure imgf000031_0001
(1-4)
Figure imgf000031_0003
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0003
Table 4
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000034_0004
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0002
Table 5
Figure imgf000037_0001
(1-6)
Figure imgf000037_0003
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0002
Table 6
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0002
Table 7
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0002
Table 8
Figure imgf000046_0001
(1-9)
Figure imgf000046_0003
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0002
Table 9
Figure imgf000049_0001
(1-10)
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0002
Table 10
Figure imgf000052_0001
(I- ID
Figure imgf000052_0003
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0002
Table 11
Figure imgf000055_0001
(1-12)
In this formula (1-12), p represents zero or one, and R , 151 represents R or a hydrogen atom, R and Xi have the meanings indicated hereinbelow.
Figure imgf000056_0001
Table 12
Figure imgf000057_0001
(1-13) In this formula (1-13), p represents zero or one and R10, R16, R 15 and Xi have the meanings indicated hereinbelow. The R15 group is located according to the numbering system in (1-13).
Figure imgf000057_0002
Figure imgf000058_0001
Figure imgf000059_0002
Table 13
Figure imgf000059_0001
(1-14)
In this formula (1-14), p represents zero or one and R 10 , R , 15 and X have the meanings indicated hereinbelow. The R1 group is located according to the numbering system in (1-14).
Figure imgf000060_0003
Table 14
Figure imgf000060_0001
(1-15) In this formula (1-15), p represents zero, and R10 and X1 have the meanings indicated hereinbelow. It is to be understood that in the following table, Identification Group I recites individual species in which Z represents;
Figure imgf000060_0002
(Zl) (Z2)
Figure imgf000061_0001
(Zl) (Z8)
wherein ^"^ re resents an attachment oint to the rest of the molecule.
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Compounds of formula (I) above may be prepared by the application or adaptation of known methods (i.e. methods heretofore used or described in the literature), for example as hereinafter described.
In the following description where symbols appearing in formulae are not specifically defined, it is to be understood that they are "as hereinbefore defined" in accordance with the first definition of each symbol in the specification.
It is to be understood that in the descriptions of the following processes the sequences may be performed in different orders, and that suitable protecting groups may be required to achieve the compounds sought.
According to a feature of the present invention compounds of formula (I), wherein R11, R12, R13, R14, R16, R17, p, Xt, X2 and X3 are as
10 7 77 defined above and in which R represents -CO2R , wherein R
79 represents R with the exclusion of the hydrogen atom, may be prepared from the corresponding compound of formula (I) wherein R represents CO2H by reaction with an alcohol of formula (II):
R33-OH
(π)
The reaction is generally carried out in the presence of an organic solvent, preferably the alcohol R33OH, optionally in the presence of an acid or base catalyst, preferably an acid catalyst such as sulphuric acid.
According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above and in which R10 represents -CO2H, may be prepared from the corresponding compound wherein R represents -CO2R 3 and R33 represents t-butyl, using an acid such as trifluoroacetic acid in a solvent such as dichloromethane at a temperature of from 0-50°C. According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above and in which R10 represents -CONR30R31, may be prepared from the corresponding compound of formula (I) wherein R10 represents -CO2H by successive treatment with a halogenating agent to give the acyl halide, followed by an amine of formula (III):
R30R31NH (HD 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.
According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above, in which R10 is -CH2NO2, -CH2SCN, -CH2CN or -CH2N3, may be prepared from the corresponding compound of formula (I) wherein R10 is -CH∑-L, where L is a leaving group, generally a sulfonate ester such as a para toluenesulfonate or a mesylate, or wherein R10 is replaced by -CH2-L', where L1 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. Such compounds are generally known in the literature, or may be prepared from known compounds by a practitioner skilled in the art. According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above, in which R10 is -C(=NR35)R32, can be prepared from the corresponding compound of formula (I) wherein R10 is -COR32 by reaction with a compound of formula (IV);
R35NH2
(IN) 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. The reaction is generally performed at a temperature of 0°C to 150°C, optionally with the physical removal of water (for example, by azeotropic distillation), or by the use of a dehydrating agent such as molecular sieves or titanium tetrachloride. According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above, and in which R10 is -CH=CHC(O)OR32 can be prepared from the corresponding compound of formula (I) wherein R10 is halogen, by reaction with a compound of formula (V): CH2=CHC(O)OR32
(V) 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 Ν,Ν- 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
50°C to 150 °C. According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above and in which R10 represents -CHR27R28 or -CR27R28R281 and R27, R28 and R281 are as defined above, may be prepared by the halogenation of the corresponding compound in which one or more of R27, R28 and R281 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.
According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as hereinbefore defined, may be prepared from the corresponding compound of formula (VI),
Figure imgf000066_0001
(VI) wherein R10, R11, R12, R13, R14, Xi and p are as hereinbefore defined by reaction with a compound of formula (VII),
Figure imgf000066_0002
(vπ) wherein X2, X3, R16 and R17 are as hereinbefore defined, and L is a leaving group, such as a halogen, usually a bromine, chlorine or iodine radical, optionally in the presence of a base, generally an amine such as triethylamine or pyridine or a metal hydride such as sodium hydride. According to a further feature of the invention, compounds of formula (I) wherein the various symbols are as defined above and R16 represents OR wherein R represents R with the exclusion of the hydrogen atom, may be prepared by the reaction of a compound of formula (VB3);
Figure imgf000067_0001
(VIII)
with an alkylating agent (to introduce a group R251 which is alkyl), generally a dialkysulfate such as dimethylsulfate, or 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.
According to a further feature of the invention, compounds of formula (VIII) wherein R10, R11, R12, R13, R14, R17, X1 ? X2 are as hereinbefore defined and X3 represents CR wherein R represents R may be prepared from the reaction of a compound of formula (IX);
Figure imgf000067_0002
(IX) with an aminomethylating agent followed by hydrolysis with an acid. 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.
According to a further feature of the present invention, compounds of formula (I) wherein the various symbols are as defined above and in which R10 represents -COCH2COR33 wherein R33 is as defined above, may be prepared from the corresponding compound in which R10 is replaced by a group COCH(CO2tBu)COR33. 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. According to a further feature of the present invention compounds of formula (I) wherein R10 represents -COF may be prepared from the corresponding compound in which R10 represents CO2H, 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.
Compounds in which R10 represents -CO2R33 and R33 represents t- butyl may be prepared by the reaction of the corresponding compound in which R10 represents -CO2H with t-butanol in 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. According to a further feature of the invention, compounds of formula (IX) may be prepared by the reaction of a compound of formula (X),
Figure imgf000069_0001
(X) wherein R10, Rn, R12, R13 and R14 are as hereinbefore defined and
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),
Figure imgf000069_0002
(XI) wherein Xi, X2 and R17 are as hereinbefore defined, optionally in the presence of a base, such as a tertiary amine, a metal carbonate or a metal hydride. Compounds of formula (XI) are generally known in the literature or may be prepared by known methods.
Intermediates of formula (I) in which R10 is replaced by COCH(CO2tBu)COR33, used above, may be prepared from the corresponding acid of formula (I) in which R10 represents CO2H by conversion to the acid chloride using a chlorinating agent such as oxalyl chloride in an inert solvent, followed by reaction with a metal salt
(preferably a magnesium salt) of a compound of formula (XII),
R33COCH2CO2t-Bu (XII) wherein R33 is as defined above. The reaction is generally performed in a solvent, such as toluene. Compounds of formula (II), (III), (IV), (V), (VI), (VII), (IX), (X) and (XI) are generally known or may be prepared by known methods. The following examples are given to illustrate the invention and to facilitate the work of the man skilled in the art to reproduce the invention. However, they have not to be understood as limiting the invention. Some of the initial steps of some examples may be already known directly or indirectly for analogous compounds. Nevertheless, such descriptions have been kept within this description to provide an easier and better practice for the man skilled in the art to reach any of the compounds of the invention.
Example 1
0.396g of methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3- hydroxypropenoate was mixed with 336mg of K2CO3, (CH3)2SO (0.16ml) and dimethylformamide (8.2ml). The mixture was stirred for 12 hours at 20°C and extracted with ether (following the addition of Na2CO3). 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).
By proceeding in a similar manner the following compounds were prepared: methyl 2-[2-methoxycarbonyl-3-(2-methyl- 1 ,3-dioxolan-2-yl) phenoxy] -3 -methoxypropenoate (compound 139, NMR (CDC13): 1.75 (s,3H), 3.70 (s,3H), 3.85 (s,3H), 3.90 (s,3H), 3.73 (m,2H), 4.00 (m,2H), 6.75 (d,lH), 7.00-7.35 (m,3H)); and methyl 2-(2-methoxycarbonyIbenzyloxy)-3-methoxypropenoate
(compound 140, NMR (CDC13): 3.6(s,3H), 3.7(s,3H), 3.8(s,3H), 5.2(s,2H), 6.95(s,lH), 7.25(t,lH), 7.5(t,lH), 7.8(d,lH), 7.9(d, lH)). Example 2
298mg of (methyl (2-t-butyloxycarbonyl 4-chlorophenoxy)-3- methoxypropenoate was mixed with CH2C12 (0.9ml) and CF3COOH
