EP0671880A1 - Selective herbicidal composition - Google Patents

Selective herbicidal composition

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Publication number
EP0671880A1
EP0671880A1 EP93915750A EP93915750A EP0671880A1 EP 0671880 A1 EP0671880 A1 EP 0671880A1 EP 93915750 A EP93915750 A EP 93915750A EP 93915750 A EP93915750 A EP 93915750A EP 0671880 A1 EP0671880 A1 EP 0671880A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
hydrogen
alkoxy
phenyl
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93915750A
Other languages
German (de)
French (fr)
Inventor
Jutta Glock
Elmar Kerber
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0671880A1 publication Critical patent/EP0671880A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the present invention relates to a selective herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in cereal crops, which comprises a herbicide and a safener (antidote) which protects the useful plants, but not the weeds, from the phytotoxic action of the herbicide, and to the use of that composition or of the combination of herbicide and safener in the control of weeds in crops of useful plants.
  • a herbicide and a safener (antidote) which protects the useful plants, but not the weeds, from the phytotoxic action of the herbicide, and to the use of that composition or of the combination of herbicide and safener in the control of weeds in crops of useful plants.
  • EP-A-0094349 discloses quinoline derivatives that protect crop plants from the phytotoxic action of herbicides of specific classes of compounds, such as phenoxy- propionic acid ester herbicides, ureas, carbamates or diphenyl ethers.
  • a selective herbicidal composition that comprises as active component, in addition to inert additives such as carriers, solvents and wetting agents, a mixture comprising
  • X is oxygen or sulfur or, when W is W 5 , may also be NH, NC(O)H or NC(O)R 62 ;
  • Y is -COOH, or an organic or inorganic salt of that acid, II , 11 o o
  • R is -OR H ;
  • Rj is one of the groups (a), (b) and (c)
  • R 2 is hydrogen, methyl or the group Q" (Ql,
  • C is hydrogen, methyl or, together with Q 4 , is -(CH 2 ) 2 -, -( ⁇ 3 -, -CH 2 CH(OH)CH 2 - or -CH 2 SCH 2 -;
  • Q 2 is hydrogen or methyl
  • Q-j is hydrogen, trifluoromethyl, ethynyl, vinyl, phenyl, cyano or C ⁇ alkoxycarbonyl, C j ⁇ alkyl, or C ⁇ alkyl substituted by hydroxy, C alkoxy, mercapto, C j ⁇ al yl- mercapto, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxy- carbonyl, C ⁇ alkoxycarbonyl, 2-propenyloxycarbonyl, cyano or by carbamoyl; and
  • Q 4 is hydrogen, methyl, hydroxymethyl, formyl or cyano; or R 2 together with R 7 is -(CH 2 ) p -, -CH 2 SCH 2 - or -CH 2 CHOHCH 2 -;
  • R 3 is hydrogen, C ⁇ alkyl, phenyl, or phenyl mono- or di-substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or by nitro;
  • R 4 is hydrogen or methyl
  • R 5 is C ⁇ alkyl, C ⁇ ghaloalkyl, phenyl, benzyl, or phenyl substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro, cyano, carboxy or by C- ⁇ alkoxycarbonyl;
  • R is hydrogen, hydroxymethyl, formyl, cyano, hydroxyimino, C ⁇ alkoxyimino, phosphono, phosphino, methylphosphino or a group COX ⁇
  • R is hydrogen; C ⁇ alkyl or C ⁇ alkyl substituted by hydroxy, C ⁇ alkoxy, mercapto, acylmercapto, C ⁇ alkylthio, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxycarbonyl, 2-propenyloxycarbonyl, cyano, carbamoyl, methylphosphino or by methylsulfoximino; trifluoromethyl; ethynyl; vinyl or vinyl substituted by chlorine or by methoxy; phenyl or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl or by methoxy; or cyano or C ⁇ alkoxy- carbonyl; R 8 is hydrogen or methyl; A is oxygen, sulfur or -NH-; m is 1, 2 or 3; n is 0, 1, 2 or 3; p is 2 or 3;
  • X j is hydroxy, C ⁇ alkoxy, C 3 ⁇ alkenyloxy, mercapto, C alkylthio, amino, C ⁇ alkyl- amino, C 2 - 4 dialkylam no or C j ⁇ alkoxyamino; or C-._ 4 al-.0xy, C 3 ⁇ alkenyloxy, mercapto, C alkylthio, amino, C ⁇ al-cylamino, C ⁇ dialkylamino or C ⁇ alkoxy- amino each substituted by phenyl, benzyloxy or by ⁇ alkoxy, or is one of the groups (d), (e) and (f)
  • Aj is oxygen, sulfur or -NH-;
  • R 9 is hydrogen, C- ⁇ alkyl or benzyl
  • R 10 is hydroxymethyl, cyano or a group COQ'
  • Q is hydroxy, C j ⁇ alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);
  • Q' is hydroxy, C 1 -C 4 alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);
  • R ⁇ is hydrogen, C 1 -C 10 al yl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, di- C r C 4 alkylamino-C 1 -C 4 alkyl, halo-Ci-Cgal yl, C -C 8 alkenyl, halo-C ⁇ -Cgalkenyl, C 3 -C 8 alkynyl, C 3 -C 7 cycloalkyl, halo-C 3 -C 7 cycloalkyl, C alkylcarbonyl, C 1 -C 4 alkylcarbonyloxy-C 1 -C 2 alkyl, allylcarbonyl, C 3 -C 7 cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen,
  • W 6 W 6
  • E is nitrogen or -CR 12 ;
  • R 12 is hydrogen, halogen, hydroxy, C 2 -C 4 a.J-.oxy, phenyl or benzyl; or phenyl substituted by C r C 4 alkyl, C r C 4 alkoxy, C j ⁇ haloalkyl or by halogen; benzyl substituted by C r C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkyl or by halogen; -COR 13 , " ⁇ " R i4 ,
  • R 13 is C r C 4 alkyl, halo-C r C 4 a-kyl, C r C 4 al oxy-C 1 -C 4 alkyl; amino, C r C 4 a---:yla ⁇ -
  • R 18 is hydrogen, methyl or, together with R 17 , is -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 - or
  • R 19 is hydrogen, methyl, fluorine, chlorine, bromine, Cj-galkoxy, C 3 - 6 alkenyloxy,
  • R 2 ⁇ is C ⁇ alkyl, C 2 . 6 alkenyl, C 3.6 cycloalkyl, C j ⁇ haloalkyl, C 1 - 3 alkoxy, C j .
