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WO1999003856A1 - Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides - Google Patents

Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides Download PDF

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Publication number
WO1999003856A1
WO1999003856A1 PCT/EP1998/004950 EP9804950W WO9903856A1 WO 1999003856 A1 WO1999003856 A1 WO 1999003856A1 EP 9804950 W EP9804950 W EP 9804950W WO 9903856 A1 WO9903856 A1 WO 9903856A1
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WIPO (PCT)
Prior art keywords
formula
compound
triazol
cyclopropyl
ethyl
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PCT/EP1998/004950
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English (en)
Inventor
Kouichi Araki
Takako Brett
Atsushi Go
Masahito Ito
John Morris
Hideshi Mukaida
Yukiko Oe
Norio Sasaki
Neil Jonathan Geach
Kei Domom
Original Assignee
Rhone-Poulenc Agriculture Limited
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Publication date
Priority claimed from GB9715160A external-priority patent/GB9715160D0/en
Priority claimed from GB9715163A external-priority patent/GB9715163D0/en
Application filed by Rhone-Poulenc Agriculture Limited filed Critical Rhone-Poulenc Agriculture Limited
Priority to AU88637/98A priority Critical patent/AU8863798A/en
Publication of WO1999003856A1 publication Critical patent/WO1999003856A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • This invention relates to novel 4-benzoylisoxazole derivatives, 5- phenylisoxazole derivatives, 2-cyano-l,3-dione derivatives, 4- 5 benzoylpyrazole derivatives, compositions containing them, processes for their preparation, intermediates in their preparation and their use as herbicides.
  • Herbicidal 4-benzoylisoxazoles are described in a number of patent publications for example European Patent Publication Numbers 10 0418175, 0487357, 0527036, 0527037, 0560482 and 0560483.
  • Herbicidal 2-cyano-l,3-diones are described in European Patent Publication Numbers 0213892, 0496630 and 0496631 and International Patent Publication No. WO 95/25099.
  • Herbicidal 5-phenylisoxazoles are described in European Patent Publication Number 0524018.
  • Herbicidal 4-benzoylpyrazoles are described in European Patent
  • the present invention provides phenyl derivatives of formula (I):
  • R represents hydrogen or -CO 2 R 4 ;
  • pi represents :- lower alkyl or lower haloalkyl; or a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more R 2 groups or one or more halogen atoms;
  • R a represents lower alkyl, lower haloalkyl, lower alkenyl or lower alkynyl
  • Rb represents hydrogen, lower alkyl, lower haloalkyl, lower alkoxy, halogen, -S(O) x R 4 , -CO 2 R 4 , -CH 2 OR 4 , -CH SR 4 or cyclopropyl; x represents zero, one or two; R2 represents:- halogen; lower alkyl which is substituted by one or more groups -OR 5 ; a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R 5 , -NR 5 R 6 , -S(O) p R 7 , -O(CH 2 ) m OR 5 , -COR 5 , -N(R 8 )SO 2 R 7 , -OR 7 , -OH, -OSO 2 R 7 ,
  • D, E, G and J independently represent CR' 4 or a nitrogen atom, with at least one of D, E, G and J representing CR 4 (when more than one CR* 4 group is present they may be the same or different); or two adjacent groups CR ⁇ 4 may form a phenyl or 5- to 7- membered heteroaromatic ring which is fused to the first ring and is optionally substituted by one or more groups R* 5 ; and when present the 5- to 7- membered heterocyclic ring contains from one to four heteroatoms in the ring which may be the same or different selected from nitrogen, oxygen and sulphur;
  • X represents -(CR 9 R 10 ) V -;
  • R 4 represents :- lower alkyl or lower haloalkyl
  • R 5 and R" which may be the same of different, each represents hydrogen or R 12;
  • R 5a and R 5 ' 3 which may be the same of different, each represents lower alkyl or lower alkoxy;
  • R 7 represents:-
  • Rl2 or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH ) W - [phenyl optionally substituted by from one to five groups R*-> which may be the same or different]; w represents zero or one; represents : - hydrogen, R 7 , or OR 16 ;
  • Rl represents:- lower alkyl, lower haloalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl or lower haloalkynyl;
  • R i 3 represents a group selected halogen, R 17 , nitro, cyano, -CO 2 R 5 , -S(O) p R 16 , -OR 16 and -NR 5 R 6 ;
  • R! 4 represents :- a group selected from hydrogen, halogen, R ⁇ 7 , nitro, cyano, -CO 2 R 5 , -S(O) p R 16 , -OR 16 , -NR 5 R 6 and cyclopropyl;
  • R 15 represents halogen, or R 2;
  • R 1 ° represents lower alkyl or lower haloalkyl;
  • R* 7 represents a straight- or branched- chain alkyl group containing one to three carbon atoms optionally substituted by one or more halogen atoms;
  • Y is oxygen or sulphur (preferably Y represents oxygen); Z represents a group selected from Rl , -NRl 8 1 9 , -SR 7 and
  • R 18 and R l independently represent hydrogen or R 7 ;
  • Q represents hydrogen, lower alkyl, lower haloalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, -CH 2 CN, -SO 2 R 4 , -SO 2 R20, -(C s H 2s )C(O)Rl2, -(C u H 2u )C(O)R20,
  • R20 represents phenyl optionally substituted by one to five groups selected from halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, nitro, cyano, -S(O) p R 7 and -NR 5 R 6 ;
  • R 1 represents R 5 or R20; R22 and R23 together with the adjacent nitrogen atom represent a piperidine, pyrrolidine, piperazine or morpholine ring; s and u represent zero or one to six; and wherein v represents the value zero when A represents a formula (A-l), (A-2) or (A-3); or when A represents a formula (A-4), v represents the value zero or one; and agriculturally acceptable salts and metal complexes thereof, which possess valuable herbicidal properties.