(0.67ml). The mixture was stirred for 2 hours at 20°C, diluted with ethyl acetate and extracted with aqueous sodium carbonate, then water. The aqueous phase was acidified with 2N HC1 and extracted with ethyl acetate. The organic layer was washed, dried and evaporated to give methyl 2-(2-carboxy-4-chIorophenoxy)-3-methoxypropenoate (compound 2, a white solid, mp 1 19-120 °C). The following compounds were similarly prepared: methyl 2-(2-carboxy-4-methylphenoxy)-3-methoxypropenoate (compound 45, mp 128-130°C); methyl 2-[2-carboxy-3-(2-methoxy- 1 - methoxycarbonyIvinyloxy)phenoxy]-3 -methoxypropenoate (compound 46, NMR (CDC13) 3.75(s,6H), 3.9(s,6H), 6.6(d,2H), 7.2(t,lH),
7.35(s,2H));
2,4-dichlorophenyl 2-(2-carboxy-4-chlorophenoxy)-(3- methoxy)thiopropenoate (compound 47,M.S. m/z 455 (M+Na+H); 431 (M-H)); methyl 2-(2-carboxy-4-chlorophenoxy)-3-(l-ethoxy carbonyl)ethoxypropenoate (compound 48, NMR (CDC1 ): 1.25(t,3H), 1.5(d,3H), 3.7(s,3H), 4.2(q,2H), 4.6(q,lH), 7.1(d,lH), 7.35(dd,lH), 7.4(s,lH), 7.85(d,lH)); methyl 2-(2-carboxy-4-chlorophenoxy)-3-prop-2-yn yloxypropenoate (compound 49, NMR (CDC13): 2.75(t, 1H), 3.8(s,3H),
4.7(d,2H), 6.9(d,lH), 7.4(dd,lH), 7.65(s,lH), 8.0(d,lH), 9.25 (bs.lH)); methyl 2-(2-carboxy-4-methoxy phenoxy ) -3 -methoxypropenoate (compound 72, NMR (CDC13): 3.80(s,3H), 3.85(s,3H), 4.00(s,3H), 6.90(d,lH), 7.00(d,lH), 7.40(s,lH), 7.55(s,lH)); butyl 2-(2-carboxy-4-chlorophenoxy)-3-methoxypropenoate
(compound 73, NMR (CDC13) 0.90(t,3H), 1.30(m,2H), 1.60(m,2H), 4.00(s,3H), 4.20(t,2H), 6.90(d,lH), 7.40(d,lH), 7.45(s, lH), 8.00(s, lH)); methyl 2-(2-carboxy-3-fluorophenoxy)-3-methoxypropenoate (compound 74, mp 104-106°C); methyl 2-(2-carboxy-3-chlorophenoxy)-3-methoxypropenoate
(compound 75, mp 151- 152 °C); methyl 2-(2-carboxy-3-methylphenoxy)-3-methoxypropenoate (compound 76, NMR (CDCI3): 2.4(s,3H), 3.7(s,3H), 3.9(s,3H), 6.7(d,lH), 6.9(d,lH), 7.15(t,lH), 7.3(s,lH)); methyl 2-(2-carboxy-4-chlorophenoxy)-3-methylthiopropenoate (compound 77, NMR (CDC13) 2.5(s,3H), 3.8(s,3H), 6.9(d,lH),
7.4(m,lH), 7.6(s,lH), 8.0(d,lH), OH peak of acid not visible); methyl 2-(2-carboxyphenoxy)-3-methoxypropenoate (compound 78, NMR (CDC13): 3.8(s,3H), 4.0(s,3H), 6.9(d,lH), 7.2(t,lH), 7.5(m,3H), 8.0(d,lH)); methyl 2-(l-carboxynaphth-2-yloxy)-3-methoxypropenoate
(compound 79, mp 145.4°C); methyl 2-(2-carboxy-3,4 difluorophenoxy)-3-methoxypropenoate (compound 80, NMR (CDC13): 7.40 (s, 1 H), 7.18 (q, 1 H), 6.70 (dt, 1 H), 4.02 (s, 3 H) and 3.80 (s, 3 H)); methyl 2-(2-carboxy-3-chloro-4-fluorophenoxy)-3- methoxypropenoate (compound 81, mp 131°C); methyl 2-(2-carboxy-4-chloro-3-fluorophenoxy)-3- methoxypropenoate (compound 82, NMR (CDC13): 3.7 (s, 3H), 3.95 (s, 3H), 6.65 (m, 1H), 7.35-7.2 (m, 2H); 19F NMR -1 11.834); methyl 2-(2-carboxy-4-difluoromethylphenoxy-3- methoxypropenoate (compound 83, NMR (CDCI3): 3.8 (s, 3H), 4.0 (s, 3H), 6.85-6.45 (t, 1H), 7.0 (d, 1H), 7.5 (s, 1H), 7.65 (m, 1H), 8.2 (m, 1H)); methyl 2-(4-bromo-2-carboxyphenoxy)-3-methoxypropenoate (compound 84, mp 142.7 - 145°C); methyl 2-(2-carboxy-4-fluorophenoxy)-3-methoxypropenoate (compound 85, mp 141.5-143.1°C); methyl 2-(3-bromo-2-carboxyphenoxy)-3-methoxypropenoate (compound 86, NMR (CDC13): 3.75(s,3H),4.0(s,3H), 6.9(d,lH), 7.2(t, lH), 7.35-7.55(m,2H)); methyl 2-(2-carboxy-3-thiocyanatomethyIphenoxy)-3- methoxypropenoate (compound 87, NMR (CDC13): 3.7(s,3H), 3.95(s,3H), 4.2(s,2H), 6.9(d,lH), 7.1(d, lH), 7.3-7.5(d,2H)); methyl 2-(3-acetoxymethyl-2-carboxyphenoxy)-3- methoxypropenoate (compound 88, NMR (CDC13): 2.1(s,3H),
3.45(s,2H), 3.75(s,3H), 4.0(s,3H), 6.9(d,lH), 7.15(d,lH), 7.35(t,lH), 7.4(s,lH)); methyl 2-(2-carboxy-3,4-dichlorophenoxy)-3-methoxypropenoate (compound 89, NMR (CDCI3): 3.7(s,3H), 4.0(s,3H), 6.8(d,lH), 7.4- 7.5(m,2H)); methyl 2-(2-carboxy-3,4-difluorophenoxy)-3-methoxypropenoate (compound 115, NMR (CDC13): 7.30 (s, 1 H), 7.12 (q, 1 H), 6.60 (dt, 1 H), 3.96 (s, 3 H), 3.90 (s, 3 H) and 3.72 (s, 3 H)); methyl 2-(2-carboxy-4-chlorophenoxy)-3-ethoxypropenoate (compound 157, NMR (CDC13): 1.35(t,3H), 3.75(s,3H), 4.2(q,2H),
6.9(d,lH), 7.4(dd,lH), 7.5(s,lH), 7.95(d,lH), 9.4 (bs,lH)); and methyl 2-(2-carboxy-4-chlorophenoxy)-3-(2- trifluoromethoxybenzyloxy)propenoate (compound 158, NMR (CDC13): 3.75(s,3H), 5.25(s,2H), 6.85(d,lH), 7.35(m,5H), 7.6(s,lH), 7.95(d,lH), 8.6 (bs,lH)).
Example 3
Similarly, the corresponding chain of reactions of examples 1 to 2 and reference examples 3, 4, 5 were followed so as to give, starting from 5-iodosalicylic acid, methyl 2-(2-carboxy-4-iodophenoxy)-3- methoxypropenoate (compound 3, mp 130-131 °C).
Example 4
A mixture of 5.13g methyl 2-(4-chloro-2-methylphenoxy)-3- methoxypropenoate, 3.56g of N-bromosuccinimide, and a catalytic amount of azobisisobutyronitrile was heated at reflux in carbon tetrachloride with light irradiation for 4 hours. The mixture was filtered through silica gel, the solvent evaporated and the residue purified by fractional recrystallisation to give methyl 2-(2-bromomethyl-4- chlorophenoxy)-3-methoxyρropenoate, NMR (CDCI3): 3.70 (s,3H), 3.9 (s,3H), 4.60 (s,2H), 6.70 (d, H), 7.20 (d,lH), 7.30 (s, lH), 7.40 (s, lH), and methyl 2-(2-dibromomethyl-4-chlorophenoxy)-3- methoxypropenoate (compound 4, NMR (CDCI3): 3.70 (s,3H), 3.9 (s,3H), 6.70 (d,lH), 7.20 (d,3H), 7.30 (s,2H), 7.90 (s,lH).
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 6
O.lg of methyl 2-(2-bromomethyl-4-chlorophenoxy)-3- methoxyacrylate, 45.3 mg of potassium carbonate, N-methylaniline (35.5μl) and toluene (1ml) were heated at 100 °C for 18 hours. Filtration, evaporation and chromatography gave methyl 2-[4-chloro-2- ((N-methyl-N-phenylamino)methyl)phenoxy]-3-methoxypropenoate (compound 6), M.S. m/z 362 (M+H).
The following compounds were similarly prepared by replacing the N-methylaniline with the nitrogen compounds shown in the following table:
Figure imgf000074_0001
Figure imgf000075_0001
Example 7
O.lg of methyl 2-(2-bromomethyl-4-chlorophenoxy)-3- methoxyacrylate, 0.068g of silver nitrite and diethyl ether (1ml) were stirred at 0 °C for 8 hours, and at ambient temperature for 60 hours. Filtration, evaporation and chromatography of the residue gave methyl 2-(4-chloro-2-(nitromethyl)phenoxy)-3-methoxypropenoate (compound 16), M.S. m/z 302 (M+H).
Example 8
To O.lg of methyl 2-(2-bromomethyl-4-chlorophenoxy)-3- methoxyacrylate in DMSO (1ml) at 0 °C was added 0.02 lg potassium cyanide. The contents were stirred at ambient temperature for 16 hours, diluted with water and extracted with diethyl ether. The organic layer was washed with saturated sodium chloride solution, dried and evaporated to give methyl 2-(4-chloro-2-(cyanomethyl)phenoxy)-3- methoxypropenoate (compound 17), M.S. m/z 282 (M+H).
Example 9
To O. lg of methyl 2-(2-bromomethylphenoxy)-3-methoxyacrylate in DMSO (1ml) at 0 °C was added 0.026g sodium thiocyanate. The contents were stirred at ambient temperature for 16 hours, diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated sodium chloride solution, dried and evaporated to give methyl 2-(4-chloro-2-(thiocyanomethyl)phenoxy)-3-methoxypropenoate (compound 18), M.S. m/z 314 (M+H).
Example 10
0.04g of methyl 2-(2-carboxy-4-chlorophenoxy)-3- methoxypropenoate, cone. H2SO (20μl) and methanol (3 ml) were stirred at ambient temperature for 18 hours and then at 60 °C for 30 minutes. The solvent was removed by evaporation and the residue partitioned between diethyl ether and aqueous sodium bicarbonate. The organic layer was separated, dried and evaporated to give 0.042g of methyl 2-(4-chloro-2-methoxycarbonylphenoxy)-3-methoxypropenoate (compound 19, NMR (CDCI3): 3.80 (3H,s), 3.85 (3H,s), 3.60 (3H,s). Similarly, using ethanol there was obtained methyl 2-(4-chloro-2- ethoxycarbonylphenoxy)-3-methoxypropenoate (compound 20, NMR (CDC13): 3.75 (s,3H), 1.30 (t,3H), 3.60 (s,3H), 4.30 (q,2H).
The following compounds were similarly prepared: methyl 2-[4-chloro-2-(prop-2-ynyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 51, M.S. m/z 325 (M+H)); methyl 2-[2-(benzyloxycarbonyl)-4-chlorophenoxy]-3- methoxypropenoate (compound 52, M.S. m/z 377 (M+H)); methyl 2-[4-chloro-2-(propyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 53, M.S. m/z 329 (M+H)); methyl 2-[2-(butyloxycarbonyI)-4-chlorophenoxy]-3- methoxypropenoate (compound 54, M.S. m/z 343 (M+H)); methyl 2-[4-chloro-2-(prop-2-yloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 55, M.S. m/z 329 (M+H)); methyl 2-[4-chloro-2-(3-chloropropyloxycarbonyI) phenoxy]-3- methoxypropenoate (compound 56, M.S. m/z 363 (M+H)); methyl 2-[4-chloro-2-(but-2-yloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 57, M.S. m/z 343 (M+H)); methyl 2-[4-chloro-2-(3-pentyIoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 58, M.S. m/z 357 (M+H)); methyl 2-[4-chloro-2-(hept-2-yloxycarbonyI)phenoxy]-3- methoxypropenoate (compound 59, M.S. m/z 385 (M+H)); methyl 2-[4-chloro-2-(octyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 60, M.S. m/z 399 (M+H)); methyl 2-[4-chloro-2-(cyclopentyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 61, M.S. m/z 355 (M+H)); methyl 2-[4-chloro-2-(2-methoxyethoxycarbonyl) phenoxyj-3- methoxypropenoate (compound 62, M.S. m/z 345 (M+H)); methyl 2-[4-chloro-2-(2-ethoxyethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 63, M.S. m/z 359 (M+H)); methyl 2-[4-chloro-2-(cyclopropylmethoxycarbonyl) phenoxy]-3- methoxypropenoate(compound 64, M.S. m/z 341 (M+H)); methyl 2-(4-methoxy-2-methoxycarbonylphenoxy)-3- methoxypropenoate (compound 65, NMR (CDCI3): 3.70(s,3H), 3.80(s,3H), 3.85(s,3H), 3.90(s,3H), 6.80(d,lH), 6.95(d,lH), 7.30(s,lH), 7.40(s,lH)); methyl 2-(4-bromo-2-methoxycarbonylphenoxy)-3- methoxypropenoate (compound 100, NMR (CDCI3): 3.70(s,3H),
3.85(s,3H), 3.9(s,3H), 6.8(d,lH), 7.30(s,lH), 7.45(d,lH), 8.00(s,lH)); methyl 2-(4-fluoro-2-methoxycarbonylphenoxy)-3- methoxypropenoate (compound 101, NMR (CDCI3): 3.70(s,3H), 3.85(s,3H), 3.90(s,3H), 6.83(m,lH), 7.10(m,lH), 7.30(s,lH), 7.55(d,lH); (19F) -122.21 (s,lF)); and methyl 2-(2-ethoxycarbonyl-3-fluorophenoxy)-3- methoxypropenoate (compound 102, NMR (CDC13) l,3(t,3H), 3.6(s,3H), 3.8(s,3H), 4.35(q,2H), 6.6(d,lH), 6.7(t,lH), 7.2(m,lH), 7.25(s, lH)). Example 11
To 0.042g of methyl 2-(2-carboxy-4-chlorophenoxy)-3- methoxypropenoate in CH2CI2 (5ml) was added oxalyl chloride (14.1 μl) and 73μl of a solution of dimethylformamide in CH2C12 (1 drop DMF in 5ml CH2CI2). The contents were heated at 40°C for 1 hour, cooled, and 0.026g 4-trifluoromethoxyaniiine in CH2CI2 (0.1ml) was added followed by triethylamine (44.9μl). The reaction was stirred at ambient temperature for 4 hours then purified by chromatography to yield 0.062g methyl 2-(4-chloro-2-N-(4-trifluoromethoxyphenyl)- aminocarbonyI)phenoxy-3-methoxypropenoate (compound 21, NMR (CDCI3): 8.0 (broad, 1H), 7.40 (s,lH), 7.15 (d,2H), 7.70 (d,2H).