  • alkylthio formyl, Cx-salkylcarbonyl, carboxy, C ⁇ alkoxycarbonyl, phenyl, or phenyl substit ⁇ uted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or by nitro; or is 2-, 3- ' or 4-pyridyl, 2- or 3-furyl or 2- or 3-thienyl;
  • R 22 is hydrogen, - alkyl, C 3 -C 6 cycloalkyl, C r C 6 haloallcyl, C 3 -C 6 alkenyl,
  • R 57 is hydrogen, hydroxy, C r C,salkoxy, Cx- alkoxyalkoxy, C- t - acyloxyalkoxy, tri- methylsilylethoxy, C C ⁇ alkylsulfonylamino, Cx-Cgalkylthio, imidazolyl, benzyl ⁇ oxy, phenoxy or thiophenoxy, or benzyloxy, phenoxy or thiophenoxy;
  • R 58 is halogen, Cj-C ⁇ haloalkyl, C- j -C ⁇ alkyl, acylamino, C 3 -C 6 cycloalkyl, halo- substituted Ci- alkoxy- carbonyl, C- t -C ⁇ alkoxy, Ci- a ⁇ lamino, di- -Cgalkylamino, C_-C 6 a---:oxyimino- alkyl, acyl, C-t-Cgalkylthio, phen
  • R 66 is Ci-C ⁇ al yl, or C r C 6 alkyl which is substituted by up to 3 fluorine atoms, 1 chlorine atom, 1 C 1 -C 4 alkoxy group, 1 C 1 -C 4 alkoxycarbonyl group, 1 dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ethynyl group or 1 phenyl group which is unsubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or -phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or NR ⁇ R ⁇ ; or OR ⁇ ;
  • R 67 is hydrogen or C 1 -C 4 alkyl
  • R 68 is hydrogen, -C ⁇ alkyl, phenyl, pyridyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted by ⁇ alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is -Cgalkylcarbonyl, trifluoro- methylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridyl- carbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, tri ⁇ fluoromethyl, methoxy or nitro; or ⁇ al oxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl,
  • R 69 is hydrogen, C C 6 alkyl or C 2 -C 6 alkenyl, or C 2 -C 6 alkenyl which is substituted by halogen or phenyl, or C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl or C 1 -C alkylthiocarbonyl- C r C 4 al yl;
  • R 24 is hydrogen or C ⁇ a-kyl
  • X 2 is hydrogen or chlorine; or of an N-acylsulfamoylphenylurea of formula lib
  • a 2 is a group
  • R- 25 and R ⁇ independently of one another, are hydrogen, C Cgalkyl, C 3 -C 8 cycloalkyl,
  • R 27 is hydrogen or C 1 -C aU--yl
  • R a is hydrogen, halogen, cyano, trifluoromethyl, nitro, C 1 -C alkyl, C 1 -C alkoxy, C r C 4 alkylthio, C r C 4 alkylsulfmyl, C r C 4 alkylsulfonyl, -COOR j ⁇ -CONR, ⁇ , -COR,,, -SO 2 NR k R m or -OSO 2 -C 1 -C 4 alkyl;
  • R g is hydrogen, halogen, cyano, nitro, C 1 -C 4 al yl, C 1 -C 4 alkylthio,
  • R b and R h independently of one another, are hydrogen, halogen, C r C alkyl, trifluoro ⁇ methyl, C r C 6 alkoxy, C r C 6 allcylthio or -COORJ;
  • R c is hydrogen, halogen, nitro, -Qalkyl or methoxy
  • R d is hydrogen, halogen, nitro, C 1 -C 4 alkyl, C 1 -C alkoxy, C 1 -C 4 alkylthio, C r C 4 alkyl- sulfinyl, C ⁇ alkylsulfonyl, -COOR j or CONR f cR-,,;
  • R e is hydrogen, halogen, C r C 4 alI yl, -COOR j , trifluoromethyl or methoxy; or R d and R-. together form a C 3 -C 4 alkylene bridge;
  • R f is hydrogen, halogen or C 1 -C alkyl
  • R x and R y independently of one another, are hydrogen, halogen, C-t-C ⁇ alkyl, C r C alkoxy, C r C al ylthio, -COOR 28 , trifluoromethyl, nitro or cyano;
  • R j , R k and R m independently of one another, are hydrogen or C 1 -C a ⁇ l; or
  • R k and R ⁇ together form a C 4 -C 6 alkylene bridge that can be interrupted by oxygen, NH or by -N(C r C 4 alkyl)-;
  • R n is C 1 -C 4 al yl, phenyl, or phenyl substituted by halogen, C 1 -C 4 alkyl, methoxy, nitro or by trifluoromethyl;
  • R 28 is hydrogen, -Cioallcyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, di- C 1 -C 4 alkylamino-C 1 -C alkyl, halo-Cj-Cgalkyl, C 2 -C 8 alkenyl, halo-C ⁇ -Cgalkenyl, C 3 -C 8 alkynyl, C 3 -C 7 cycloalkyl, halo-C 3 -C 7 cycloalkyl, C r C 8 alkylcarbonyl, allyl- carbonyl, C 3 -C 7 cycloal ylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C r C 4 alkyl, halo-C 1 -C 4 al
  • E 2 is nitrogen or methine
  • R 29 is -CC1 3 , phenyl or halo-substituted phenyl
  • R 30 and R 31 independently of one another, are hydrogen or halogen
  • R 32 is C r C 4 alkyl; or of a chloroacetamide of formula Ed
  • R3 3 and R 34 independendy of one another, are C- Cgalkyl or C ⁇ alkenyl;
  • R 35 and R 36 independently of one another, are hydrogen or C r C 6 alkyl; or R 33 and R34 together are
  • R 37 and R 38 independen ⁇ y of one another, are C 1 -C 4 alkyl; or R 37 and R 38 together are -(CH2)5-;
  • R 39 is hydrogen, C 1 -C alkyl or ⁇
  • R54 an ⁇ 55' independ ⁇ endy of one another, are hydrogen or C 1 -C 4 alkyl; or of an oxime of formula Eh
  • R 63 is hydrogen or chlorine
  • R.54 is cyano or trifluoromethyl; or of a phenylpyrimidine of formula IIi
  • R 65 is hydrogen or methyl.
  • halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and die various isomeric pentyl, hexyl, heptyl, octyl, nonyl and decyl radicals.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.
  • Haloalkoxy is, for example, fiuoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetra- fluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromemoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio or isomeric pentylthio, preferably methylthio and ethylthio.
  • Alkenyl is to be understood as being straight-chain or branched alkenyl, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl, 2-hexenyl or 3-heptenyl. Preference is given to alkenyl radicals having a chain length of 2 or 3 carbon atoms.
  • alkynyl radicals occurring in the definitions of die substituents may be straight-chain or branched, such as, for example, ethynyl, propargyl, 3-butynyl, 1-methylpropargyl, 1-pentynyl or 2-hexynyl. Ethynyl and propargyl are preferred.
  • Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopropyl, cyclopentyl or cyclohexyl.
  • Alkoxycarbonyl is, for example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and etiioxy- carbonyl.