  • lower alkyl means a straight- or branched- chain alkyl group having one to six carbon atoms
  • 'lower haloalkyl' means a straight- or branched- chain alkyl group having one to six carbon atoms, substituted by one or more halogens;
  • 'lower alkoxy' means a straight- or branched- chain alkoxy group having one to six carbon atoms;
  • 'lower haloalkoxy means a straight- or branched- chain alkoxy group having one to six carbon atoms, substituted by one or more halogens;
  • 'lower alkenyl' means a straight- or branched- chain alkenyl group having two to six carbon atoms;
  • 'lower haloalkenyl' means a straight- or branched- chain alkenyl group having two to six carbon atoms, substituted by one or more halogens;
  • 'lower alkynyl' means a straight- or branched- chain alkynyl group having three to six carbon atoms;
  • 'lower haloalkynyl' means a straight- or branched- chain alkynyl group having three to six carbon atoms, substituted by one or more halogens; 'halogen' means a fluorine, chlorine, bromine or iodine atom.
  • agriculturally acceptable salts salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
  • the salts are water-soluble.
  • Suitable salts with bases include alkali metal (eg. sodium and potassium), alkaline earth metal (eg. calcium and magnesium), ammonium and amine (eg. diethanolamine, triethanolamine, octylamine, mo ⁇ holine and dioctylmethylamine) salts.
  • Suitable acid addition salts 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.
  • substituents R and R to R23 may contribute to optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.
  • the compounds of the invention in certain aspects of their properties, for example their control of weeds found in maize and soya such as Abutilon theophrasti. or in rice for example Echinochloa oryzicola and Lindernia procumbens. show advantageous properties over known compounds.
  • the present invention includes 4-benzoylisoxazole derivatives of formula (la):
  • the present invention includes 5-phenylisoxazole derivatives of formula (lb):
  • the present invention includes 2-cyano-l,3-dione derivatives of formula (Ic):
  • Compounds of formula (Ic) may exist in enolic tautomeric forms that may give rise to geometric isomers around the enolic double bond.
  • metal complexes compounds in which one or both of the oxygen atoms of the 1,3-dione of formula (Ic) act as chelating agents to a metal cation.
  • examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminium.
  • the present invention also includes 4-benzoylpyrazole derivatives of formula (Id):
  • references to compounds of formula (I) means reference to a compound of formula (la), (lb), (Ic) or (Id).
  • R ⁇ > is selected from pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-l-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl and 1,2,3,4-tetrazol-l-yl (1,2,3-triazol-l-yl and l,2,3-triazol-2-yl are more preferred, and 1,2,4-triazol-l-yl is most preferred).
  • R ⁇ is a ring of formula (II) wherein R 14 represents hydrogen, halogen or R 17 .
  • R 14 represents hydrogen, halogen or R 17 .
  • R 14 represents hydrogen, halogen or R 17 .
  • the 5- and 6- positions of phenyl are unsubstituted.
  • R represents hydrogen or CO 2 R 4 wherein R 4 represents a straight- or branched- chain alkyl group containing up to three carbon atoms.
  • R* represents cyclopropyl or 1 -methylcyclopropyl
  • R2 represents halogen, a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; a group selected from nitro, cyano, -S(O) p R 7 , -OR 7 and -CH S(O) q R 7 wherein R 7 represents lower alkyl or lower haloalkyl; or benzyl optionally substituted by -S(O) pR 16 wherein R 16 represents lower alkyl; or two groups R together with adjacent carbon atoms of the phenyl ring form a second phenyl ring.
  • n represents one or two.
  • CH 2 COR20 or CH 2 R 0 are preferred.
  • a preferred class of compounds of formula (la) above are those wherein :- R represents hydrogen or -CO 2 R 4 ;
  • R! represents cyclopropyl or 1 -methylcyclopropyl
  • R2 represents :- a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from halogen, nitro, -S(O)pR 7 , -OR 7 , -CH 2 S(O) q R 7 , -CH 2 NR8R1 1 , -N(R 8 )SO 2 R 7 , -N(R 8 )CO 2 R 7 , -CH 2 P(O)R 5a R 5b and benzyl optionally substituted by -S(O) p R 16 ; or two groups R2 together with adjacent carbon atoms of the phenyl ring form a second phenyl ring; n represents zero, one or two;
  • R3 represents a 5-membered heteroaromatic ring of formula (II) which is selected from pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-l-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl, 1,2,3,4-tetrazol-l-yl, indazol-1-yl, benzotriazol-1-yl, benzimidazol-1-yl and indol-1-yl, which are substituted by one or two groups R 1 (and wherein one or two R ⁇ groups are present);
  • R 4 represents methyl or ethyl
  • R 7 and R 8 independently represent lower alkyl or lower haloalkyl;
  • Rl 1 represents -SO 2 R 7 or CO 2 R 7 ;
  • R l4 represents hydrogen, halogen, a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or -S(O) p Rl6, NO 2 or CO 2 R 5 wherein
  • R 5 represents lower alkyl
  • Rio represents lower alkyl
  • R represents hydrogen or -CO 2 R 4 wherein R 4 represents ethyl
  • Rl represents cyclopropyl
  • R2 represents:- halogen; a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from -S(O) p R 7 , -CH 2 S(O) q R 7 , -OR 7 and benzyl optionally substituted by -S(O) p R 16 ; or two groups R2 together with adjacent carbon atoms of the phenyl ring form a second phenyl ring; or two groups R2 together with adjacent carbon atoms form a 1 ,4- benzoxathian ring;
  • R3 represents a pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl, 1,2,4-triazol-l-yl, 1,2,3,4-tetrazol-l-yl or benz-1,2,3- triazol-1-yl ring substituted by one or two R 14 groups, wherein R 14 represents hydrogen, optionally halogenated methyl or -S(O)pR 16 ;
  • R 7 and R 1 represent methyl or ethyl; and n represents 0, 1 or 2.