The following amides were similarly prepared by using the appropriate amines;
Figure imgf000079_0001
Figure imgf000080_0001
The following compounds were similarly prepared: methyl 2-[2-(benztriazol- 1 -yloxycarbonyl)-4-chlorophenoxy]-3- methoxypropenoate (compound 66, M.S. m/z 404 (M+H)); methyl 2-[4-chloro-2-(4-nitrophenoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 67, M.S. m/z 408 (M+H)); methyl 2-[4-chloro-2-(2,4,5-trichlorophenoxycarbonyl)phenoxy]-3-methoxypro penoate (compound 68, M.S. m/z 482 (M+H)); methyl 2-[4-chloro-2-(2,3,4,5,6- pentachlorophenoxycarbonyl)phenoxy]-3-methoxypropenoate (compound 69, M.S. m/z 550 (M+H)); methyl 2-[4-chloro-2-(ethylcarbamoyl)phenoxy]-3- methoxypropenoate (compound 70, M.S. m/z 314 (M+H)); methyl 2-[4-chloro-2-(ethyIthiocarbonyl)ρhenoxy]-3- methoxypropenoate (compound 71, M.S. m/z 331 (M+H)); methyl 2-{4-chloro-2-[N'-(2- chlorophenyl)hydrazinocarbonyl]phenoxy} -3-methoxypropenoate (compound 50, NMR (CDCI3): 3.75(s,3H), 3.95(s,3H), 6.65(d,lH), 6.8(m,2H), 7.0(m,lH), 7.1(m,lH) 7.25(m,2H), 7.4(s,lH), 7.95(d,lH), 9.5 (m,lH)); methyl 2-{4-chloro-2-[N'-(2,4-dichlorophenyl)hydrazino carbonyl]phenoxy} -3-methoxypropenoate (compound 92, NMR (CDCI3): 3.75(s,3H), 4.0(s,3H), 6.65(d, lH), 6.85(d, l H), 6.95(d, lH), 7.1(dd,lH), 7.35(m,2H), 7.4(s,lH), 8.0(d,lH), 9.7(d, lH)); methyl 2-{4-chloro-2-[N'-(3- trifluoromethylphenyl)hydrazinocarbonyl]phenoxy } -3- methoxypropenoate (compound 93, NMR (CDCI3): 3.8(s,3H),
4.0(s,3H), 6.5(d,lH), 6.85(d,lH), 7.15(m,3H), 7.35(m,2H), 7.45(s,lH), 8.0(d,lH), 9.65(d,lH)); methyl 2-[2-(2,2,2-trifluoroethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 94, NMR (CDCI3): 3.6(s,3H), 3.8(s,3H), 4.6(q,2H), 6.85(d,lH), 7.0(t,lH), 7.3(s,lH), 7.4(t,lH),
7.85(d,lH)); methyl 2-[4-chIoro-2-(2,2,2-trichloroethoxycarbonyl) phenoxy]-3- methoxypropenoate (compound 95, NMR (CDC13): 3.7(s,3H), 3.85(s,3H), 4.95(s,2H), 6.85(d,lH), 7.3(s,lH), 7.4(d,lH), 7.9(d,lH)); methyl 2-{4-chloro-2-[(l-hydroxy-2-methylprop-2- yl)carbamoyl]phenoxy} -3-methoxypropenoate (compound 96, NMR (CDCI3); 1.35(s,6H), 3.70(s,2H), 3.75(s,3H), 3.95(s,3H), 6.80(d,lH), 7.29(d,lH), 7.40(s,lH), 7.90(s,IH), 7.95(bs,lH)); methyl 2-[4-methyl-2-(2,2,2-trifluoroethoxycarbonyl) phenoxy]- 3-methoxypropenoate (compound 97, NMR (CDC13) 2.30 (s,3H), 3.70
(s, 3H), 3.90 (s, 3H), 4.65 (q, 2H), 6.80 (d, 1H), 7.25 (d, 1H), 7.30 (s, lH), 7.70 (s, 1H)); methyl 2-(3-fluoro-2-hexylthiocarbonylphenoxy)-3- methoxypropenoate (compound 98, M.S. m/z 371 (M+H)); methyl 2-[4-fluoro-2-(2-ethoxyethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 99, NMR (CDC13): 1.22 (t, 3H), 3.58 (d, 2H), 3.70 (s, 3H), 3.75 (m, 2H), 3.86 (s, 3H), 4.45 (m, 2H), 6.85 (m, 1H), 7.08 (m, 1H), 7.30 (s, 1H), 7.55 (m, 1H);,9F: -122.30 (s)); methyl 2-[4-chloro-2-(diphenylmethyleneimino- oxycarbonyl)phenoxy]-3-methoxypropenoate (compound 128, NMR
(CDC13): 3.65(s,3H), 3.80(s,3H), 6.75(d,lH), 7.30-7.70(m,13H)); methyl 2-[4-chloro-2-(methylcarbamoyI)phenoxy]-3- methoxypropenoate (compound 156, M.S. m/z 300 (M+H)); methyl 2-{4-chloro-2-[N'-(4- fluorophenyl)hydrazinocarbonyl]phenoxy } -3-methoxypropenoate (compound 159, NMR (CDCI3): 3.75(s,3H), 4.0(s,3H), 6.4(d,lH),
6.9(m,5H), 7.35(dd,lH), 7.4(s,lH), 8.0(d,lH), 9.6(d,lH)); methyl 2-{4-chloro-2-[N'-(4- methoxyphenyl)hydrazinocarbonyl]phenoxy } -3-methoxypropenoate (compound 160, NMR (CDC13): 3.75(s,6H), 3.95(s,3H),), 6.85(m,6H), 7.3(dd,lH), 7.45(s,lH), 8.0(d,lH), 9.6(bs,lH)); methyl 2-[2-(2,2,2-trichloroethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 161, NMR (CDC13): 3.6(s,3H), 3.8(s,3H), 4.9(s,2H), 6.85(d,lH), 7.O(t,lH), 7.3(s,lH), 7.4(t,lH), 7.9(d,lH)); methyl 2-[3-fluoro-2-(2,2,2-trifluoroethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 162, NMR (CDC13): 3.6(s,3H), 3.8(s,3H), 4.6(q,2H), 6.6(d,lH), 6.7(t,lH), 7.25(m,2H)); methyl 2-[4-chloro-2-(2,2,2-trifluoroethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 163, NMR (CDC13): 3.7(s,3H), 3.85(s,3H), 6.85(d,lH), 7.3(s,lH), 7.4(d,lH), 7.85(d,lH)); methyl 2-[3-fluoro-2-(2,2,2-trichloroethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 164, M.S. m/z 401/403/405 (M+H)); and methyl 2-(2-ethylthiocarbonyl-3-fluorophenoxy)-3- methoxypropenoate (compound 165, m/z 315 (M+H)+).
Example 12
O.lg of methyl 2-(2-formyl-4-chlorophenoxy)-3- methoxypropenoate was suspended in ethanol (2 ml) and 0.033g of acethydrazide was added. The mixture was stirred at ambient temperature for 18 hours. The precipitate was filtered off, washed with a small amount of ethanol and dried to give methyl 2-(4-chloro-2- acetylaminoiminomethylenephenoxy)-3-propenoate (compound 35), M.S. m/z 327 (M+H).
The following compounds were prepared in a similar manner from the following reactants:
Figure imgf000083_0001
The following compounds were prepared in a similar manner from the corresponding hydrazines in the presence of sodium acetate: methyl 2-[2-(pyrid-2-ylhydrazonomethylene)phenoxy]-3- methoxypropenoate (compound 130, NMR (CDC13): 8.34 (s, 1 H), 8.28 (s, 1 H). 8.14 (d, 1 H), 8.04 (d, 2 H), 7.60 (t, I H), 7.38 (d, 1 H), 7.36 (s, 1 H), 7.22 (t, 1 H), 7.06 (t, 1 H), 6.82-6.72 (m, 2 H), 3.90 (s, 3 H) and 3.74 (s, 3 H)); methyl 2-[4-chloro-2-(N-methylsulphonylhydrazono methylene)phenoxy]-3-methoxypropenoate (compound 131, M.S. m/z 363/365 (M+H)); methyl 2-[4-chloro-2-(2,4,6- trichlorophenylhydrazonomethylene)phenoxy]-3-methoxypropenoate (compound 132, M.S. m/z 463/465/467 (M+H)); methyl 2-{4-chloro-2-[N-(4-morpholinyl)iminomethylene]phenoxy}-3- methoxypropenoate (compound 133, M.S. m/z 355/357 (M+H)); methyl 2-[4-chloro-2-(pyrid-2-ylhydrazonomethylene)phenoxy]-3- methoxypropenoate (compound 134, M.S. m/z 362/364 (M+H)); methyl 2-[4-chloro-2-(4- fluorophenylhydrazonomethylene)phenoxy]-3-methoxypropenoate (compound 135, M.S. m/z 379/381 (M+H)); methyl 2- [4-chloro-2-(4-nitrophenylhydrazonomethylene)phenoxy]-3- methoxypropenoate (compound 136, M.S. m/z 406/408 (M+H)); and methyl 2-{4-chloro-2-[N- (dimethylthiocarbamoyl)hydrazonomethylene]phenoxy } -3- methoxypropenoate (compound 137, M.S. m/z 372/374 (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). By proceeding in a similar manner: 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, 30μl of triethylamine, 3.4 mg of triphenylphosphine, 40μl 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-
(2-methoxycarbonylethenyl)phenoxy)-3-methoxypropenoate (compound 44), M.S. m/z 327 (M+H). Example 15
By proceeding according to Example 2 starting from methyl 2-(2- t-butoxycarbonyl-3-formylphenoxy)-3-methoxypropenoate, there was prepared a mixture of methyl 2-(2-carboxy-3-dihydroxymethylphenoxy)- 3 -methoxypropenoate (compound 90, NMR (CDC13): 3.6(s,3H), 3.8(s,3H), 6.5(s,lH), 6.85(d,lH), 7.15(d,lH), 7.3(s,lH), 7.5(d,lH)) and methyl 2-(3-hydroxyphthaIid-7-yIoxy)-3-methoxypropenoate (compound 91, NMR (CDCI3): 3.6(s,3H), 3.8(s,3H), 6.4(s,lH),
6.8(d,lH), 7.0(d,lH), 7.3(s,lH), 7.5(t,lH)). Example 16