  • Alkoxyalkyl is, for example: methoxymethyl, ethoxymethyl, propoxymethyl, methoxy- ethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl or propoxypropyl.
  • Alkylthioalkyl is, for example: methylthiomethyl, ethylthiomethyl, methylthioethyl, ethyl- thioethyl or isopropylthioethyl.
  • Alkylaminoalkyl is, for example: methylaminoethyl, dimethylaminoethyl, ethylamino- ethyl or diethylaminoethyl.
  • Cyanoalkyl is, for example: cyanomethyl, cyanoethyl or cyanopropyl.
  • Halocycloalkyl is, for example: 2,2-dichlorocyclopropyl or pentachlorocyclohexyl.
  • Alkylsulfonyl is, for example: methylsulfonyl, ethylsulfonyl, propylsulfonyl or butyl- sulfonyl. Methyl- and ed yl-sulfonyl are preferred.
  • Phenyl and thienyl also as part of a substituent such as phenoxy', thiophenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, can generally be unsub ⁇ stituted or substituted by further substituents.
  • the substituents may be in the ortho-, meta- and/or para-position(s) or in 2-, 3-, 4- or 5-position of the thienyl ring, respectively.
  • Preferred substituent positions are the ortho- and para-positions to the ring-linkage point.
  • Preferred substituents are halogen atoms.
  • Suitable salts of the free carboxylic acid are, especially, alkali metal salts such as lithium, sodium, potassium; alkaline earth metal salts such as magnesium or calcium; or salts of manganese, copper, zinc or iron; or salts of organic ammonium bases, such as ammonia, primary, secondary or tertiary alkylamines, such as methylammonium, dietiiylammonium, methylammonium, morpholinium, tetrabutylammonium, benzyltrimethylammonium, phosphonium, sulfonium, sulfoxonium or pyridinium.
  • alkali metal salts such as lithium, sodium, potassium
  • alkaline earth metal salts such as magnesium or calcium
  • salts of manganese, copper, zinc or iron or salts of organic ammonium bases, such as ammonia, primary, secondary or tertiary alkylamines, such as methylammonium, dietiiylammonium, methyl
  • the invention relates also to salts that the compounds of formula I are capable of forming with amines, alkali and alkaline earth metal bases or quaternary ammonium bases.
  • those salts also include hydrazonium salts that may be formed by compounds of formula I wherein R 2 is the group Q". Salt formation can also be effected by die addition of a strong acid to die pyrimidine moiety of d e compounds of formula I. Suitable acids for that purpose are hydrochloric acid, hydrobromic acid, sulfuric acid or nitric acid.
  • Alkali metal and alkaline earth metal hydroxides that are especially suitable as salt formers are the hydroxides of lidiium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.
  • amines suitable for die formation of ammonium cations are botii ammonia and primary, secondary and tertiary C r C 4 alkylamines, C 1 -C 4 -hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-o
  • Examples of quaternary ammonium bases are generally the cations of ammonium halides, for example the tetramethylammonium cation, d e trimethylb ⁇ nzylammonium cation, the triethylbenzylammonium cation, die tetraethylammonium cation, the trimethylethyl- ammonium cation, and also the ammonium cation.
  • Y is preferably -COOH, or an organic or inorganic salt of that acid, o
  • tiiat group special preference is given to those compounds wherein R 12 is hydrogen, halogen, -OCH 3 or -COR 13 , wherein R 13 is especially ⁇ alkyl. Preference is also given to tiiose compounds wherein W is W ! and
  • compositions according to the invention are used, a herbicid ⁇ ally active pyrimidine of formula I, the above-mentioned preferences being given special mention, and as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula Eg
  • tiiose compositions according to die invention tiiat comprise a herbicide of formula I, special mention being made of the above-mentioned prefe ⁇ ed substituents, and a herbicide-antagonistically effective amount of a safener of formula lib wherein R 25 is C-i-C ⁇ alkyl, especially methyl, R 2 g is hydrogen or C 1 -C alkyl, R 27 is
  • a 2 is a group , wherein R ⁇ is
  • R g is hydrogen, mediyl or methoxy, ⁇ is methyl or methoxy, and R ⁇ R ⁇ and R f are hydrogen.
  • compositions according to die invention comprise a herbicide of formula I, special mention being made of die above-mentioned preferred substituents, and a herbicide-antagonistically effective amount of a safener of formula He wherein R 29 is preferably phenyl or halo-substituted phenyl, R 30 is 2-Cl, R 32 is ⁇ methyl and E is methine.
  • compositions according to die invention comprise a herbicide of formula I, me above-mentioned preferred substituents being given special mention, and a herbicide-antagonistically effective amount of a safener of formula Ed wherein R 33 and
  • R ⁇ are allyl, or R 33 and R ⁇ together are ; or R 33 and R 34 together are
  • R37. 3 8 an d R39 ai -- eac ⁇ methyl; or R 39 is hydrogen; or R 37 and R 3 g together are
  • R, ⁇ , R 50 , R5 1 and R 52 are preferably hydrogen.
  • compositions according to die invention comprise as herbicide a compound of formula If
  • Y is -COOCH 3 and R 12 is hydrogen; or b) Y is -COOCH 3 and R 12 is methylcarbonyl; or c) Y is -COOCH 3 and R 12 is ethylcarbonyl; or d) Y is -COOH and R 12 is hydrogen; or e) Y is -COOH and R 12 is fluorine; or f) Y is -COOH and R 12 is methoxy; or g) Y is 2-chlorophenylhydrazinoyl and R 1 is methoxy; or h) Y is 2-fluorophenylhydrazinoyl and R 12 is methoxy; or i) Y is o-tolylhydrazinoyl and R 12 is methoxy; or j) Y is -NHNHC(CH 3 ) 3 and R 12 is hydrogen; or k) Y is 2-phenylhydrazinoyl and R 12 is hydrogen; or
  • Y is 2-fluorophenylhydrazinoyl and R 12 is hydrogen; m) Y is 2-trifluoromethylphenylhydrazinoyl and R 12 is hydrogen; or n) Y is o-tolylhydrazinoyl and R 12 is hydrogen; or o) Y is 4-chlorophenylhydrazinoyl and R 12 is hydrogen;
  • Y is -NH- CH- C - NH 2 and R 12 is hydrogen; or C 2 H 5
  • a 2 is die group and R 26 is hydrogen; or of a compound of formula Ee
  • a 2 is die group H and R 26 is hydrogen; or of a compound of formula Ee
  • a 2 is the group and R 26 is med yl
  • a 2 is die group and R 26 is mediyl.