  • a further particularly preferred class of compounds of formula (la) above are those wherein: -
  • R represents hydrogen or -CO 2 R 4 wherein R 4 represents ethyl
  • Rl represents cyclopropyl
  • R2 represents :- halogen; a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from -S(O) p R 7 , -CH 2 S(O) q R 7 , -OR 7 and benzyl optionally substituted by -S(O) p R 16 ; or two groups R2 together with adjacent carbon atoms of the phenyl ring form a second phenyl ring;
  • R3 represents a pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl, 1,2,4-triazol-l-yl or 1,2,3,4-tetrazol-l-yl ring substituted by one or two R 14 groups, wherein R 14 represents hydrogen, optionally halogenated methyl or -S(O)pR 16 ; R 7 and R 1 represent methyl or ethyl; and n represents 0, 1 or 2.
  • a further particularly preferred class of compounds of formula (la) above are those wherein:-
  • R represents hydrogen or -CO 2 R 4 wherein R 4 represents ethyl; Rl represents cyclopropyl;
  • R2 represents :- halogen, optionally halogenated methyl, -S(O)pCH3, OCH3 or benzyl optionally substituted by -S(O) p CH3;
  • R3 represents imidazol-1-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl or 1,2,4-triazol-l-yl, optionally substituted on the ring carbon atoms by one or two methyl groups; and n represents one or two.
  • a most preferred class of compounds of formula (la) above are those wherein:- R represents hydrogen or -CO 2 R 4 wherein R 4 represents ethyl; R! represents cyclopropyl;
  • R represents 2-CF3 and R ⁇ represents 4-(l,2,3-triazol-l-yl), 4-
  • R2 represents 4-CF3 and R ⁇ represents 2-(l,2,3-triazol-l-yl), 2- (l,2,3-triazol-2-yl) or 2-(l,2,4-triazol-l-yl).
  • R a represents methyl or ethyl
  • Q represents a group selected from hydrogen, lower alkyl, lower alkenyl, lower alkynyl, -SO 2 R 4 , -SO R 2 0, .(C s H 2s )C(O)R 12 , and
  • R represents :- a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a group selected from halogen, nitro, -S(O)pR 1 ; -ORl 5
  • n zero, one or two;
  • X represents -(CH 2 ) V -;
  • R3 represents a 5-membered heteroaromatic ring of formula (II) which is selected from pyrazol-1-yl, imidazol-1-yl,
  • R D represents hydrogen or methyl
  • R 8 , R 9 and R ⁇ 2 independently represent C1.4 alkyl or haloalkyl
  • R 1 1 represents -SO R 12 or CO 2 R 12 ;
  • R 16 represents C 1.4 alkyl;
  • R 17 represents phenyl optionally substituted by C 1.3 alkyl.
  • R a represents methyl
  • Q represents a group selected from hydrogen, C1.4 alkyl, C 2 _4 alkenyl, C3.4 alkynyl, -SO 2 R 4 , -SO 2 R 0, -(C s H 2s )C(O)R 12 , and -(C U H 2U )C(O)R2 U ; or methyl or ethyl substituted by a group selected from CO 2 R 9 and R 2 ; s and u represent zero or one;
  • R2 represents :- a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a group selected from halogen, nitro, -S(O) p R 1 2 ) -OR*2 and -CH 2 S(O) q R 12 ; or benzyl optionally substituted by -S(O) p R 16 ; n represents one; X represents a bond;
  • R3 is selected from pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-l-yl, 1,2,3-triazol-l-yl, l,2,3-triazol-2-yl and 1,2,3,4-tetrazol-l-yl, the ring systems of which are substituted by one or two R 14 groups; z represents one;
  • R represents hydrogen or methyl
  • R 9 , R 12 , RI 4 and R 16 represent C1.4 alkyl; and R20 represents phenyl optionally substituted by methyl.
  • R a represents methyl
  • Rb represents hydrogen or methyl
  • Q represents a group selected from hydrogen, C ⁇ .4 alkyl, C 2 _4 alkenyl, C3.4 alkynyl, -SO 2 R 4 , -SO 2 R 2 0, -(CH ) s C(O)R 12 , and
  • X represents a bond
  • R represents a 1,2,4-triazol-l-yl ring
  • z represents one
  • R 9 and R*2 represent C1.4 alkyl
  • R20 represents phenyl optionally substituted by methyl.