A mixture of methyl 2-(2-carboxy-3-fluorophenoxy)-3- methoxypropenoate (0.05g), propargyl bromide (0.278 mmol) and potassium carbonate was stirred and heated in acetonitrile at 70°C for 4 hours. Water was added to the cooled mixture, which was then extracted (ether), dried and evaporated to give methyl 2-[3-fluoro-2- (prop-2-ynyloxycarbonyl)phenoxy]-3-methoxypropenoate (compound 103, 0.047g, M.S. m/z 309 (M+H)). By proceeding in a similar manner the following compounds were prepared: methyl 2-(2-benzyloxycarbonyl-3-fluorophenoxy)-3- methoxypropenoate (compound 104, M.S. m/z 361 (M+H)); methyl 2-[3-fluoro-2-(2-methoxyethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 105, M.S. m/z 329 (M+H)); methyl 2-[2-(2-ethoxyethoxycarbonyl)-3-fluorophenoxy]-3- methoxypropenoate (compound 106, M.S. m/z 343 (M+H)); methyl 2-[3-fluoro-2-(tetrahydrofuran-2-ylmethoxycarbonyl) phenoxy]-3-methoxypropenoate (compound 107, M.S. m z 355 (M+H)); methyl 2-[2-(3-chloropropyloxycarbonyl)-3-fluorophenoxy]-3- methoxypropenoate (compound 108, M.S. m/z 347/349 (M+H)); methyl 2-(2-butyloxycarbonylphenoxy)-3-methoxypropenoate (compound 109, NMR (CDC13): 0.9(t,3H), 1.4(m,2H), 1.65(m,2H), 3.6(s,3H), 3.8(s,3H), 4.25(t,2H), 6.8(d,lH), 7.0(t,lH), 7.2(s,lH), 7.3(t,lH), 7.75(d,lH)); methyl 2-(2-pentyloxycarbonylphenoxy)-3-methoxypropenoate (compound 110, NMR (CDC13): 0.9(t,3H), 1.4(m,4H), 1.75(m,2H), 3.7(s,3H), 3.9(s,3H), 4.3(t,2H), 6.85(d,lH), 7.0(t,lH), 7.3(s,lH), 7.4(t,lH), 7.85(d,lH)); methyl 2-(2-octyloxycarbonylphenoxy)-3-methoxypropenoate
(compound 111, NMR (CDCI3): 0.9(t,3H), 1.3(m,6H), 1.8(m,4H), 3.2(t,2H), 3.7(s,3H), 3.9(s,3H), 4.3(t,2H), 7.15(m,lH), 7.3(m,2H), 7.6(m,lH), 7.7(d,lH)); methyl 2-[2-(3-chloropropyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 112, NMR (CDCl3): 2.2(t,2H),
3.7(t,2H), 3.75(s,3H), 3.9(s,3H), 4.5(t,2H), 7.2(d,lH), 7.35(m,2H), 7.6(m,lH), 7.7(d,lH)); methyl 2-[2-(prop-2-ynyloxycarbonyl)phenoxy]-3- methoxypropenoate (compound 1 13, NMR (CDCI3): 2.5(t, lH), 3.7(s,3H), 3.9(s,3H), 4.9(d,2H), 6.9(d, l H), 7.1(t, lH), 7.3(s,lH),
7.4(m, lH), 7.9(d, lH)); and methyl 2-(2-benzyloxycarbonyIphenoxy)-3-methoxypropenoate (compound 114, NMR (CDC13): 3.7(s,3H), 3.9(s,3H), 5.4(s,2H), 6.9(d, lH), 7.0(t,lH), 7.4(m,7H), 7.9(d,lH)). Example 17 A solution of 4-methylbenzyl bromide (0.05g) in N,N- dimethylformamide was added to a suspension of potassium fluoride (0.034g) in N.N-dimethylformamide. A solution of methyl 2-(2- carboxy-3-methylphenoxy)-3-methoxypropenoate (O.lg) in N,N- dimethylformamide was added and the mixture stirred overnight. Water and ethyl acetate were added and the organic phase dried (magnesium sulphate) and evaporated to give methyl 2-[3-methyl-2-(4-methyl benzyloxycarbonyl)phenoxy]-3-methoxypropenoate (compound 117, O.lg, NMR (CDC13): 2.25(s,3H), 2.35(s,3H), 3.65(s,3H), 3.8(s,3H), 5.35(s,2H), 6.6(d,lH), 6.8(d,lH), 7.1-7.2(m,3H), 7.25-7.4(m,3H)). By proceeding in a similar manner the following compounds were prepared: methyl 2-[2-(2-ethoxyethoxycarbonyl)-3,4-difluorophenoxy]-3- methoxypropenoate (compound 118, NMR (CDC13): 1.2(t,3H), 3.55(q,2H), 3.7(s,3H), 3.75(t,2H), 3.8(s,3H), 4.5(t,2H), 6.6(d,lH), 7.1(q,lH), 7.25(s,lH)); methyl 2-[3,4-difluoro-2-(4-methylbenzyloxycarbonyl) phenoxy]- 3-methoxypropenoate (compound 119, NMR (CDC13): 2.4(s,3H), 3.65(s,3H), 3.85(s,3H), 6.6(d,lH), 7.0-7.2(m,3H), 7.25-7.4(m,3H)); methyl 2-(2-benzyloxycarbonyl-3,4-difluorophenoxy)-3- methoxypropenoate (compound 120, NMR (CDCl3):3.6(s,3H),
3.7(s,3H), 5.3(s,2H), 6.5(dd,lH), 7.0(q,lH), 7.1-7.4(m,6H)); methyl 2-[2-(4-methylbenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 121, NMR (CDC13): 2.45(s,3H), 3.7(s,3H), 3.85(s,3H), 5.5(s,2H), 6.9(d,lH), 7. I(t,3H), 7.2-7.3(m,3H), 7.45(t, 1 H), 7.85(d,2H), 8.05(d, 1 H)); methyl 2-[4-fluoro-2-(4-methylbenzoylmethoxycarbonyl) phenoxy]-3-methoxypropenoate (compound 122, NMR (CDC13): 2.37 (s, 3H), 3.65 (s, 3H), 3.80 (s, 3H), 5.45 (s, 2H), 6.80 (m, IH), 7.05 (m,lH), 7.20 (m, 2H), 7.25 (s, IH), 7.65 (m, IH), 7.80 (m, 2H); 19F : - 122.08 (s)); methyl 2-[2-(4-nitrobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 123, NMR (CDCI3): 8.34 (d, 2 H), 8.14
(d, 2 H), 8.00 (d, 1 H), 7.44 (t, 1 H), 7.28 (s, 1 H), 7.06 (t, 1 H), 6.90 (d, 1 H), 5.50 (s, 2 H), 3.88 (s, 3 H) and 3.70 (s, 3 H)); methyl 2-[2-(3,4-dichlorobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 124, NMR (CDCI3): 8.06 (s, 1 H), 8.00 (d, 1 H), 7.80 (d, 1 H), 7.58 (d, 1 H), 7.44 (t, 1 H), 7.34 (s, 1 H), 7.08 (t,
1 H), 6.90 (d, 1 H), 5.44 (s, 2 H), 3.86 (s, 3 H) and 3.72 (s, 3 H)); methyl 2-[2-(4-cyanobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 125, NMR (CDC13): 8.08 (d, 2 H), 8.00 (d, 1 H) 7.80 (d, 2 H), 7.44 (t, 1 H), 7.34 (s, 1 H), 7.18 (t, 2 H), 7.08 (t, 1 H), 6.90 (d, 1 H), 5.48 (s, 2 H), 3.88 (s, 3 H) and 3.74 (s, 3 H)); methyl 2-[4-chloro-2-(benzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 126, NMR (CDCI3): 7.96 (d, 1 H), 7.90 (d, 2 H), 7.54 (t, 1 H), 7.42 (t, 2 H), 7.30 (dd, 1 H), 7.26 (s, 1 H), 6.68 (d, 1 H), 5.48 (s, 2 H), 3.78 (s, 3 H) and 3.64 (s, 3 H)); methyl 2-[2-(benzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 127, NMR (CDC13): 7.98 (d, 1 H), 7.92 (d, 2 H), 7.56 (t, 1 H), 7.42 (t, 2 H), 7.36 (t, 1 H), 7.28 (s, 1 H), 7.02 (t, 1 H), 6.76 (d, 1 H), 5.48 (s, 2 H), 3.80 (s, 3 H) and 3.62 (s, 3 H)); and methyl 2-[2-(4-fluorobenzoylmethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 166, NMR (CDC13): 8.08-7.96 (m, 3 H),
7.44 (t, 1 H), 7.34 (s, 1 H), 7.18 (t, 2 H), 7.08 (t, 1 H), 6.90 (d, 1 H), 5.50 (s, 2 H), 3.88 (s, 3 H) and 3.70 (s, 3 H)). Example 18
Using the method of Example 2 but starting from methyl 2-[2-(2- t-butoxycarbonyl-3-cyclopropyl-3-oxopropanoyl)-4-chlorophenoxy]-3- methoxypropenoate, there was prepared: methyl 2-[4-chloro-2-(3- cyclopropyl-3-oxopropanoyl)phenoxy]-3-methoxypropenoate (compound 129, NMR (CDC13): 0.95 (m, 2H), 1.20 (m, 2H), 1.80 (m, IH), 3.75 (s, 3H), 3.90 (s, 3H), 6.70 (s, IH), 6.80 (d, IH), 7.3 (m, IH), 7.40 (s, IH), 7.90 (d, IH), 16.25 (s, IH)). Example 19 Ethane- 1,2-dithioI (0.05ml), followed by boron trifluoride etherate
(0.01ml) were added to a solution of methyl 2-(4-chloro-2- formyIphenoxy)-3-methoxypropenoate (O.lg) in dichloromethane and stirred overnight. Sodium carbonate solution was added, the mixture stirred and the organic phase dried (magnesium sulphate) and evaporated to give methyl 2-[4-chloro-2-(l,3-dithiolan-2-yl)phenoxy]-
3-methoxypropenoate (compound 138, O.lg, m/z 347/349 (M+H)). Example 20
A mixture of methyl 2-[2-methoxycarbonyl-3-(2-methyl-l,3- dioxolan-2-yl)phenoxy] -3 -methoxypropenoate (0.3 lg) and 4- toluenesulphonic acid monohydrate (34mg) in acetone was stirred at reflux overnight. A further addition of 4-toIuenesulphonic acid (17mg) was made, and after 4 hours at reflux, the mixture was evaporated, extracted (ethyl acetate), washed (sodium carbonate solution), dried (sodium sulphate), evaporated and crystallised (aqueous methanol) to give methyl 2-(3-acetyl-2-methoxycarbonylphenoxy)-3- methoxypropenoate (compound 141, 0.12g, NMR (CDC13): 2.57 (s,3H), 3.72 (s,3H), 3.85 (s,3H), 3.95 (s,3H), 7.02 (d, IH), 7.32-7.50 (m,3H) NMR (CDC13) 2.57 (s,3H), 3.72 (s,3H), 3.85 (s,3H), 3.95 (s,3H), 7.02 (d, IH), 7.32-7.50 (m,3H)). Example 21
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. The organic phase was dried (magnesium sulphate), evaporated and purified by chromatography on silica gel eluting with ethyl acetate/toluene (1:9) to give methyl 2-[4-chloro-2-( 1 - hydroxyethyl)phenoxy]-3-methoxypropenoate (compound 142, 24mg, NMR (CDCb): 1.50(d,3H), 3.70(s,3H), 3.90(s,3H), 5.30(m,lH), 6.70(d,lH), 7.10(d,lH), 7.35(s,lH), 7.40(s, lH) NMR (CDC13) 1.50(d,3H), 3.70(s,3H), 3.90(s,3H), 5.30(m,lH), 6.70(d,lH), 7.10(d,lH), 7.35(s,IH), 7.40(s,lH)).