  • tiiat group of compositions according to d e invention special preference is made of tiiose that comprise as herbicide a compound of formula If wherein
  • Y is -COOCH 3 and R 12 is hydrogen; or b) Y is -COOCH 3 and R 12 is ethylcarbonyl; or c) Y is -COOH and R 12 is hydrogen; or
  • a 2 is die group and R 26 is hydrogen; or of a compound of formula Ee
  • a 2 is the group and R 26 is hydrogen
  • a 2 is the group and R 26 is methyl
  • a 2 is the group and R 6 is mediyl.
  • herbicides of formula I can advantageously also be combined wid the safeners mentioned in the following Tables 9 and 10 to form compositions according to the invention:
  • compositions according to die invention comprise die following herbicide/safener combinations:
  • the invention relates also to a method for the selective control of weeds in crops of useful plants, which meti od comprises treating die useful plants, the seeds or seedlings thereof or the cultivated area diereof with a herbicidally effective amount of the pyrimidine of formula I and a herbicide-antagonistically effective amount of a safener of formula Ha, lib, He, ⁇ d, Eh or IIi, simultaneously or independendy of one another.
  • Crop plants that can be protected against die damaging effect of the above-mentioned herbicides by die safeners of formula Ea, lib, Ec, Ed, Eh or Hi are especially those tiiat are important in the food and textile sectors, for example sugar cane and, especially, sorghum, maize, rice and other species of cereal (wheat, rye, barley, oats), most especially wheat and maize.
  • the weeds to be controlled may be bom monocotyledonous and dicotyledonous weeds.
  • Cultivated areas will be understood as meaning areas of land in which the crop plants are already growing or in which the seed of tiiose crop plants has already been sown, and also ground intended for growing those crop plants.
  • a safener or antidote of formula Ha, Eb, He, Ed, Hh or Hi can, depending on die intended use, be used to pre-treat the seed of die crop plant (dressing die seeds or seedlings) or can be introduced into die soil before or after sowing has taken place. It can, however, also be applied by itself or together witii the herbicide before or after the emergence of die plants.
  • the treatment of the plant or the seed witii die safener can therefore in principle take place independendy of die time of application of die phytotoxic chemical.
  • the plant can, however, also be treated by applying die phytotoxic chemical and the safener simultan ⁇ eously (tank mixture).
  • Preemergence treatment includes botii treatment of the cultivated area before sowing and treatment of cultivated areas in which seed has been sown but in which die plants have not yet grown.
  • the rate of application of die safener relative to tiiat of die herbicide depends largely on die mode of application.
  • die mode of application which is effected either using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide
  • d e ratio of safener to herbicide is generally from 1:100 to 10:1, preferably from 1:20 to 1:1, and especially 1:1.
  • much lower amounts of safener are required relative to die rate of application of herbicide per hectare of cultivated area.
  • the rate of application of herbicide is generally from 0.001 to 2 kg/ha, but preferably from 0.05 to 1 kg/ha.
  • safener/kg of seed In the case of seed-dressing, 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, will generally be applied. If die safener is applied in liquid form by seed soaking shortly before sowing, then it is advantageous to use safener solutions that comprise the active ingredient in a concentration of 1 to 10000 ppm, preferably 100 to 1000 ppm.
  • the compounds of formula H or combinations of compounds of formula Ea, Eb, Ec, Hd, Eh or Ei witii the herbicides of formula I to be antagonised are advantageously used togetiier with die adjuvants conventionally employed in formulation technology, and are dierefore formulated in known manner, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances.
  • die methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance witii die intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula E, or a combination of the compound of formula Ha, Eb, Ec, Hd, Eh or Ei with die herbicide of formula I to be antagonised, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding d e active ingredients witii extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, preferably die fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and tiieir ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomediyl or monoethyl etiier, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
  • aromatic hydrocarbons preferably die fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted na
  • the solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmoriUonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand.
  • a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood as comprising mixtures of surfactants.
  • Botii so-called water-soluble soaps and water-soluble syndietic surface-active compounds are suitable anionic surfactants.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Fatty acid mediyltaurin salts may also be mentioned.
  • syndietic surfactants especially fatty sulfonates, fatty sulfates, sulfonated benzunidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C 8 -C 22 alkyl radical which also includes die alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise die salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of die phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ediylene oxide, or phospholipids.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro ⁇ carbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are the water-soluble adducts of polyethylene oxide widi polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol etiier groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenolpoly ethoxy edianols, castor oil polyglycol ethers, polypropylene/polyethylene ojtide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyetiianol.
  • Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8 -C 2 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in die form of halides, mediyl sulfates or ethyl sulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the agrochemical compositions usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula Ea, Eb, He, Ed, Eh or Ei or a mixture of antidote and herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid adjuvant and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • Seed dressing a) Dressing the seeds with a wettable powder formulation of a compound of formula Ea, lib, He, Ed, Eh or Hi by shaking in a vessel until the formulation is evenly distributed over the surface of die seeds (dry dressing). Approximately 1 to 500 g of a compound of formula Ha, Hb, Ec, Ed, Eh or Ei (4 g to 2 kg of wettable powder) are used per 100 kg of seed.
  • Dressing d e seed or treating die germinated seedling are naturally the preferred mediods of application since the active ingredient treatment is directed wholly at the target crop.
  • a liquid formulation of a mixture of antidote and herbicide (ratio of the one to the other from 10:1 to 1:100) is used, die rate of application of herbicide being 0.01 to 5.0 kg per hectare.
  • a tank mixture of this type is applied before or after sowing.
  • the antidote is introduced in d e form of an emulsifiable concentrate, wettable powder or granules into the open, sown seed furrow and tiien, after covering the seed furrow, die herbicide is applied preemergence in die normal manner.
  • a solution of a compound of formula Ea, Hb, Ec, Ed, Hh or Hi is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and allowed to dry. If desired, a coating may be applied (coated granules) that allows the active ingredient to be released in metered amounts over a specific period of time.
  • Emulsifiable concentrates compound mixture calcium dodecylbenzenesulfonate castor oil polyethylene glycol etiier (36 moles of ethylene ojride) tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) cyclohexanone xylene mixture 65 %
  • Emulsions of any desired concentration can be produced from such concentrates by dilution witii water.
  • the active ingredient is dissolved in methylene chloride, die solution is sprayed onto die carrier, and die solvent is subsequendy evaporated off in vacuo.
  • Dusts compound mixture highly dispersed silicic acid talcum kaolin - 90 %
  • Wettable powders compound mixture sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphdialene- sulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 moles of ediylene oxide) - 2 % highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 %
  • the active ingredient is thoroughly mixed widi the adjuvants and die mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
  • Emulsifiable concentrates compound mixture 10 % octylphenol polyethylene glycol etiier (4-5 moles of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether
  • Emulsions of any required concentration can be obtained from tiiis concentrate by dilution witii water.
  • Ready-for-use dusts arc obtained by mixing the active ingredient witii the carriers and grinding die mixture in a suitable mill.