  • a further particularly preferred class of compounds of formula (Id) above are those wherein:-
  • R a represents methyl
  • R represents hydrogen or methyl
  • Q represents a group selected from hydrogen, C1.4 alkyl, C 2 _4 alkenyl, C3.4 alkynyl, -SO 2 R 4 , -SO 2 R 2 0, -C(O)R 12 , and -(CH 2 ) U C(O)R20; or -CH 2 R 2 0 ;
  • u represents zero or one;
  • R2 represents :- halogen or a straight- or branched- chain alkyl group containing up to three carbon atoms substituted by one or more halogen atoms;
  • n and z represent one;
  • X represents a bond
  • R3 represents a 1,2,4-triazol-l-yl ring
  • R ⁇ 2 and R l 6 represent Ci .4 alkyl
  • R20 represents phenyl optionally substituted by methyl.
  • R a represents methyl
  • Rb represents hydrogen or methyl
  • Q represents -SO 2 R 2 0, CH 2 COR 0 0 r CH 2 R 0 ;
  • X represents a bond
  • R3 represents a 1,2,4-triazol-l-yl ring
  • z represents one
  • R20 represents phenyl optionally substituted by methyl.
  • Particularly important compounds of the invention include: ethyl 5-cyclopropyl-4-[4-(l,2,4-triazol-l-yl)-2- trifluoromethylbenzoyl]isoxazole-3-carboxylate (Compound 1) ethyl 5-cyclopropyl-4-[4-(3-methylthio- 1 ,2,4-triazol- 1 -yl)-2- trifluoromethylbenzoyl]isoxazole-3-carboxylate (Compound 2) ethyl 5-cyclopropyl-4-[4-( 1 ,2,4-triazol- 1 -yl)naphth- 1 - oyl]isoxazole-3-carboxylate (Compound 3) ethyl 5-cyclopropyl-4-[2-chloro-4-(l,2,4-triazol-l- yl)benzoyl]isoxazole-3-carboxylate (Compound 4),
  • compounds of formula (la) or (lb) in which R represents hydrogen and R 1 , R2, R , X, z and n are as defined above may be prepared by the reaction of a compound of formula (III):
  • Hydroxylamine hydrochloride is generally preferred.
  • L is alkoxy, for example ethoxy, or N,N-dialkylamino, for example dimethylamino.
  • the reaction is generally carried out in an organic solvent such as ethanol or acetonitrile or a mixture of a water-miscible organic solvent and water, preferably in a ratio of organic solvent: water of from 1 :99 to 99: 1 , optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate at a temperature from room temperature to the boiling point of the solvent.
  • a base or acid acceptor such as triethylamine or sodium acetate
  • R* is as hereinbefore defined and Y' represents a carboxy group or a reactive derivative thereof (such as a carboxylic acid chloride or carboxylic ester), or a cyano group, with an appropriate organometallic reagent such as a Grignard reagent or an organolithium reagent.
  • the reaction is generally carried out in an inert solvent such as ether or tetrahydrofuran at a temperature from 0°C to the reflux temperature of the mixture.
  • compounds of formula (la) or (lb) wherein R represents -CO 2 R 4 and R 1 , R2, R3, X 5 z and n are as defined above, may be prepared by the reaction of a salt of a compound of formula (V):
  • Preferred salts include sodium or magnesium salts.
  • the reaction is generally performed in an inert solvent such as dichloromethane or acetonitrile at a temperature between room temperature and the reflux temperature of the mixture.
  • the salt of a compound of formula (V) is generally prepared in-situ by treating the compound of formula (V) with a base. Examples of suitable bases include alkaline earth metal alkoxides such as magnesium methoxide.
  • suitable bases include alkaline earth metal alkoxides such as magnesium methoxide.
  • Compounds of formula (V) wherein X represents -(CR 9 Rl ⁇ ) v - and v represents zero are novel and therefore constitute a further feature of the present invention.
  • compounds of formula (la) and (lb) wherein R, R 1 , R2, R3, X, z and n are as defined above, may be prepared by the reaction of a compound of formula (VII) or (VIII) respectively:
  • compounds of formula (Ic) may be prepared from the corresponding compound of formula (la) or (lb) in which R is as defined above.
  • R represents a hydrogen atom
  • the reaction is preferably carried out by treatment with a base.
  • suitable bases include alkali or alkaline earth metal hydroxides, alkoxides such as sodium ethoxide or organic bases such as triethylamine.
  • R represents -CO 2 R 4
  • the conversion is generally carried out by a hydrolytic reaction.
  • the hydrolytic reaction may be performed in the presence of an acid or base. Acidic hydrolysis may be achieved for example using aqueous hydrochloric acid.
  • Basic hydrolysis may be achieved for example using sodium hydroxide in a mixture of alcohol and water.
  • the reactions are preferably carried out at a temperature between 20°C and the reflux temperature of the mixture.
  • compounds of formula (Ic) in which R , R2, R3, X, Z and n are as defined above may also be prepared by the reaction of a benzoyl chloride of formula (IX):
  • R!C( O)CH 2 CN (X) wherein R is as hereinbefore defined.
  • the reaction is generally performed in the presence of a base, in a solvent or solvent mixture.