Example 22
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. The organic phase was washed (water), dried (magnesium sulphate) and evaporated to give methyl 2-[4-chloro-2-(diazoacetyl)phenoxy]-3- methoxypropenoate (compound 143, 1.08g, NMR (CDCI3): 3.75 (s, 3H), 3.90 (s, 3H), 6.55 (s, IH), 6.80 (d, IH), 7.30 (d, IH), 7.40 (m, IH), 7.85 (s, IH)). Example 23
3-Acetamidophenylboronic acid (67mg) was added to a solution of methyl 2-(2-carboxy-4-iodophenoxy)-3-methoxypropenoate (0.15 mmol) in sodium carbonate solution (0.45mmol). Palladium (II) acetate (a catalytic amount) was added and the mixture stirred at 20°C overnight under nitrogen. The mixture was diluted (water), acidified, extracted
(dichloromethane), dried (magnesium sulphate) and evaporated to give methyl 2-[4-(3-acetamidophenyl)-2-carboxyphenoxy]-3- methoxypropenoate (compound 144, 7mg, NMR (CDC13): 2.2 (s, 3H), 3.8 (s, 3H), 4.0 (s, 3H), 7.0 (d, IH), 7.6-7.25 (m, 6H), 8.2 (s, IH)). By proceeding in a similar manner the following compounds were prepared: methy 1 2- { 2-carboxy-4-[3-fluoro-4-phenyl]phenylphenoxy } -3- methoxypropenoate (compound 145, NMR (CDCI3): 3.8 (s, 3H), 4.0 (s, 3H), 7.05 (d, IH), 7.65-7.35 (m, 9H), 7.75 (m, IH), 8.35 (m, IH)); methyl 2-[2-carboxy-4-(naphth-2-yl)phenoxy]-3- methoxypropenoate (compound 146, NMR (CDCI3): 3.75 (s, 3H), 3.95
(s, 3H), 7.0 (d, IH), 7.45 (m, 3H), 7.9-7.6 (m, 5H), 8.0 (m, IH), 8.4 (m, IH)); methyl 2-[4-(4-benzyloxyphenyl)-2-carboxyphenoxy]-3- methoxypropenoate (compound 147, NMR (CDCI3): 3.8 (s, 3H), 4.0 (s, 3H), 5.1 (s, 2H), 7.15-7.95 (m, 3H), 7.5-7.3 (m, 8H), 7.6 (m, IH), 8.25
(d, IH)); and methyl 2-[2-carboxy-4-(benzo- 1,3- dioxolan-5-yl)phenoxy]-3-methoxypropenoate (compound 148, NMR CDCI3): 3.8 (s, 3H), 4.0 (s, 3H), 6.0 (s, 2H), 6.85 (d, IH), 7.05-6.95 (m, 3H), 7.45 (s, IH), 7.6 (m, IH), 8.2 (m, IH)). Example 24
Using the procedure of Example 16 but replacing the potassium carbonate by potassium t-butoxide and using ether as solvent the following compounds were prepared: methyl 2-[4-chloro-2-(methoxymethoxycarbonyl)phenoxy]-3- methoxypropenoate (compound 149, NMR (CDC13): 7.80 (d, 2 H), 7.28
(dd, 1 H), 7.26 (s, 1 H), 6.76 (d, 1 H), 5.40 (s, 2 H), 3.80 (s, 3 H), 3.64 (s, 3 H) and 3.48 (s, 3 H)); and methyl 2- { 2-[2-(methoxyethoxy)methoxycarbonyl]phenoxy } -3- methoxypropenoate (compound 150, NMR (CDCl3): 7.86 (d, 2 H), 7.34 (t, 1 H), 7.26 (s, 1 H), 6.98 (t, 1 H), 6.82 (d, 1 H), 5.50 (s, 2 H), 3.86-
3.78 (m, 2 H), 3.78 (s, 3 H), 3.64 (s, 3 H), 3.58-3.50 (m, 2 H) and 3.32 (s, 3 H)).
Example 25
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. The solid was filtered and the filtrate washed (water), dried (magnesium sulphate) and evaporated to give methyl 2-[4-chloro-2-(fluorocarbonyI)phenoxy]-3-methoxypropenoate (compound 151, 45mg, NMR (CDC13): 3.75(s,3H), 3.90(s,3H), 6.90(d,lH), 7.40(s,lH), 7.50(d,lH), 7.95(s,lH); l9F NMR 10.44 (s,lF). Example 26
A mixture of methyl 2-(3-bromomethyl-2- methoxycarbonylphenoxy)-3-methoxypropenoate (0.15g), N- methylmorpholine N-oxide (0. lg), and 4A molecular sieves was stirred overnight in acetonitrile, filtered and ethyl acetate and water added. The organic phase was dried (magnesium sulphate), evaporated and the residue purified by chromatography on silica gel eluting with cyclohexane/ethyl acetate to give methyl 2-(3-formyl-2- methoxycarbonylphenoxy)-3-methoxypropenoate (compound 152, 0.045mg, NMR (CDC13): 3.6(s,3H), 3.8(s,3H), 3.95(s,3H), 7.05(d,lH), 7.25(s,lH), 7.4-7.5(m,2H)).
Example 27
By proceeding according to Example 4 starting from methyl 2-(2- t-butoxycarbonyl-3-methylphenoxy)-3-methoxypropenoate, methyl 2-(3-dibromomethyl-2-carboxyphenoxy)-3- methoxypropenoate (compound 153, NMR (CDC13): 3.65(s,3H),
3.75(s,3H), 6.8(d,lH), 7.1(d,lH), 7.25(s,lH), 7.5(s,lH), 7.55(t,lH)); and methyl 2-(3-dibromomethyl-2-methoxycarbonylphenoxy)-3- methoxypropenoate (compound 167, NMR (CDCI3): 3.65(s,3H), 3.8(s,3H), 3.9(s,3H), 6.7(d,lH), 6.8(s,lH), 7.2(s,lH), 7.3(t,lH), 7.6(d, 1 H)) were similarly prepared.
Example 28
By using the method of Example 4 but starting from methyl 2- (phthalid-7-yloxy)-3-methoxypropenoate, there was prepared methyl 2- (3-bromophthaIid-7-yloxy)-3-methoxypropenoate (compound 154, NMR (CDCI3): 3.65(s,3H), 3.85(s,3H), 6.85(d, 1 H), 7.1 (d, 1 H), 7.25-
7.35(m,2H), 7.5(t,lH)). Example 29
By using the method of Example 4 but starting from methyl 2-(2-t- butoxycarbonyl-3-methylphenoxy)-3-methoxypropenoate, there was prepared methyl 2-(phthalid-7-yloxy)-3-methoxypropenoate (compound 155, NMR (CDC13): 3.7(s,3H), 3.85(s,3H), 5.25(s,2H), 6.8(d,lH),
7.05(d,lH), 7.4(s,lH), 7.55(t,lH)).
Reference Example 1
By proceeding according to Example 1, methyl 2-(4-chloro-2- methyIphenoxy)-3-methoxypropenoate was prepared from methyl 2-(4- chloro-2-methylphenoxy)-3-hydroxyρropenoate, 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. Reference Example 2
To 2.06g sodium hydride (60% dispersion in mineral oil) in dimethylformamide (20ml) cooled to 0 °C was added ethyl formate (53.33ml) and 12.0g of methyl (2-bromo-4-chlorophenoxy)acetate in 80ml of dimethylformamide. The cooling bath was removed and the contents stirred at ambient temperature for 1 hour. Sodium carbonate solution was added and the contents extracted with ether. The aqueous phase was separated, acidified to pH4 with HClaq. and extracted with ether. The ethereal layer was washed with saturated sodium chloride solution, dried and evaporated to give methyl 2-(2-bromo-4- chlorophenoxy)-3-hydroxypropenoate. M.S. m/z 308 (M+H).
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.
Reference Example 3
Cone. H2SO 1.54(ml) was added to a stirred suspension of anhydrous MgSO4 in CH2C12. 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 NaHCO3 (220ml) and the mixture stirred for 20 minutes. The organic phase was separated, washed with brine, dried and evaporated to give t-butyl 5-chloro-2- hydroxybenzoate, NMR (CDC13): 11 (lH,s), 7.7 (lH,s), 7.35 (lH,d), 6.9(1 H,d), 1.6 (s, 9H).
Reference Example 4
3.6g of t-butyl 5-chIoro 2-hydroxybenzoate were heated to reflux during 2.5 hours with 2.2ml of methyl bromoacetate and 4.3g of K2CO3 in acetonitrile. The mixture was cooled, diluted with water and extracted with ethyl acetate. The organic layer was washed and dried to give methyl (2-t-butyloxycarbonyl-4-chlorophenoxy) acetate, NMR (CDC13): 7.7 (lH,s), 7.35 (lH,d), 6.8(lH,d) 4.7 (s,2H), 3.8 (3H,s),1.6 (9H,s). By proceeding in a similar manner were prepared: methyl (4-chloro-2-methylphenoxy)acetate, NMR (CDC13): 4.6 (s, 2H) 3.8 (s), Rf=0.44 on silica TLC, Et2O Hexane eluent 1:1 v/v, and methyl (2-bromo-4-chlorophenoxy)acetate, MS m/z 279 (M+H).
Reference Example 5 0.95g of methyl (2-t-butyloxycarbonyl-4-chlorophenoxy) acetate were mixed with 7.5ml of t-butoxy bis(dimethylamino)methane. The mixture was heated for 2 hours at 80°C, then cooled, diluted with water and extracted with CH2C12. The organic layer was dried, filtered and purified by chromatography to give methyl 2-(2-t-butyloxycarbonyl-4- chlorophenoxy)-3-N-dimethylaminopropenoate, N.M.R. 7.7 (lH,s) 7.35
(lH,d), 7.15 (lH,s), 6.9 (lH,d), 3.6 (3H,s), 3.0 (s, 6H) 1.6 (9H,s).
50mg of methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3-N- dimethylaminopropenoate were mixed at 0°C with tetrahydrofuran (1.3ml) and 0.436ml aqueous HC1 (2M). The mixture was stirred for 12 hours at 20°C, then evaporated, washed with brine and extracted with ether. The organic layer is dried and purified by chromatography, so as to give methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)-3- hydroxypropenoate, M.S. m/z 327 (M-H). Reference Example 6 t-Butyl 5-chIorosalicylate (1.6g) was dissolved in acetone (35ml) and potassium carbonate (4.84g) and methyl 2-bromo-2-butenoate
(1.25g) was added. The contents were heated to reflux for 24 hours, cooled and filtered. Concentration in vacuo gave an oil that was purified by chromatography to give 2.1g methyl 2-(2-t-butyloxycarbonyl-4- chIorophenoxy)but-2-enoate. NMR (CDC13): 1.6 (s, 9H), 1.75 (d, 3H), 3.65 (s, 3H), 6.7 (m, 2H), 7.25 (m, IH), 7.70 (m, IH).
Reference Example 7
510 mg of methyl 2-(2-t-butyloxycarbonyl-4-chlorophenoxy)but- 2-enoate was dissolved in dichloromethane and cooled to -20°C . HC1 gas was bubbled through it for 5 minutes and the solution was allowed to warm to ambient temperature. After 30 minutes the*contents were washed several times with water and dried. Removal of solvent gave 0.4 lg of methyl 2-(2-carboxy-4-chlorophenoxy)but-2-enoate. NMR (CDC13): 1.90 (d, 3H), 3.75 (s, 3H), 6.75 (d, IH) 6.90 (q, IH), 7.40 (m, IH), 8.00 (m, IH). Reference Example 8
To 130 mg of ethyl 2-chloro-3-oxopropanoate dissolved in 2ml of isopropanol and 162 μl of triethylamine was added methyl thiosalicylate dropwise. The contents were stirred at ambient temperature for 30 minutes and at reflux for 3 hours. The solvent was removed in vacuo and the residue partitioned between water and ether. The organic layer was discarded and the aqueous layer acidified at pH4 and extracted with ether. The ethereal layer was separated, dried, concentrated and purified by column chromatography to give 36 mg of ethyl 3-oxo-2-(2- methoxycarbonyI)thiophenoxypropanoate, M.S m/z 283 (M+H). 1 1.1 mg of ethyl 3-oxo-2-(2-methoxycarbonyl)thiophenoxy propanoate was dissolved in 0.5 ml DMF and dimethylsulfate (5.6 μl) added followed by 1 1.4 mg of potassium carbonate. The contents were stirred at ambient temperature for 24 hours then 2.5 ml of sodium carbonate solution (2N) was added and the contents extracted with ether. The ethereal extract was dried and concentrated to give 9.6mg ethyl 3- methoxy-2-(2-methoxycarbonyl)thiophenoxy-2-propenoate. NMR (CDCI3): 1.05 (t, 3H), 3.8 (3, 3H), 3.9 (s, 3H), 4.1 (q, 2H), 7.05 (m, 2H),
7.25 (m, IH), 7.9 (m, IH) 8.0 (s, IH).
Reference Example 9
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
(magnesium sulphate) and evaporated to give methyl 2-[2-(2-t- butoxycarbonyl-3-cyclopropyl-3-oxopropanoyl)-4-chlorophenoxy]-3- methoxypropenoate (1.49g).
According to a feature of the present invention, there is provided a method for controlling the growth of weeds (i.e. undesired vegetation) at a locus which 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. For this purpose, 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. By the term "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. By the term "post- emergence application" is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
For example, 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 puφurea, 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.
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. When applied to a crop-growing area, the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop. In general, taking these factors into account, 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.
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. For this puφose 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.