  • Extruder granules compound mixture 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %
  • the active ingredient is mixed and ground witii the adjuvants, and die mixture is subsequently moistened witii water.
  • the mixture is extruded and tiien dried in a stream of air.
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened witii polyethylene glycol.
  • Non-dusty coated granules are obtained in tiiis manner.
  • the finely ground active ingredient is intimately mixed with die adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution witii water.
  • Example B3 Safener action on maize and wheat:
  • Example B5 Safener action on wheat, barley and rice:
  • Example B6 Safener action on maize and wheat:
  • Example B7 Safener action on maize and wheat:

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Abstract

A selective herbicidal composition for the control of grasses and weeds in crops of useful plants comprises (a) a herbicidally effective amount of a pyrimidine of formula (I), wherein the substituents are defined in claim 1 and (b) as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula (IIa), wherein R24 is hydrogen or C1-C8alkyl and X2 is hydrogen or chlorine; or of an N-acylsulfamoylphenylurea of formula (IIb), wherein the substituents are defined in claim 1, or of a 1-phenylazole-3-carboxylic acid derivative of formula (IIc), wherein the substituents are defined in claim 1, or of a chloroacetamide of formula (IId), wherein the substituents are defined in claim 1, or of an oxime of formula (IIh), wherein the substituents are defined in claim 1, or of a phenylpyrimidine of formula (IIi), wherein the substituents are defined in claim 1.

Description

Selective herbicidal composition
The present invention relates to a selective herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in cereal crops, which comprises a herbicide and a safener (antidote) which protects the useful plants, but not the weeds, from the phytotoxic action of the herbicide, and to the use of that composition or of the combination of herbicide and safener in the control of weeds in crops of useful plants.
When herbicides are used, considerable damage may be caused to the crop plants depending on such factors as the concentration of herbicide and the mode of application, the species of crop plant, the nature of the soil and climatic conditions, for example period of exposure to light, temperature and rainfall. In particular, severe damage can be caused if, in the course of crop rotation, crop plants that are resistant to the herbicides are followed by other crop plants that have no or only insufficient resistance towards the herbicides.
In order to counter that problem, various compounds have already been proposed that are capable of specifically antagonising the damaging effect of the herbicide on the crop plant, that is to say of protecting the crop plant without at the same time significandy affecting the herbicidal action against the weeds to be controlled. It has been found that the proposed safeners are often very species- or type-specific both as regards the crop plants and as regards the herbicide and in some cases also as a function of the mode of application, that is to say a specific safener is often suitable only for a specific crop plant and a specific class of herbicidal compound.
For example, EP-A-0094349 discloses quinoline derivatives that protect crop plants from the phytotoxic action of herbicides of specific classes of compounds, such as phenoxy- propionic acid ester herbicides, ureas, carbamates or diphenyl ethers.
It has now been found that very specific safeners selected from the classes of the N-acyl- sulfamoylphenylureas, quinoline derivatives, chloroacetamides and 1-phenylazole- 3-carboxylic acid derivatives are suitable for protecting crop plants from the phytotoxic action of a specific class of pyrimidine herbicides.
There is therefore proposed according to the invention a selective herbicidal composition that comprises as active component, in addition to inert additives such as carriers, solvents and wetting agents, a mixture comprising
a) a herbicidally effective amount of a pyrimidine of formula I
wherein
X is oxygen or sulfur or, when W is W5, may also be NH, NC(O)H or NC(O)R62;
-c— H -c — R
Y is -COOH, or an organic or inorganic salt of that acid, II , 11 o o
\ _ ,c — N ~ R66 , or the possible salts of these groups;
H
R is -ORH;
Rj is one of the groups (a), (b) and (c)
R2 is hydrogen, methyl or the group Q" (Ql,
wherein
C is hydrogen, methyl or, together with Q4, is -(CH2)2-, -( Α 3-, -CH2CH(OH)CH2- or -CH2SCH2-;
Q2 is hydrogen or methyl;
Q-j is hydrogen, trifluoromethyl, ethynyl, vinyl, phenyl, cyano or C^alkoxycarbonyl, Cj^alkyl, or C^alkyl substituted by hydroxy, C alkoxy, mercapto, Cj^al yl- mercapto, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxy- carbonyl, C^alkoxycarbonyl, 2-propenyloxycarbonyl, cyano or by carbamoyl; and
Q4 is hydrogen, methyl, hydroxymethyl, formyl or cyano; or R2 together with R7 is -(CH2)p-, -CH2SCH2- or -CH2CHOHCH2-;
R3 is hydrogen, C^alkyl, phenyl, or phenyl mono- or di-substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or by nitro;
R4 is hydrogen or methyl; R5 is C^alkyl, C^ghaloalkyl, phenyl, benzyl, or phenyl substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro, cyano, carboxy or by C-^alkoxycarbonyl;
R, is hydrogen, hydroxymethyl, formyl, cyano, hydroxyimino, C^alkoxyimino, phosphono, phosphino, methylphosphino or a group COX^
R is hydrogen; C^alkyl or C^alkyl substituted by hydroxy, C^alkoxy, mercapto, acylmercapto, C^alkylthio, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxycarbonyl, 2-propenyloxycarbonyl, cyano, carbamoyl, methylphosphino or by methylsulfoximino; trifluoromethyl; ethynyl; vinyl or vinyl substituted by chlorine or by methoxy; phenyl or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl or by methoxy; or cyano or C^alkoxy- carbonyl; R8 is hydrogen or methyl; A is oxygen, sulfur or -NH-; m is 1, 2 or 3; n is 0, 1, 2 or 3; p is 2 or 3;