  • bases include metal hydrides, hydroxides or alkoxides (e.g. sodium or lithium hydride, sodium hydroxide, potassium hydroxide, magnesium ethoxide or magnesium methoxide).
  • Suitable solvents include for example tetrahydrofuran; hydrocarbons such as toluene; or halogenated hydrocarbons such as dichloromethane.
  • the reaction is generally performed at a temperature from 0°C to the reflux temperature.
  • compounds of formula (Ic) in which Rl, R2, R3, X, Z and n are as defined above may also be prepared by the reaction of an acid chloride of formula
  • compounds of formula (Ic) in which R 1 , R2, R3 ; X, Z and n are as defined above may also be prepared by the reaction of a benzoyl chloride of formula (IX) above wherein R2, R3, X ; Z and n are as hereinbefore defined, with a beta-ketonitrile of formula (X) wherein Rl is as hereinbefore defined, via an intermediate of formula (XII):
  • R , R2, R3, ⁇ ? z and n are as hereinbefore defined.
  • the formation of the intermediate of formula (XII) may be carried out in the presence of a mild base such as an organic base e.g. triethylamine, in an inert solvent such as acetonitrile or dichloromethane at a temperature between room temperature and the reflux temperature of the mixture.
  • a mild base such as an organic base e.g. triethylamine
  • an inert solvent such as acetonitrile or dichloromethane
  • the rearrangement of the intermediate of formula (XII) to a compound of formula (Ic) is generally carried out in situ in an inert solvent such as acetonitrile or dichloromethane in the presence of a catalyst such as a source of cyanide.
  • sources of cyanide are acetone cyanohydrin or an alkali metal cyanide such as potassium cyanide, optionally in the presence of a crown
  • compounds of formula (Ic) in which R , R , R , X, z and n are as defined above may be prepared by the reaction of an acid chloride of formula R COCl wherein R is as hereinbefore defined, with a beta-ketonitrile of formula (XI) wherein R2, R3, X, Z and n are as hereinbefore defined via an intermediate of formula (XIII):
  • the compounds of formula (XIV) may exist as the tautomer (XlVa) and both forms may be used.
  • the reaction is generally performed in the presence of a coupling agent, generally a carbodiimide such as N,N - dicyclohexylcarbodiimide.
  • a coupling agent generally a carbodiimide such as N,N - dicyclohexylcarbodiimide.
  • One to 1.5 equivalents of the coupling agent are generally used.
  • the reaction is preferably conducted in the presence of a base such as an alkali metal carbonate preferably potassium carbonate, and in a solvent such as an alcohol for example t-amyl alcohol, t-butanol or i-propanol, and at a temperature of about 20°C to the reflux temperature of the solvent and preferably 50-100°C.
  • a base such as an alkali metal carbonate preferably potassium carbonate
  • a solvent such as an alcohol for example t-amyl alcohol, t-butanol or i-propanol
  • compounds of formula (Id) wherein R a , Rb ; R2 5 R3 ? ⁇ ; n and z are as defined above and Q represents hydrogen may also be prepared by the reaction of a compound of formula (XIV) or (XlVa) above with an acid chloride of formula (IX) wherein R2, R , X, n and z are as defined above, to give an ester of formula (XVI):
  • the first stage of this process to give the ester intermediates of formula (XVI) is generally performed in the presence of a base such as potassium carbonate, triethylamine or pyridine, and in a solvent such as toluene, acetone, dichloromethane, acetonitrile or tetrahydrofuran, at a temperature of from 0-60°C.
  • a base such as potassium carbonate, triethylamine or pyridine
  • a solvent such as toluene, acetone, dichloromethane, acetonitrile or tetrahydrofuran, at a temperature of from 0-60°C.
  • the rearrangement process to give the compounds of formula (Id) wherein Q is hydrogen is generally performed using a Lewis acid such as aluminium chloride; or preferably using a base for example potassium carbonate or calcium hydroxide.
  • One to ten equivalents of the base are used, optionally in the presence of a solvent such as acetone, methyl ethyl ketone, t-amyl alcohol, t- butanol, dioxan, toluene or xylene, at a temperature of 50-150°C.
  • a solvent such as acetone, methyl ethyl ketone, t-amyl alcohol, t- butanol, dioxan, toluene or xylene
  • the rearrangement process is preferably performed in the presence of a catalytic amount of the corresponding compound of formula (XIV).
  • the rearrangement process may be performed in the presence of a source of cyanide in the presence of a base.
  • Cyanide sources include metal cyanides for example alkali metal cyanides such as sodium cyanide, hydrogen cyanide, or cyanhydrins of dialkyl ketones preferably acetone cyanhydrin.
  • cyanide source Generally up to 0.5 equivalent (preferably 0.1 equivalent) of cyanide source is employed.
  • Suitable bases include trialkylamines such as triethylamine, or pyridine or alkali metal carbonates such as potassium carbonate. Generally 1-4 equivalents (preferably 2 equivalents) of the base is used.
  • Solvents which may be used include toluene, acetonitrile, dichloromethane or preferably 1,2-dichloroethane. The reaction is generally performed at a temperature of from 0°C-60°C (generally at 20°C-30°C).
  • compounds of formula (Id) wherein R a , Rb, R2 ; R3 ? ⁇ ; n and z are as defined above and Q represents hydrogen may also be prepared by the reaction of a compound of formula (XIV) above with an aryl halide of formula (XVII):
  • XVII wherein R , R , X, n and z are as defined above and T represents a bromine or iodine atom, in the presence of carbon monoxide and a palladium, nickel, cobalt or rhodium catalyst preferably bis(triphenylphosphine)palladium (II) chloride.