Examples of such non-crop-growing areas 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. When used for such puφoses 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.
Pre- or post-emergence application, and preferably pre-emergence application, in a directional or non-directional fashion (e.g. by directional or non-directional spraying) at application rates between 50g and 5000g, and preferably between 50g and 2000g, most preferably between lOOg and lOOOg of active material per hectare are particularly suitable for this puφose. When used to control the growth of weeds by pre-emergence application, the compounds of formula (I) may be incoφorated 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.
Where especially prolonged weed control is required, the application of the compounds of formula (I) may be repeated if required.
According to a further feature of the present invention, there are provided 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. The term "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. Preferably, 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. nonyl- or octyl-phenols, or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates. Suitably, the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g. from 0.05% to 10% by weight, of surface-active agent but, if desired, 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.
Examples of 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. The solid compositions
(which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula (I) with solid diluents or by impregnating the solid diluents or carriers with solutions of the compounds of formula (I) in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders.
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 incoφorate a surface-active agent. Suitable liquid diluents for incoφoration 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.
When desired, 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.
Unless otherwise specified, the following percentages are by weight. 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. 10 to 30%, of one or more compounds of formula (I), from 0 to 25% of surface-active agent and from 10 to 90%, e.g. 45 to 85%, of water miscible solvent, e.g. triethylene glycol, or a mixture of water-miscible solvent and water; 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. 2 to 10%, of surface-active agent and from 5 to 95%, e.g. 20 to 60%, of solid diluent, e.g. clay, granulated with the addition of water to form a paste and then dried and, 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.
Examples of other pesticidally active compounds which may be included in, or used in conjunction with, the herbicidal compositions of the present invention include 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 ,3-dioxo- 1 ,3,4,5,6,7-hexahydroisoindol-2-yl)- phenyl]-acrylate, clopyralid, which is 3,6-dichloropyridine-2-carboxyIic acid, cyanazine [2-chloro-4-(l-cyano-l-methylethylamino)-6- ethylamino-l,3,5-triazine], 2,4-D [2,4-dichlorophenoxy-acetic acid], dicamba [3,6-dichloro-2-methoxybenzoic acid], dichloφrop-P, which is
(R)-2-(2,4-dichlorophenoxy)propionic acid, difenzoquat [1,2- dimethyl- 3,5-diphenyl-pyrazolium salts], diflufenican, which is 2',4'-difluoro-2- (α,α,α,-trifluoro-m-tolyloxy)nicotinanilide, fenoxaprop-p-ethyl, which is (R)-2-[4-(6-chloro- 1 ,3-benzoxazol-2-yloxy)phenoxy]propionic acid, flampropmethyl, which is [methyl N-2-(N- benzoyl-3-chIoro-4- fluoroanilino)-propionate], flumetsulam, which is 2',6'-difluoro-5- methylf 1 ,2,4]triazolo[ 1 ,5-α]pyrimidine-2-sulfonanilide, fluometuron, which is [N'-(3-trifluoro- methyIphenyl)-N,N-dimethylurea], flupyrsulfuron, which is 2-[2-(4,6-dimethoxypyrimidin-2- ylcarbamoylsulfamoyl)]-6-trifluoromethylpyridine-3-carboxyIic acid, flurtamone, which is (R.S 5-methylamino-2-phenyI-4-(α,α.,α,-trifluoro- m-toIyI)furan-3(2H)-one, iodosulfuron, which is 2-(4-methyl-6- methoxy- 1 ,3,5-triazyn-2-ylcarbamoylsulfamoyl)-4-iodobenzoic acid, ioxynil, which is 4 hydroxy-3,5-di-iodobenzonitrile, isopropyl 2-chloro- 5-[4-chloro-5-( 1 , 1 -difluoromethoxy)- 1 -methyl- lH-pyrazol-3-yl]-4- fluorobenzoate, isoproturon, which is 3-(4-isopropylphenyl)-l,l- dimethylurea, (R)-2-[4-(6-chIorobenzoxazol-2- yloxy)phenoxy]propionic acid, JV-485, which is 5-[4-bromo-l-methyl- 5-(trifluoromethyl)-lH-pyrazol-3-yl]-2-chloro-4-fluoro-benzoic acid, mecoprop-P, which is (R)-2-(4-chloro-o-tolyloxy)propionic acid, metosulam, which is 2',6',-dichloro-5,7-dimethoxy-3'- methyl[l,2,4]triazolo[l,5-α]pyrimidine-2-sulfonanilide, metsulfuron- methyl, which is methyl 2-(4-methoxy-6-methyl-l,3,5-triazin-2- ylcarbamoylsulfamoyl)benzoate, pendimethalin, which is /V-(l- ethylpropyl)-2,6-dinitro-3,4-xylidine, picolinafen, which is N-(4- fluorophenyl)-6-(3-trifluoromethylphenoxy)-pyridine-2-carboxamide, insecticides, e.g. synthetic pyrethroids, e.g. permethrin and cypermethrin, and 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:
Active Ingredient 20% w/v
N-Methylpyrrolidinone (NMP) 25% w/v
Calcium dodecylbenzenesulphonate (CaDDBS) 4% w/v (Arylan CA) Nonylphenol ethylene oxide propylene oxide condensate (NPEOPO) (Synperonic NPE 1800) 6% w/v Aromatic solvent (Solvesso) to 100 volumes by stirring NMP, active ingredient (Compound 1), CaDDBS, NPEOPO and Aromatic solvent until a clear solution is formed, and adjusting to volume with Aromatic solvent.
Example C2
A wettable powder is formed from:
Active Ingredient 50% w/w Sodium dodecylbenzenesulphonate
(Arylan SX85) 3% w/w
Sodium methyl oleoyl taurate
(Arkopon T) 5% w/w
Sodium polycarboxylate (Sopropon T36) 1 % w/w Microfine silicon dioxide (Tixosil 38) 3% w/w
China clay 38% w/w by blending the above ingredients together and grinding the mixture in an air jet mill.
Example C3
A suspension concentrate is formed from: Active Ingredient 50% w/v
Antifreeze (Propylene glycol) 5% w/v
Ethoxylated tristyrylphenol phosphate
(Soprophor FL) 0.5% w/v
Nonyl phenol 9 mole ethoxylate
(Ethylan BCP) 0.5% w/v
Sodium polycarboxylate (Sopropon T36) 0.2% w/v
Attaclay (Attagel) 1.5% w/v
Antifoam (Rhodorsil AF426R) 0.003% w/v
Water to 100 volumes by stirring the above ingredients together and milling in a bead mill.
Example C4
A water dispersible granule is formed from: Active Ingredient 50% w/w
Sodium dodecylbenzenesulphonate
(Arylan SX 85) 3% w/w
Sodium methyl oleoyl taurate (Arkopon T) 5% w/w
Sodium polycarboxylate (Sopropon T36) 1% w/w Binder (Sodium lignosulphonate) 8% w/w
China clay 30% 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. Optionally the active ingredient may be ground either on its own or admixed with some or all of the other ingredients.
The following non-limiting examples illustrate the invention.
EXPERIMENTAL EXAMPLE 1
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.
Two weeks after treatment the percent reduction in plant growth, compared to an untreated control, was assessed.
Compounds 1, 2, 5, 42, 43, 45, 62, 74, 85, 131, 132, 133, 134, 135, 136, 137, 140, 149, 159, gave 100% reduction in the growth of one or more weed species. Compounds 3, 6, 7, 8, 18, 19, 20, 35, 36, 38, 39, 40, 44, 49, 50,
51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 63, 64, 66, 68, 75, 76, 78, 79, 80, 81, 82, 83, 84, 87, 88, 89, 90, 92, 93, 94, 97, 99, 100, 101, 109, 110, 112, 113, 114, 1 15, 116, 118, 119, 120, 122, 123, 125, 126, 128, 129, 130, 138, 150, 152, 156, 160, 163, 166, gave at least 80% reduction in the growth of one or more weed species.
Compounds 10, 12, 15, 16, 26, 28, 31, 65, 67, 69, 71, 73, 77, 86, 91, 95, 96, 103, 111, 121, 124, 127, 145, 146, 148, 154, 155, 157, 161, 162, 164, 167, gave at least 70% reduction in the growth of one or more weeds species.
EXPERIMENTAL EXAMPLE 2
Seed of the various weed species, as listed in example 1, were sown and grown up to a 1-3 leaves stage. A post-emergence application of herbicide, dissolved in a mixture of acetone and water, was applied at a rate of 62g/ha.
Two weeks after treatment the percent reduction in plant growth, compared to an untreated control, was assessed.
Compounds 2, 49, 50, 51 , 72, 78, 81 , 82, 83, 84, 85, 88, 90, 92, 93, 94, 95, 99, 101, 1 18, 1 19, 120, 131, 132, 133, 134, 135, 136, 137, 140, 149, 152, 153, 156, 167, gave 100% reduction in the growth of one or more weed species. Compounds 3, 4, 5, 10, 16, 18, 19, 20, 35, 43, 45, 46, 47, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 73, 74, 75, 76, 77, 79, 80, 86, 87, 89, 91, 96, 97, 98, 100, 102, 103, 109, 110, 111, 112, 113, 114, 115, 116, 117, 121, 122, 123, 124, 125, 126, 128, 129, 130, 138, 141, 150, 154, 155, 157, 158, 159, 160, 161, 162, 163, gave at least 80% reduction in the growth of one or more weed species.
Compounds 17, 21, 26, 42, 48, 139, 142, 143, 144, 145, 146, 148, gave at least 70% reduction in the growth of one or more weed species.
In another aspect of the invention there is provided 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.
By "non-phytotoxic" is meant an amount of the antidote which causes at most minor or no injury to the desired crop species. By "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. Preferably 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.
Examples of the 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):
R70-CO-NR72R71
Figure imgf000109_0001
wherein R 70 can be selected from the group consisting of haloalkyl; haloalkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; Ν-Ν-alkynylcarbamylalkyl; Ν- alkenylcarbamylalkoxyalkyl; Ν-alkyl-Ν-alkynylcarbamylalkoxyalkyl; alkynyloxy; haloalkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonalkyl; alkyl thioalkyl; haloalkylcarbonyloxyalkyl; alkoxycarboalkyl; haloalkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyloxyalkyl; hydroxyalkyl; alkoxysulfonoalkyl; furyl; thienyl; alkyldithiolenyl; thienalkyl; phenyl; substituted phenyl wherein the substituents can be selected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxy and salts thereof, and haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein the substituents can be selected from halogen, alkyl, alkoxy, and halophenoxy, phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenylalkyl; halophenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl; alkyny lcarbamy lpyridinyl ; dialkenylcarbamylbicycloalkenyl and alkynylcarbamylbicycloalkenyl;
71 72
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; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxy carboalkeny 1; haloalkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkylcarbamyloxyalkyl; alkoxycarbonyl; haloalkoxycarbonyl; halophenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein said substituents can be selected from alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalimido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido and alkylcarboalkenyl; phenylsulfonyl; substituted phenylalkyl wherein said substituents can be selected from halogen or alkyl; dioxyalkylene; halophenoxyalkylamido-alkyl; alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl- substituted furyl; furylalkyl; pyridyl; alkylpyridyl; alkoxyazolyl; tetrahydrofurylalkyl; 3-cyano-thienyl; alkyl substituted thienyl; 4,5- polyalkylene thienyl; α-haloalkylacetamidophenylalkyl; α- haloalkylacetamidonitrophenylalkyl; α- haloalkylacetamidohalophenylalkyl; and cyanoalkenyl; or R 71 and R 72 when taken together can form a structure consisting of piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; moφholyl; azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidinyl; furyloxazolidinyl; thienyloxazolidinyl; pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; C3 spirocycloalkyl-oxazolidinyl: alkylaminoalkenyl; alkylideneimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; -tetrahydro- or perhydroquinolyl or isoquinolyl; indolyl or di- or perhydroindolyl; and which combined R 71 and R 72 members can be substituted with those independent R 71 and R 72 radicals enumerated above; or
(ii) one of the following compounds: α-[(cyanomethoxy)imino]benzeneacetonitrile; α-[( 1 ,3-dioxolan-2- ylmethoxy)imino]-benzeneacetonitrile; O-[3-dioxolan-2-ylmethyl]- 2,2,2-trifluoromethyl-4'-chloroacetophenone oxime; benzenemethamine, which is N-[4-(dichIoromethylene)-l,3-diotholan-2-ylidene]-α-methyl, hydrochloride; diphenylmethoxy acetic acid methyl ester; 1,8-naphthalic anhydride; 4,6-dichloro-2-phenylpyrimidine; 2-chloro-N-[l-(2, 4, 6- trimethylphenyl)ethenyl]acetamide; ethylene glycol acetal of 1,1- dichloroacetone; benoxacor, which is 4-dichloroacetyl-3,4-dihydro-3- methyl-2H-l,4-benzoxazine; dichlormid, which is N,N-dialIyl-2,2- dichloroacetamide; fenclorim, which is 4,6-dichloro-2- phenylpyrimidine; furilazole which is (RS)-3-dichloroacetyl-5-(2- furanyl)-2,2-dimethyloxazolidine; cloquintocet (5-chloroquinoline-8- yloxy acid) or a salt or ester thereof such as cloquintocet-mexy which is (l-methyIhexyl(5-chloroquinoline-8-yloxy) acetate); fenchlorazole, which is ( 1 -(2,4-dichlorophenyl)-5-trichloromethyl)- 1 H- 1 ,2,4-triazole-3- carboxylic acid), or a salt or ester thereof such as fenchlorazole-ethyl, which is (ethyl l-(2,4-dichlorophenyl)-5-trichloromethyl)-lH- 1,2,4- triazole-3-carboxylate); mefenpyr-ethyl, which is (diethyl l-(2,4- dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylate); 5,5- diphenylisoxazolinone-3-carboxylic acid; and R29148, which is 2,2- dichloro- 1 -(2,2,5-trimethyloxazoIidin-3-yl)-ethanone.