Xj is hydroxy, C^alkoxy, C3^alkenyloxy, mercapto, C alkylthio, amino, C^alkyl- amino, C2-4dialkylam no or Cj^alkoxyamino; or C-._4al-.0xy, C3^alkenyloxy, mercapto, C alkylthio, amino, C^al-cylamino, C^dialkylamino or C^alkoxy- amino each substituted by phenyl, benzyloxy or by ^alkoxy, or is one of the groups (d), (e) and (f)
wherein
Aj is oxygen, sulfur or -NH-;
R9 is hydrogen, C-^alkyl or benzyl;
R10 is hydroxymethyl, cyano or a group COQ';
Q is hydroxy, Cj^alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d); and
Q' is hydroxy, C1-C4alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);
Rπ is hydrogen, C1-C10al yl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di- CrC4alkylamino-C1-C4alkyl, halo-Ci-Cgal yl, C -C8alkenyl, halo-C^-Cgalkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C alkylcarbonyl, C1-C4alkylcarbonyloxy-C1-C2alkyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C alkyl, halo-CrC4alkyl, halo- C1-C4alkoxy and C1-C alkoxy; or is furoyl or thienyl; or CrC4alkyl substituted by phenyl, halophenyl, Cι-C4alkylphenyl, CrC4alkoxyphenyl, halo-CrC alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-Cι-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C^Cgalkylthiocarbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynylt--iocarbonyl, carbamoyl, mono-CrC4alkyl- aminocarbonyl, di-C1-C alkylaminocarbonyl, tri-Cj-Cgalkylsilyl or by di-Cx-Cgalkyl-phenylsilyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, Cι-C4alkyl, halo-C1-C alkyl, halo-C C4alkoxy and Cj-C4alkoxy or is monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; oxetan-3-yl or dioxan-2-yl that are unsubstituted or substituted by one or two C1-C4alkyl radicals; or C1-C a--k;yl substituted by cyano, nitro, carboxy or by Ci-Cgal ylthio-Cj-Cgalkoxycarbonyl; or the groups -N=C(CH3)2 or -CH2CH2ON=C(CH3)2;
or W and Y together form a group W4
or W and Y together form a group W5 );
or W and Y together form a group W6 (W6);
E is nitrogen or -CR12;
R12 is hydrogen, halogen, hydroxy, C2-C4a.J-.oxy, phenyl or benzyl; or phenyl substituted by CrC4alkyl, CrC4alkoxy, Cj^haloalkyl or by halogen; benzyl substituted by CrC4alkyl, CrC4alkoxy, CrC4haloalkyl or by halogen; -COR13, "^"Ri4 ,
N-R15
-S(O)qR!6, (4,6-dimethoxy-pyrimidin-2-yl)-oxy; C1-C alkyl that is unsubstituted or substituted by halogen; ethenyl that is unsubstituted or substituted by C1-C alkyl, phenyl, halogen, cyano or C1-C4alkoxycarbonyl; ethynyl that is unsubstituted or substituted by halogen, CrC4alkyl or phenyl; phenoxy or phenylthio that are unsubstituted or substituted by C1-C alkyl, C1-C4alkoxy, or halogen; R13 is CrC4alkyl, halo-CrC4a-kyl, CrC4al oxy-C1-C4alkyl; amino, CrC4a---:ylaπ--no, di-C1-C4alkylamino, C2-C4haloalkylamino, di-C2-C4haloalkylamino, C1-C4alkoxy- alkylamino, di-C1-C4alkoxyalkylamino, C3-C alkenylamino, diallylamino, -N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperidazino, -O-N=C(CH3)-CH3 or -O-CH2-CH2-O-N=C(CH3)-CH3; R1 is hydrogen, Cj-Cjoalkyl that is unsubstituted or substituted by acyl or by cyano; C1-C4alkoxy-C1-C4alkyl, CrC4alkylthio-C1-C4alkyl, CrC4alkylsulfonyl- C1-C4alkyl, CrC4alkylsulfιnyl-CrC4alkyl, or phenyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, Cj^alkyl, halo-C C alkyl, halo-C_-C4alkoxy and CrC4alkoxy; R15 is hydroxy, Cj-C-toalkyl that is unsubstituted or substituted by halogen; - alkoxy that is unsubstituted or substituted by halogen, benzyloxy, CrC6alkoxycarbonyl, C3-C6cycloalkyl, acyl, di-CrC4alkylamino or by CrC6alkoxy; phenyl, phenoxy or benzyloxy each of which is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo- C1-C4alkyl, halo-C1-C alkoxy and Cj^alkoxy; C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C4alkoxyamino, C1-C alkylamino, phenylamino, -OSi(CH3)3, C2-C8alkenyloxy or C3-C8alkynyloxy; q is the number 0, 1 or 2; R16 is Cj-Cjoalkyl that is unsubstituted or substituted by halogen; phenyl that is unsubstituted or substituted by up to three identical or different substituents selected from halogen, CrC alkyl, halo-C1-C alkyl, halo-C1-C alkoxy and CrC4alkoxy; C2-Cgalkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl or halo- C3-C7cycloalkyl; R17 is hydrogen, C^galkyl, C3.6cycloalkyl, Cι.6alkyl that is monosubstituted by chlorine or mono- to hexa-substituted by fluorine; phenyl or thienyl, or phenyl mono- or di- substituted by fluorine, chlorine, methyl or by methoxy; R18 is hydrogen, methyl or, together with R17, is -(CH2)2-, -(CH2)3-, -(CH2)4- or
-(CH2)5- ; R19 is hydrogen, methyl, fluorine, chlorine, bromine, Cj-galkoxy, C3-6alkenyloxy,
C3. alkynyloxy, C3^cycloalkyl-C1.2alkoxy, C4.6cycloalkoxy, or C^alkoxy that is monosubstituted by cyano, Cι.2alkoxy or by chlorine or mono- to hexa-substituted by fluorine; C^galkylthio or cyano; R20 is hydrogen, C^alkyl, C1.3alkylthio or, together with R21, is -(CH2)4-, -(CH2)5-,
-S(CH2)2S- or -S(CH2)3S- ; R2ι is C^alkyl, C2.6alkenyl, C3.6cycloalkyl, Cj^haloalkyl, C1-3alkoxy, Cj.3alkylthio, formyl, Cx-salkylcarbonyl, carboxy, C^alkoxycarbonyl, phenyl, or phenyl substit¬ uted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or by nitro; or is 2-, 3- ' or 4-pyridyl, 2- or 3-furyl or 2- or 3-thienyl; R22 is hydrogen, - alkyl, C3-C6cycloalkyl, CrC6haloallcyl, C3-C6alkenyl,
C3-C6alkynyl, C3-C6haloalkenyl, C3-C6haloalkynyl, phenyl or benzyl, or phenyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or by halogen; benzyl substituted by C1-C al yl, C1-C alkoxy, C1-C haloalkyl or by halogen; halogen, hydroxy, -CHO, -COOH, phenoxy, cyano, phenylthio, -CONH , -OCHO, C2-C^a]Jcanoyloxy, C2-C5alkoxycarbonyloxy, C2-C3al ylcarbamoyloxy, or di(C1-C2alkoxy)phosphonyl; R23 is hydrogen, CrC6alkyl or CF3; r is 0, 1, 2 or 3; s is 0, 1, 2 or 3; m is 0, 1 or 2;