  • a base generally a trialkylamine such as triethylamine in a solvent which may be water and a phase transfer catalyst for example tetrabutylammonium bromide.
  • compounds in which p or q is one or two may be prepared by the oxidation of the sulphur atom of the corresponding compounds in which p or q is 0 or 1.
  • the oxidation of the sulphur atom is generally carried out using for example 3-chloroperoxybenzoic acid in an inert solvent such as dichloromethane at a temperature from -40°C to room temperature.
  • an inert solvent such as dichloromethane
  • Compounds of formula (III) may be prepared by the reaction of compounds of formula (V) with either a trialkyl orthoformate such as triethyl orthoformate or a dimethylformamide dialkyl acetal such as dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate
  • a dimethylformamide dialkyl acetal such as dimethylformamide dimethyl acetal.
  • reaction with a trialkyl orthoformate can be carried out in the presence of acetic anhydride at the reflux temperature of the mixture and the reaction with dialkylformamide dialkyl acetal can be carried out optionally in the presence of an inert solvent at a temperature from room temperature to the reflux temperature of the mixture.
  • Compounds of formula (V) may be prepared by the reaction of an acid chloride of formula (IX) with a metal salt of a compound of formula (XVIII):
  • Acid chlorides of formula (IX) may be prepared by the reaction of a benzoic acid of formula (XV) with a chlorinating agent, for example thionyl chloride at the reflux temperature of the mixture.
  • a chlorinating agent for example thionyl chloride
  • the benzoyl chlorides may also be prepared by reaction of the benzoic acid with oxalyl chloride in a solvent such as 1,2-dichloroethane at from ambient to reflux temperature.
  • Esters of formula (XX) may be prepared from acids of formula (XV) according to known methods.
  • XXII Compounds of general formula (XXII) may be prepared by the reaction of a ketonitrile of formula (XI) or a ketoester of formula
  • Beta-ketonitriles of formula (X) may be prepared from acid chlorides of formula R 1 COC1 by a number of methods well known in the chemical literature. For example, see Krauss, et al, Synthesis, 1983, 308, or Muth, et al, J. Org. Chem, 1960, 25, 736.
  • beta- ketonitriles of formula (X) may be prepared by the reaction of an ester of formula R!-CO 2 Et, wherein R 1 is as hereinbefore defined, with acetonitrile. This reaction is described in the literature, for example see the article by Abramovitch and Hauser, J.Am. Chem. Soc, 1942, 64,
  • Beta-ketonitriles of formula (XI) may be prepared from benzoyl chlorides of formula (IX) or from corresponding ethyl benzoates in a manner analogous to the preparation of beta-ketonitriles of formula (X) set forth above.
  • Benzoic acids of formula (XV) or esters of formula (XX) in which R 2 , R3, R 24 , X, z and n are as defined above may be prepared by the reaction of the corresponding compound of formula (XV) or (XX) in which R3 is replaced by a Y 2 (Y 2 is as defined above preferably fluorine), with a compound of formula R ⁇ -H using the same procedure as described above for the preparation of compounds of formula (la) and (lb) from compounds of formula (VII) and (VIII).
  • Ethyl 5-cyclopropyl-4-(4-fluoro-2- trifluoromethyl)benzoylisoxazole-3-carboxylate (0.74g) was added to a suspension of sodium hydride (60%, 0.12g) and 1,2,4-triazole (0.2 lg) in dry N,N-dimethylformamide at 20°C. The solution was stirred for 3 hours, poured into water, extracted (ethyl acetate), dried (magnesium sulphate) and evaporated.
  • Hydroxylamine hydrochloride (0.45 g) was added to a stirred solution of 3-cyclopropyl-2-dimethylaminomethylene- 1 -[4-(l ,2,4- triazol-l-yl)-2-trifluoromethylphenyl]propan-l ,3-dione in ethanol. After 2 hours, water was added and the mixture extracted with dichloromethane, washed with water, dried (magnesium sulphate) and evaporated.
  • Example 3 To a suspension of magnesium turnings (0.20g) and methanol was added a catalytic amount of carbon tetrachloride at 20°C.The mixture was stirred until dissolved, and a suspension of 3 -cyclopropyl- 1- [2- (l,2,4-triazol-l-yl)phenyl]propan-l,3-dione (1.44g) in methanol was added. The mixture was warmed to 60°C, then evaporated and the residue dissolved in toluene. Ethyl chloroximidoacetate (0.9 lg) was added and the mixture stirred overnight.
  • Example 4 A mixture of 18-crown-6 (1.06g) and 37% w/w potassium fluoride on basic alumina (0.69g) was added portionwise to a mixture of ethyl 5- cyclopropyl-4-(2-fluoro-4-trifluoromethylbenzoyl)isoxazole-3- carboxylate (1.48g) and 1,2,4-triazole (0.28g) in acetonitrile.
  • Example 5 m-Chloroperbenzoic acid (0.18g) was added to a stirred solution of ethyl 5-cyclopropyl-4-[4-(3-methylthio-l,2,4-triazol-l-yl)-2- trifluoromethylbenzoyl]isoxazole-3-carboxylate (0.44g) in dichloromethane at 20°C. After 2 hours the mixture was washed with sodium metabisulphite solution and potassium carbonate solution.