Especially preferred antidotes for use in the present invention include: cloquintocet, cloquintocet-mexyl, fenchlorazole, fenchlorazole- ethyl, benoxacor and R29148.
The following non-limiting examples illustrate the invention.
EXPERIMENTAL EXAMPLE 3
An experiment was carried-out to examine the damage on maize and wheat following post-emergence applications of compounds of formula (I) (hereafter "the Herbicide") and flurilazole, benoxacor, dichlormid, cloquintocet, fenchlorazole, naphthalic anhydride and R29148, alone and in tank mixtures.
The 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).
Individual components and mixtures of Compound 2, Compound 82 and cloquintocet-mexyl were applied late post-emergence of the weeds and crop. _ i j j _
The percent reduction in plant growth, compared to an untreated control was assessed 12 and 25 days after treatment (DAT). The following tables summarise the results obtained.
Table A Post-emergence treatment of a natural population of ■alium aparine with Compound 2 and cloquintocet-mexyl
Figure imgf000114_0001
Table B Effect of Compound 2 and cloquintocet-mexyl on Triticum aestivum
Figure imgf000114_0002
Table C Post-emergence treatment of a natural population of Galium aparine with Compound 82 and cloquintocet- mexyl
Figure imgf000114_0003
Table D Effect of Compound 82 and cloquintocet-mexyl on Triticum aestivum
Figure imgf000114_0004
EXPERIMENTAL EXAMPLE 5
Representative compounds for formula (I), Compounds 2 and 82 and cloquintocet-mexyl, were applied as technical materials prepared in acetone to a locus comprising a drilled population of Galium aparine and wheat (Triticum aestivum).
Individual components and mixtures of Compound 2, Compound 82 and cloquintocet-mexyl were applied late post-emergence of the weeds and crop.
The percent reduction in plant growth, compared to an untreated control was assessed 20 and 33 days after treatment (DAT).
The following tables summarise the results obtained.
Table E Post-emergence treatment of a drilled population of
Galium aparine with Compound 2 and cloquintocet-mexyl
Figure imgf000115_0001
Table F Effect of Compound 2 and cloquintocet-mexyl on Triticum aestivum
Figure imgf000115_0002
Table G Post-emergence treatment of a drilled population of Galium aparine with Compound 82 and cloquintocet- mexyl
Figure imgf000116_0001
Table H Effect of Compound 82 and cloquintocet-mexyl on Triticum aestivum
Figure imgf000116_0002
According to a further feature of the present invention, there is provided 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.

Claims

1. An aryl vinyl ether derivative of general formula (I):-
Figure imgf000117_0001
(I) wherein: p is 0 or 1 ,
X1 is O, NH or S;
X2 is O, S, NR18 or a simple bond;
X3 is N or CR19;
R17 and R18 independently represent a hydrogen atom or an optionally substituted group R20, R21, R22 or R23, wherein;
R20 represents a lower alkyl radical;
R21 represents a lower alkenyl radical;
R22 represents a lower alkynyl radical;
R23 represents a -(CH2)m-phenyl radical; m represents zero or one;
R16 is R24 or OR25 or SR25, NR25R26 or alkyl substituted by alkoxycarbonyl;
R24 , R25 and R26 independently have one of the meanings given for
R 18.
R19 has one of the meanings given for R ; R10 represents a radical selected from; -CH2NO2) -CHR27R28,-CR27R28R281, -CR30R29R291, -CO-NR30R31, -CH2NR30R31, -CH=CR3IR32, -CH2N(R30)S(O)qR33, -C(O)SR32, -CH2C(O)SR32, -(CH2)zCO2R32, -CO2R32, -CH=CHC(O)OR32, -C(R32)=N-NR30R31, -C(R32)=N-NH-C(O)lower alkyl, -COR32, -C(O)OC(O)R32, -C(=N-OH)R32, -C≡CCOOR32, -CH2SCN,
-CH2NCO, -CH2NCS, -CH2N3, -CH2CN, -CH2OSCN, -CH2OCN, -CH2N(R30)CO2R33, -CH2OSO2R33, -CH2SO2OR33, -CH2OCO2R33, -CH=CHNR33R34, -C(O)ONR33R34, -C(=NR35)R32, -CH2P(O)R35 R36 , -CH2 OP(O)R35R36, -CH2OC(O)NR30R36, -CH2OCH2C(O) (optionally substituted phenyl), -CO2N=C (optionally substituted phenyl)2, N- succinimidomethyl, N-phthalimidomethyl, a tetrazolyl group (especially 1-tetrazolyl), -CONHNHR30, -CO2CH2CO (optionally substituted phenyl, or a saturated or unsaturated 5-7 membered heterocyclic ring containing from 1-3 hetero atoms selected from O, N and S), -CO2CH2 (saturated or unsaturated 5-7 membered heterocyclic ring containing from 1-3 hetero atoms selected from O, N and S), CO2 R32a, COCH2COR33, COCHN2, CONH (lower alkyl substituted by hydroxy), - CH(OH)(lower alkyl), C(R32)=N-NH-C(S)NRa, C(R32)=N-NH (optionally substituted unsaturated 5-7 membered heterocyclic ring containing from 1-3 atoms selected from O, N and S), C(R32)=N-NR30aR3 la, C(R32)=N-NHSO2R33 and C(O)F; z represents one, two, three or four; q represents zero or two; Ra represents H or lower alkyl; R32 represents an optionally substituted N-linked imidazole or triazole ring optionally fused to a benzene ring;
R30a and R31a 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 NRa group in the ring; R27, R28 and R281 represent the same or different halogen atoms;
R29 and R291 represent OR37 or SR37 or, R29 and R291 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 , R and R independently represent hydrogen, lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted -(CH2)m-phenyl;
R33 and R34 represent R32 with the exclusion of the hydrogen atom; R35 and R36 represent a hydrogen atom or a radical which may be any of the following ; alkyl, alkoxy or optionally substituted phenyl;
R37represents lower alkyl, lower haloalkyl, lower alkenyl or lower haloalkenyl ;
Rπand R13 each independently represent hydrogen or alkyl, or R11 and R13 may be together a simple bond creating a double bond with the carbon atom to which they are attached, or
R11 and R13 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 or a bicyclic ring, these rings being optionally substituted by from one to four R15 radicals, each ring containing at most eight ring members, preferably at most six, wherein R15 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 haloalkyl, lower haloalkenyl, lower haloalkynyl, halocycioalkyl, lower haloalkoxy, lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkylsulfonyl, nitro, amino, lower alkylamino, lower dialkylamino, optionally substituted phenoxy, lower alkylcarbonylamino, carbamoyl, 975 lower alkylcarbamoyl, lower dialkylcarbamoyl, -CH2SCN, SF5, -CR30=N-R31, -CR30=NOR31, -CR30=NNR30 R31, -CR30R29R291, alkoxyalkyl, CRbRcRa, CORa, optionally substituted phenyl or naphthyl; or alkenyloxy substituted by alkoxycarbonyl or CO2H;
Rb and Rc together with the C atoms to which they are attached form a 5 or 6 -membered cyclic acetal group;
or R10Rl lR12C-C(R13)(R14)- represents a group (A), (B), (C), (D) or (E):
Figure imgf000121_0001
wherein Rd, Re, Rf, Rg and Rh represent H, lower alkyl, halogen or OH, and n represents the values 0, 1, 2 or 3; R151 represents R15 or a hydrogen atom; R12 and R14 each independently represent hydrogen or alkyl or may form a simple bond, creating a double bond together where Rl ' and R13 are together a single divalent radical; preferably with the following provisos; i) when RlV 'R12C-C(RI 3)(R14)- represents a phenyl ring optionally substituted by R15; R10 represents -CO2 R32, CONR30R31, CHR27R 28 of CR 27 R28 R28i^ where R32 represents alkyl or haloalkyl;
R30 and R31 represent H or alkyl, and R27, R28 and R281 are as defined above; p is zero; X, is O; X2 is O; X3 is CH; R16 is OR25; then R15 is not a monohalomethyl group; ii) when R'V 'R12C-C(R13)(R14)- represents a group
EtO2C-CH=CH-; p is 1 ; Xi is S; X2 is a bond; R17represents phenyl; X3 is CH; then R16 is not NH2 or NMe2; iii) when R11, R12, R13, R14 each represent H; p is 1; X, is S, X2 is O; R17 represents Et; X3 is N; R16 represents -NH(4-nitrophenyl); R10 is not CO2H or CONHPh; iv) when Ru, R12, R13, R14 each represent H; p is zero; X! is S, X2 is O; R17 represents Et; X3 is N; R16 represents -NH(4-nitrophenyl); R10 is not CO2H or CONH2; v) when p represents zero; Xt is O; X2 is a bond; R17 represents H; X3 is CH; R16 represents NMe2; RI0RπR12C-C(RI3)(R14)- represents a 5-methyl-2-R10-substituted-thien-3-yl group; R10 is not CO2H or CO2Me; vi) when R , R , R and R each represent H; p is zero; Xi is S; X is O, R17 represents H; X3 is N; R16 represents -NH(4-nitrophenyl); R10 is not CO2H; vii) when R10 represents CO2Et; Ru, R12, R13 and R14 each represent H; p is zero;
Figure imgf000122_0001
is S; X2 is NH, R17 represents phenyl; X3 is CMe; R16 is not NH2 or NHMe; and viii) when p is zero; Xi is O; X2 is O; R17 represents Me; X3 is CH; R16 represents OMe; R'V 'R12C-C(R13)(R14)- represents a 1 ,3- dimethyl-4- R10-substituted-pyrazoI-5-yl group; R10 is not 4-chlorobenzoyl; and agriculturally acceptable salts and metal complexes thereof.
2. An aryl vinyl ether derivative of formula (I) as defined in claim 1 wherein: p is O or 1,
X' is O, NH or S; X2 is O, S, NR18 or a simple bond; X3 is N or CR19;
17 1 R
R and R independently represent a hydrogen atom or an optionally substituted group R20, R21, R22 or R23,wherein; R20 represents a lower alkyl radical;
91
R represents a lower alkenyl radical;
99
R represents a lower alkynyl radical; R23 represents a -(CH2)m-phenyl radical; m represents zero or one; R16 is R24 or OR25 or SR25 or NR^R26;
R24 R25 and R26 independently have one of the meanings given for
R 18.