R57 is hydrogen, hydroxy, CrC,salkoxy, Cx- alkoxyalkoxy, C-t- acyloxyalkoxy, tri- methylsilylethoxy, C Cβalkylsulfonylamino, Cx-Cgalkylthio, imidazolyl, benzyl¬ oxy, phenoxy or thiophenoxy, or benzyloxy, phenoxy or thiophenoxy; R58 is halogen, Cj-Cβhaloalkyl, C-j-Cβalkyl, acylamino, C3-C6cycloalkyl, halo- substituted Ci- alkoxy- carbonyl, C-t-C^alkoxy, Ci- a^lamino, di- -Cgalkylamino, C_-C6a---:oxyimino- alkyl, acyl, C-t-Cgalkylthio, phenyl, benzyl, phenylamino or benzylamino; R59 is halogen, C- Cgalkyl, C C6alkoxy, C-t-Cgalkylamino, di-Cj-Cgalkylamino, C-j-Cδhaloalkyl, C- Cghaloalkoxy, nitro, hydroxy, cyano, CrC6alkoxyal oxy, Ci-Cfialkoxycarbonylalkoxy, Ci-Cgalkylthioalkoxy, Ci- alkylthio, Cj-Cgalkoxy- al yl, C2-Cgalkenyl, C3-C6allcynyl, benzyloxy or phenoxy; R-50 is halogen, C C6alkyl, C^Cghaloalkyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C2-C6alkenyloxy, C3-C6alkynyloxy, Cx-Cgalkoxycarbonyl, Cj- alkoxy, Cx-Cgalkylamino, di-Ci-Cgalkylamino, phenyl, benzyl, C1-C6alkoxy- iminoal yl, acyl, Cj- alkylthio, phenylamino or benzylamino; R61 is hydrogen, hydroxy, -Cgalkoxy, Cj-Cβalkoxyalkoxy, Cj- acyloxyalkoxy, trimethylsilylethoxy, C1-C6alkylsulfonylamino, Cj-Cealkylthio, imidazolyl, benzyl¬ oxy, phenoxy or thiophenoxy, or benzyloxy, phenoxy or thiophenoxy; R62 is CrC6alkyl or C1-C6alkoxy;
R66 is Ci-Cβal yl, or CrC6alkyl which is substituted by up to 3 fluorine atoms, 1 chlorine atom, 1 C1-C4alkoxy group, 1 C1-C4alkoxycarbonyl group, 1 dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ethynyl group or 1 phenyl group which is unsubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or -phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or NR^R^; or OR^;
R67 is hydrogen or C1-C4alkyl;
R68 is hydrogen, -Cβalkyl, phenyl, pyridyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted by ^alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is -Cgalkylcarbonyl, trifluoro- methylcarbonyl, C3-C6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridyl- carbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, tri¬ fluoromethyl, methoxy or nitro; or ^al oxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or Ci-C^alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy; and
R69 is hydrogen, C C6alkyl or C2-C6alkenyl, or C2-C6alkenyl which is substituted by halogen or phenyl, or C1-C4alkoxycarbonyl-C1-C4alkyl or C1-C alkylthiocarbonyl- CrC4al yl;
and
b) as safener, a herbicide-antagonistically effective amount of a quinoline derivative of formula Ha
wherein
R24 is hydrogen or C^ a-kyl and
X2 is hydrogen or chlorine; or of an N-acylsulfamoylphenylurea of formula lib
wherein
A2 is a group
R-25 and R^, independently of one another, are hydrogen, C Cgalkyl, C3-C8cycloalkyl,
C3-C6alkenyl, , or C1-C4alkyl substituted by
C1-C4alkoxy or by or R! and R2 together form a C4-C6alkylene bridge that can be interrupted by oxygen, sulfur, SO, SO2, NH or by -N(CrC4alkyl)-;
R27 is hydrogen or C1-C aU--yl;
Ra is hydrogen, halogen, cyano, trifluoromethyl, nitro, C1-C alkyl, C1-C alkoxy, CrC4alkylthio, CrC4alkylsulfmyl, CrC4alkylsulfonyl, -COORjτ -CONR,^, -COR,,, -SO2NRkRm or -OSO2-C1-C4alkyl;
Rg is hydrogen, halogen, cyano, nitro, C1-C4al yl, C1-C4alkylthio,
CrC4alkylsulfmyl, CrC4al-cylsulfonyl, -COORj, -CONR^, -COR,., -SOiNRj-Rπ-, -OSO2-C1-C4alkyl, CrC6alkoxy, or CrC6alkoxy substituted by CrC4alkoxy or by halogen; C3-C6alkenyloxy, or C3-C6alkenyloxy substituted by halogen; or C3- C6alkyny loxy ; or Ra and Rb together form a C3-C4alkylene bridge that can be substituted by halogen or by C1-C4alkyl, or a C3-C4alkenylene bridge that can be substituted by halogen or by CrC4alkyl, or a C alkadienylene bridge that can be substituted by halogen or by CrC4alkyl;
Rb and Rh, independently of one another, are hydrogen, halogen, CrC alkyl, trifluoro¬ methyl, CrC6alkoxy, CrC6allcylthio or -COORJ;
Rc is hydrogen, halogen, nitro, -Qalkyl or methoxy;
Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C alkoxy, C1-C4alkylthio, CrC4alkyl- sulfinyl, C^alkylsulfonyl, -COORj or CONRfcR-,,;
Re is hydrogen, halogen, CrC4alI yl, -COORj, trifluoromethyl or methoxy; or Rd and R-. together form a C3-C4alkylene bridge;
Rf is hydrogen, halogen or C1-C alkyl;
Rx and Ry, independently of one another, are hydrogen, halogen, C-t-C^alkyl, CrC alkoxy, CrC al ylthio, -COOR28, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm, independently of one another, are hydrogen or C1-C a^l; or
Rk and Rπ, together form a C4-C6alkylene bridge that can be interrupted by oxygen, NH or by -N(CrC4alkyl)-;
Rn is C1-C4al yl, phenyl, or phenyl substituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl;
R28 is hydrogen, -Cioallcyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di- C1-C4alkylamino-C1-C alkyl, halo-Cj-Cgalkyl, C2-C8alkenyl, halo-C^-Cgalkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, CrC8alkylcarbonyl, allyl- carbonyl, C3-C7cycloal ylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, CrC4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy; or is furoyl or thienyl; or C C4alkyl substituted by phenyl, halophenyl, C1-C alkyl- phenyl, C1-C alkoxyphenyl, halo-C1-C alkylphenyl, halo-C1-C alkoxyphenyl, C1-Cfialkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxy- carbonyl, C3-C8alkynyloxycarbonyl, Cj-Cgalkylthiocarbonyl, C3-C8alkenylthio- carbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, mono-Cι-C4alkylaminocarbonyl or by di-Cι-C4al ylaminocarbonyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, Cj^alkyl, halo-C1-C alkyl, halo-Cj-C4alkoxy and Cj^alkoxy or monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two CrC4alkyl radicals; or dioxan-2-yl that is unsubstituted or substituted by one or two CrC alkyl radicals; or C O^a- yl substituted by cyano, nitro, carboxy or by Cj-Cgal-ylthio-Ci-Cgalkoxycarbonyl; or of a l-phenylazole-3-carboxylic acid derivative of formula lie
wherein
E2 is nitrogen or methine;
R29 is -CC13, phenyl or halo-substituted phenyl;
R30 and R31, independently of one another, are hydrogen or halogen; and
R32 is CrC4alkyl; or of a chloroacetamide of formula Ed
R33 o \ II
N-C — CHC12 (πd)
R /
■-34
wherein
R33 and R34, independendy of one another, are C- Cgalkyl or C^^alkenyl;
or R33 and R34 together are ; wherein
R35 and R36, independently of one another, are hydrogen or CrC6alkyl; or R33 and R34 together are
R37 and R38, independenύy of one another, are C1-C4alkyl; or R37 and R38 together are -(CH2)5-;
R39 is hydrogen, C1-C alkyl or ^
or R33 and
wherein
R.40. R4I' R42» R43» R 4» 45' 6' R47> 48» R49» R50» R5I' Rs2> s3» R54 an^ 55' independ¬ endy of one another, are hydrogen or C1-C4alkyl; or of an oxime of formula Eh
wherein
R63 is hydrogen or chlorine and
R.54 is cyano or trifluoromethyl; or of a phenylpyrimidine of formula IIi
wherein
R65 is hydrogen or methyl.