  • Example 8 To a solution of l,3-dimethyl-5-[4-(l,2,4-triazol-l -yl)-2- trifluoromethylbenzoyloxy]-l H-pyrazole (1.93g) in t-amyl alcohol was added a catalytic amount of l,3-dimethyl-5-hydroxy-l H-pyrazole and potassium carbonate (0.76g) at 20°C. The reaction mixture was warmed to 100°C, stirred for 4 hours and cooled. After extraction with ether the aqueous layer was acidified (aqueous citric acid), extracted
  • 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 phenyl derivative of formula (I) or an agriculturally acceptable salt or metal complex thereof.
  • the phenyl 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 (i.e. grass) weeds by pre- and/or post-emergence application.
  • pre-emergence application is meant application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil.
  • post- emergence application is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
  • the compounds of formula (I) may be used to control the growth of: broad-leafed weeds, for example, Abutilon theophrasti, Amaranthus retroflexus. Bidens pilosa.
  • Chenopodium album Galium aparine. Ipomoea spp. e.g. Ipomoea pu ⁇ urea. Sesba ia exaltata. Sinapis arvensis, Solanum nigrum and Xanthium strumarium, and grass weeds, for example Alopecurus myosuroides, A vena fatua. Digitaria sanguinalis. Echinochloa crus-galli. Sorghum bicolor, Eleusine indica and Setaria spp. e.g. Setaria faberii or Setaria viridis. and sedges, for example, Cyperus 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.
  • the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop.
  • application rates from 0.01kg to 2kg 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, soya beans, 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
  • soya beans, field and dwarf beans peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape,
  • 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 from 0.25kg to 2.0kg, and preferably from 0.25kg to 1.0kg 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 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 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) When used to control the growth of weeds by pre-emergence application, 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 phenyl derivatives 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 (I) are dissolved in other components.
  • compositions are used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
  • the compositions contain from 0.05 to 90% by weight of one or more compounds of formula (I).
  • the herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
  • Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
  • 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.
  • 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.
  • suitable solid diluents or carriers are aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent 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 inco ⁇ orate a surface-active agent.
  • Suitable liquid diluents for inco ⁇ oration in the liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and 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 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.
  • Herbicidal compositions according to the present invention may also comprise the compounds of formula (I) 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.
  • synthetic pyrethroids e.g permethrin and cypermethrin
  • fungicides e.g. carbamates, e.g. methyl N-(l-butyl-carbamoyl- benzimidazol-2-yl)carbamate
  • triazoles e.g. 1 -(4-chloro-phenoxy)- 3,3-dimethyl-l-(l,2,4-triazol-l-yl)-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, may, if desired, be utilised in the form of conventional derivatives, for example alkali metal and amine salts and esters.
  • Example Cl An emulsifiable concentrate is formed from:
  • NMP N-Methylpyrrolidinone
  • a wettable powder is formed from:
  • Active ingredient 50% w/w
  • a suspension concentrate is formed from:
  • Attaclay (Attagel) 1.5% w/v
  • Example C4 A water dispersible granule is formed from:
  • Active ingredient 50% w/w Sodium dodecylbenzenesulphonate
  • 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.
  • 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.
  • weeds Abutilon theophrasti, Amaranthus retroflexus, Galium aparine. Ipomoea pu ⁇ urea, Xanthium strumarium;
  • Grassweeds Alopecurus myosuroides, A vena fatua. Echinochloa crus-galli. Setaria viridis;
  • the seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil .
  • the compounds of the invention were applied to the soil surface, containing the seeds, as described in (a).
  • a single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After treatment the pots were placed on capillary matting kept in a glass house, and watered overhead . Visual assessment of crop damage was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots.
  • Weed control Post-emergence
  • the weeds and crops were sown directly into John Innes potting compost in 75 mm deep, 70 mm square pots except for Amaranthus which was pricked out at the seedling stage and transferred to the pots one week before spraying. The plants were then grown in the greenhouse until ready for spraying with the compounds used to treat the plants.
  • the compounds used to treat the plants were applied to the plants as described in (a). A single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
  • Paddy post-emergence application in greenhouse Paddy field soil was filled in 170 cm 2 plastic pots, a suitable amount of water and chemical fertilisers were added thereto and kneaded to convert it to a state of a paddy.
  • Paddy rice plants (variety; Koshihikari), that had been grown in advance in a greenhouse to a stage of two leaves, were transplanted to each pot (two seedlings per pot). Then in each pot there were sown predetermined amounts of seeds of Echinochloa orvzicola. Monochoria vaginalis, Lindernia procumbens and Sci ⁇ us iuncoides respectively, and water was added to a depth of 3 cm.

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Abstract

L'invention concerne les composés de formule (I), dans laquelle A désigne (A-1), (A-2), (A-3) ou (A-4), z désigne un ou deux; lorsque z est égal à deux les groupes XR3 peuvent être identiques ou différents; R3 désigne un noyau hétéroaromatique à 5 chaînes de formule (II) dans laquelle D, E, G et J désignent indépendamment CR14 ou un atome d'azote, au moins un des D, E, G et J désignant CR14 (lorsque plus d'un groupe CR14 est présent ils peuvent être identiques ou différents); ou deux groupes CR14 adjacents peuvent former un noyau hétéroaromatique phényl ou présentant entre 5 et 7 chaînons qui est condensé au premier noyau et est éventuellement substitué par un ou plusieurs groupes R15; et lorsqu'il est présent, le noyau hétérocyclique présentant entre 5 et 7 chaînons comporte entre un et quatre hétéroatomes dans le noyau qui peut(vent) être identique(s) ou différent(s) et être sélectionné(s) parmi azote, oxygène et soufre; X désigne -(CR9R10)v-; et leur utilisation en tant qu'herbicides.