R19 has one of the meanings given for R16;
R10 represents a radical selected from; -CH2NO2, -CHR27R28,-CR27R28R281, -CR30R29R291, -CO-NR30R31,
-CH2NR30R31, -CH=CR31R32, -CH2N(R30)S(O)qR33, -C(O)SR32, -CH2 C(O)SR32, -CH2CO2R32, -CO2R32, -CH=CHC(O)OR32, -C(R32)=N-N R30 R31, -C(R3 )=N-NH-C(O)lower alkyl, -COR32, -C(O)OC(O)R32, -C(=N- OH)R32, -OCCOOR32, -CH2SCN, -CH2NCO, -CH2NCS, -CH2N3, -CH2CN, -CH2OSCN, -CH2OCN, -CH2N(R30)CO2R33, -CH2OSO2R33, -CH2SO2OR33,
-CH2OCO2R33, -CH=CHNR33R34, -C(O)ONR33R34, -C(=NR35)R32, - CH2P(O)R35 R36 , -CH2OP(O)R35R36, -CH2OC(O)NR30R36, -CH2OCH2C(O) (optionally substituted phenyl), -CO2N=C (optionally substituted phenyl)2, N-succinimidomethyl, N-phthalimidomethyl or a tetrazolyl group (especially I -tetrazolyl); q represents zero or two;
R27, R28 and R281 represent the same or different halogen atoms;
R29 and R291 represent OR37 or SR37 or,
R29 and R291 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 , R and R independently represent hydrogen, lower alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted -(CH2)m-phenyl; R and R represent R with the exclusion of the hydrogen atom;
R35 and R36 represent a hydrogen atom or a radical which may be any of the following ; alkyl, alkoxy or optionally substituted phenyl;
R37represents lower alkyl, lower haloalkyl, lower alkenyl or lower haloalkenyl ; R and R each independently represent hydrogen or alkyl, or
R and R may be together a simple bond creating a double bond with the carbon atom to which they are attached, or
R11 and R13 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, or a bicyclic ring, these rings being optionally substituted by an R15 radical, each ring containing at most eight ring members, preferably at most six, wherein R15 represents a halogen atom, hydroxy, cyano, lower alkoxycarbonyl, lower alkyl, lower alkenyl, lower alkynyl, optionally substituted cycloalkyl, lower alkoxy, lower alkylthio, lower alkylsulfonyl, lower alkylsulfonyl, lower haloalkoxycarbonyl, lower haloalkyl, lower haloalkenyl, lower haloalkynyl, halocycioalkyl, lower haloalkoxy, lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkylsulfonyl, nitro, amino, lower alkylamino, lower dialkylamino, optionally substituted phenoxy, lower alkylcarbonylamino, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, SF5, - CR30=N-R31, -CR30=NOR31, -CR30=NN R30 R31 or -
CR30R29R29. ; R151 represents R1 or a hydrogen atom; R and R each independently represent hydrogen or alkyl or may form a simple bond, creating a double bond together where Ru and R13 are together a single divalent radical; with the proviso that when R10RUR12C-C(R13)(R14)- represents a phenyl ring optionally substituted by R15; R10 represents -CO2 R32,
CONR30R31, CHR27R28 or CR27 R28 R281, wherein R32 represents alkyl or haloalkyl; R30 and R31 represent H or alkyl, and R27, R28 and R281 are as defined above; p is zero; Xj is O; X2 is O; X3 is CH; R16 is OR25; then R15 is not a monohalomethyl group; and agriculturally acceptable salts and metal complexes thereof.
11 1 ^
3. A compound according to claim 1 or 2 wherein R and R form a phenyl ring substituted by a halogen atom.
4. A compound according to claim 1, 2 or 3 wherein X3 represents CR19, wherein R 9 is a hydrogen atom.
5. A compound according to any one of claims 1 to 4 wherein
X2 represents an oxygen atom.
6. A compound according to any one of claims 1 to 5 wherein X\ represents an oxygen atom.
7. A compound according to any one of claims 1 to 6 wherein R17 represents methyl.
8. A compound according to claim 1 wherein R16 is mefhoxy.
9. A compound according to claim 1 wherein R is -CHR27R28 (in which R27 and R28 are bromine), or -COR32 or -CO2R32 (in which R32 is lower alkyl or hydrogen), or -CH2OSO2R33 (R33 represents substituted phenyl), or -CH2NO2, or -CH2OCH2C(O)Ph, or
-CH OTs, or -C(R32)=N-NHSO R33 (in which R32 is hydrogen and R33 is lower alkyl), or -C(R32)=N-NH-C(S)NRa (in which R32 is hydrogen and Ra is lower alkyl), or -C(R32)=N-NR30R31(in which R32 and R30 are hydrogen and R31 is optionally substituted -(CH2)m-phenyl), or -C(R32)=N-N30aR31a (in which R32 is hydrogen, and R30a and R31a together with the N atom to which they are attached form a 6 membered saturated heterocyclic ring containing an additional O and NRa group in the ring), or -C(R32)=N-NH(optionally substituted unsaturated 6 membered heterocyclic ring containing a nitrogen atom) (in which R32 is p hydrogen), or -C(O)F, or -CO2CH2CO(optionally substituted phenyl), or -CO2R32a (in which R32a is an optionally substituted N-linked triazole ring fused to a benzene ring), or -CO-NR30R31(in which R30 is hydrogen and R31 is lower alkyl), or
-CONHNHR30 (in which R30 is optionally substituted -(CH2)m-phenyl), or -C(R32)=N-NH-C(O)lower alkyl (in which R32 is hydrogen), or -C(O)SR32 (in which R32 is lower alkyl) or -CH(OH)lower alkyl, or -COCHN2, or -CR30R29R291 (in which R30 is hydrogen, and R29 and R291 together form a divalent radical with which the carbon atom to which they are attached forms a 5 membered optionally substituted thioacetal ring), or -C(=N-OH)R32 (in which R32 is lower alkyl), or -(CH2)zCO2R32 (in which R32 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxyalkyl, optionally substituted -(CH2)m-phenyl); or R10RnR12C-C(R13)(R14)- represents a group A in which Rd and
Re represent hydrogen or halogen; and
R15 is -COR , or halogen, or lower alkyl, or lower alkoxy, or lower haloalkoxy, or lower alkoxycarbonyl, or CRbRcRa (in which Rb and Rc form a 5 membered cyclic acetal group and in which Ra represents hydrogen).
10. A compound according to claim 1 or 2 wherein R10 represents -COR32 or CO2R32 and R32 represents lower alkyl or hydrogen.
11. A compound according to claim 1 wherein:
Rn and R13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups; X3 is CR19 wherein R represents a hydrogen atom; Xi and X2 each represent an oxygen atom;
R16 and R17 each represent a methyl group; and R10 is -CO2R32.
12. A compound according to claim 1 wherein:
R1 ' and R13 form a phenyl or naphthyl ring substituted by one or more halogen, alkyl or haloalkyl groups; X3 is CR19 wherein R19 represents a hydrogen atom; Xi and X2 each represent an oxygen atom;
R16 and R17 each represent a methyl group; and R10 is -CO2R32 in which R32 is lower alkyl or hydrogen.
13. A herbicidal composition which comprises as active ingredient a herbicidally effective amount of an aryl vinyl ether derivative of general formula (I) according to any one of claims 1 to 12 or an agriculturally acceptable salt or metal complex thereof, in association with an agriculturally acceptable diluent or carrier and/or surface active agent.
14. A method for controlling weeds at a locus which comprises applying to the locus a herbicidally effective amount of an aryl vinyl ether derivative of general formula (I) according to any one of claims 1 to 12 or an agriculturally acceptable salt or metal complex thereof.
15. A method according to claim 14 in which the locus is an area used, or to be used, for growing of crops and the compound is applied at an application rate from lg to lOOOg per hectare.
16. A method of reducing phytotoxicity to crop plants caused by an aryl vinyl ether derivative of formula (I) according to any one of claims 1 to 12 or an agriculturally acceptable salt or metal complex thereof, which comprises applying generally to the crop plant locus or crop plant seed an antidotally effective amount of an antidote effective to said compound.
17. A product comprising: (a) an aryl vinyl ether derivative as defined in claim 1 or an agriculturally acceptable salt or metal complex thereof, and (b) an antidote, as a combined preparation for simultaneous, separate or sequential use, in controlling the growth of weeds at a locus, e.g. crop locus.
18. A process for the preparation of a compound of general formula (I) as defined in claim 1 which comprises: a) where R11, R12, R13, R14, R16, R17, p, X,, X2 and X3 are as defined in claim 1, and R10 represents -CO2R33, wherein R33 represents R32 with the exclusion of the hydrogen atom, the esterification of the corresponding compound of formula (I) wherein R10 represents CO2H, with an alcohol of formula (II);
3975 . -,1«26_ PCT/EP99/05470
R33-OH
(ID wherein R33 is as defined in claim 1 ; b) where the various symbols are as defined in claim 1 and R10 represents -CO2H, the acid hydrolysis of the corresponding compound wherein R10 represents -CO2R33 and R33 is t-butyl; c) where the various symbols are as defined in claim 1, and R10 represents -CONR30R31, the reaction of the corresponding compound of formula (I) wherein R10 represents -CO2H by conversion to the acyl halide, followed by reaction with an amine of formula (YE):
R30R31NH
(DT) wherein R30 and R31 are as defined in claim 1; d) where the various symbols are as defined in claim 1, and
R10 is -CH2NO2, -CH2SCN, -CH2CN or -CH2N3 the reaction of the corresponding compound of formula (I) wherein R10 = -CH2-L where L is a leaving group, or wherein Y = -CH2-L is replaced by -CH2-L , where L1 is a leaving group, with the metal salt of the appropriate nitro, thiocyano, cyano or azido anion respectively; e) where the various symbols are as defined in claim 1, and R10 is -C(=NR35)R32, the reaction of the corresponding compound of formula (I) wherein R10 is -COR32 with a compound of formula (IV);
R35NH2 (IN) wherein R35 is as defined in claim 1 ; f) where the various symbols are as defined in claim 1 , and R10 is -CH=CHC(O)OR32, the reaction of a compound of formula (I) wherein R10 is halogen with a compound of formula (V): CH2=CHC(O)OR32
(V) wherein R32 is as defined in claim 1 ; g) where the various symbols are as defined in claim 1 and
R10 represents -CHR27R28 or -CR27R28R281 wherein R27, R28 and R281 are as defined in claim 1, the halogenation of the corresponding compound in which one or more of R27, R28 and R281 are replaced by hydrogen atoms; h) where the various symbols are as defined in claim 1, the reaction of a compound of formula (NI),
Figure imgf000129_0001
(VI) wherein R10, R11, R12, R13, R14, , pp aanncd Xi are as defined in claim 1, with a compound of formula (NIT),
Figure imgf000129_0002
(vπ) wherein X2, X3, R16 and R17 are as defined in claim 1 and L2 is a leaving group; i) where the various symbols are as defined in claim 1 and R16 represents OR251, wherein R251 represents R25 with the exclusion of the hydrogen atom, the alkylation of a compound of formula (ND3),
Figure imgf000129_0003
(VIE) wherein the various symbols are as defined in claim 1 ; j) where the various symbols are as defined in claim 1 and R10 represents -COCH2COR33 wherein R33 is as defined in claim 1, the hydrolysis of the corresponding compound in which R10 is replaced by a group -COCH(CO2tBu)COR33; k) where the various symbols are as defined in claim 1 and R10 represents -COF, the fluorination of the corresponding compound in which R10 represents CO2H; and 1) where the various symbols are as defined in claim 1 and
R10 represents -CO2R33 and R33 represents t-butyl, the esterification of the corresponding compound in which R10 represents -CO2H.
19. A process according to claim 1 substantially as hereinbefore described.
20. A herbicidal composition according to claim 13 substantially as hereinbefore described.
21. A method according to claim 14 substantially as hereinbefore described .
PCT/EP1999/005470 1998-07-16 1999-07-16 Aryl vinyl ether derivatives and their use as herbicides Ceased WO2000003975A2 (en)

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