PCT/EP1998/004950 1997-07-18 1998-07-15 Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides WO1999003856A1 (fr)

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WO2000035916A1 (fr) * 1998-12-15 2000-06-22 Aventis Cropscience S.A. 4-benzoylisoxazoles herbicides
WO2000068204A1 (fr) * 1999-05-08 2000-11-16 Bayer Aktiengesellschaft Cetones de benzoyle substituees, leur procede de preparation et leur utilisation comme herbicides
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
WO2001010850A1 (fr) * 1999-08-10 2001-02-15 Nihon Bayer Agrochem K.K. Derives herbicides de tetrazolinone
JP2001114769A (ja) * 1999-08-10 2001-04-24 Nippon Bayer Agrochem Co Ltd テトラゾリノン誘導体及び除草剤
WO2001079199A1 (fr) * 2000-04-18 2001-10-25 Idemitsu Kosan Co., Ltd. Derives de l'acetylene et herbicides en contenant
WO2002090336A1 (fr) * 2001-05-09 2002-11-14 Bayer Cropscience Ag Arylcetones substituees
WO2001053275A3 (fr) * 2000-01-17 2003-04-17 Bayer Ag Arylcetones substituees
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7153813B2 (en) 2002-02-19 2006-12-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
US8658798B2 (en) 2007-08-03 2014-02-25 Bayer Cropscience Ag Herbicide triazolylpyridine ketones

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EP0282944A2 (fr) * 1987-03-17 1988-09-21 Nissan Chemical Industries Ltd. Dérivés de pyrazole et herbicides les contenant
EP0487357A1 (fr) * 1990-11-22 1992-05-27 Rhone-Poulenc Agriculture Ltd. Dérivés de 4-benzoyl isoxazoles
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WO2000035916A1 (fr) * 1998-12-15 2000-06-22 Aventis Cropscience S.A. 4-benzoylisoxazoles herbicides
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
RU2250902C2 (ru) * 1999-05-06 2005-04-27 Байер Акциенгезелльшафт Замещенные бензоилизоксазолы и гербицидное средство на их основе
US6838415B1 (en) 1999-05-06 2005-01-04 Bayer Aktiengesellschaft Substituted benzoylisoxazoles and the use thereof as herbicides
US6762152B1 (en) 1999-05-08 2004-07-13 Bayer Aktiengesellschaft Substituted benzoyl ketones, methods for producing them and their use as herbicides
WO2000068204A1 (fr) * 1999-05-08 2000-11-16 Bayer Aktiengesellschaft Cetones de benzoyle substituees, leur procede de preparation et leur utilisation comme herbicides
RU2245330C2 (ru) * 1999-05-08 2005-01-27 Байер Акциенгезельшафт Замещенные бензоилкетоны и гербицидное средство на их основе
US6790810B2 (en) * 1999-08-10 2004-09-14 Nihon Bayer Agrochem K.K. Tetrazolinone derivatives
US6624121B1 (en) 1999-08-10 2003-09-23 Nihon Bayer Agrochem K.K. Herbicidal tetrazolinone derivatives
KR100730019B1 (ko) 1999-08-10 2007-06-20 바이엘 크롭사이언스 케이. 케이. 제초성 테트라졸리논 유도체
JP2001114769A (ja) * 1999-08-10 2001-04-24 Nippon Bayer Agrochem Co Ltd テトラゾリノン誘導体及び除草剤
WO2001010850A1 (fr) * 1999-08-10 2001-02-15 Nihon Bayer Agrochem K.K. Derives herbicides de tetrazolinone
US6936570B2 (en) 1999-08-10 2005-08-30 Nihon Bayer Agrochem, K.K. Tetrazolinone derivatives
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US6727206B2 (en) 1999-09-30 2004-04-27 Bayer Aktiengesellschaft Substituted aryl ketones
WO2001053275A3 (fr) * 2000-01-17 2003-04-17 Bayer Ag Arylcetones substituees
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
WO2001079199A1 (fr) * 2000-04-18 2001-10-25 Idemitsu Kosan Co., Ltd. Derives de l'acetylene et herbicides en contenant
WO2002090336A1 (fr) * 2001-05-09 2002-11-14 Bayer Cropscience Ag Arylcetones substituees
US7112554B2 (en) 2001-05-09 2006-09-26 Bayer Cropscience Ag Substituted arylketones
US7456133B2 (en) 2001-05-09 2008-11-25 Bayer Cropscience Ag Substituted arylketones
US7153813B2 (en) 2002-02-19 2006-12-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
US8658798B2 (en) 2007-08-03 2014-02-25 Bayer Cropscience Ag Herbicide triazolylpyridine ketones
US8927458B2 (en) 2007-08-03 2015-01-06 Bayer Cropscience Ag Herbicide triazolylpyridine ketones

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