In the definitions used in tiiis description, the generic terms given, as well as the individual definitions of the substituents obtainable by combining individual subsidiary terms, include, for example, the following individual substituents; this list does not represent a limitation of die invention.
In the diagrammatic representation of the substituents Wj, W2 and W3 the linkage point to the substituent Y is always at the upper free valency. For example, in the substituent Wj the linkage point to substituent Y is in the ortho-position relative to substituent E.
In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
Alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and die various isomeric pentyl, hexyl, heptyl, octyl, nonyl and decyl radicals.
Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl and dichlorofluoromethyl.
Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy. Haloalkoxy is, for example, fiuoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetra- fluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromemoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio or isomeric pentylthio, preferably methylthio and ethylthio.
Alkenyl is to be understood as being straight-chain or branched alkenyl, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl, 2-hexenyl or 3-heptenyl. Preference is given to alkenyl radicals having a chain length of 2 or 3 carbon atoms.
The alkynyl radicals occurring in the definitions of die substituents may be straight-chain or branched, such as, for example, ethynyl, propargyl, 3-butynyl, 1-methylpropargyl, 1-pentynyl or 2-hexynyl. Ethynyl and propargyl are preferred.
Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopropyl, cyclopentyl or cyclohexyl.
Alkoxycarbonyl is, for example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and etiioxy- carbonyl.
Alkoxyalkyl is, for example: methoxymethyl, ethoxymethyl, propoxymethyl, methoxy- ethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl or propoxypropyl.
Alkylthioalkyl is, for example: methylthiomethyl, ethylthiomethyl, methylthioethyl, ethyl- thioethyl or isopropylthioethyl.
Alkylaminoalkyl is, for example: methylaminoethyl, dimethylaminoethyl, ethylamino- ethyl or diethylaminoethyl.
Cyanoalkyl is, for example: cyanomethyl, cyanoethyl or cyanopropyl.
Halocycloalkyl is, for example: 2,2-dichlorocyclopropyl or pentachlorocyclohexyl.
Alkylsulfonyl is, for example: methylsulfonyl, ethylsulfonyl, propylsulfonyl or butyl- sulfonyl. Methyl- and ed yl-sulfonyl are preferred. Phenyl and thienyl, also as part of a substituent such as phenoxy', thiophenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, can generally be unsub¬ stituted or substituted by further substituents. The substituents may be in the ortho-, meta- and/or para-position(s) or in 2-, 3-, 4- or 5-position of the thienyl ring, respectively. Preferred substituent positions are the ortho- and para-positions to the ring-linkage point. Preferred substituents are halogen atoms.
In the further substituents tiiat are composed of several basic elements, the elements are as defined above by way of example. In ti ose cases also, the lists do not represent a limitation of the invention: they are of an illustrative nature only.
Suitable salts of the free carboxylic acid are, especially, alkali metal salts such as lithium, sodium, potassium; alkaline earth metal salts such as magnesium or calcium; or salts of manganese, copper, zinc or iron; or salts of organic ammonium bases, such as ammonia, primary, secondary or tertiary alkylamines, such as methylammonium, dietiiylammonium, methylammonium, morpholinium, tetrabutylammonium, benzyltrimethylammonium, phosphonium, sulfonium, sulfoxonium or pyridinium.
The invention relates also to salts that the compounds of formula I are capable of forming with amines, alkali and alkaline earth metal bases or quaternary ammonium bases. Within the scope of the present invention, those salts also include hydrazonium salts that may be formed by compounds of formula I wherein R2 is the group Q". Salt formation can also be effected by die addition of a strong acid to die pyrimidine moiety of d e compounds of formula I. Suitable acids for that purpose are hydrochloric acid, hydrobromic acid, sulfuric acid or nitric acid.
Alkali metal and alkaline earth metal hydroxides that are especially suitable as salt formers are the hydroxides of lidiium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.
Examples of amines suitable for die formation of ammonium cations are botii ammonia and primary, secondary and tertiary CrC4alkylamines, C1-C4-hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl- octylamine, dimemylamine, diediylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctyl- amine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diedιanolamine, N-ethyl- propanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, diemanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethyl- amine and ethoxyethylamine; heterocyclic amines, such as pyridine, quinoline, isoquino- line, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary aryl- amines, such as anilines, metiioxyanilines, ethoxyanilines, o,m,p-toluidines, phenylene- diamines, benzidines, naphthylamines and o,m,p-chloroanilines; but especially triethyl¬ amine, isopropylamine and diisopropylamine.
Examples of quaternary ammonium bases are generally the cations of ammonium halides, for example the tetramethylammonium cation, d e trimethylbεnzylammonium cation, the triethylbenzylammonium cation, die tetraethylammonium cation, the trimethylethyl- ammonium cation, and also the ammonium cation.
When the substituents Ra and R together form a C3-C4alkylene, C3-C4alkenylene or C alkadienylene bridge, each of which may be substituted by halogen or by C1-C4alkyl, there are formed, together with the phenyl ring to which the bridge is bonded, binuclear systems, such as 1 ,2,3,4- tetrahydronaphtiialene, l-chloro-2-methyl-3,4-dihydro- naphthalene, indanes, 1,2-dihydronaphthalene, indene, naphthalene, 2-methylnaphthalene, 1-n-butylnaphdιalene, 2-ethylnaphthalene or 1-chloronaphthalene.
When d e substituents Rd and Rς together form a C3-C alkylene bridge, tiiere are formed, togedier with the ring system to which tiiey are bonded, polynuclear systems, such as 2,3-tetramethylenethiophene, 2,3-trimethylenedιiophene, 2,3-tetramethylenefuran,
3,4-tetramethylenepyridine or
Compounds of formula I, or salts uiereof, that are preferred for use in the composition according to the invention arc those wherein W is W1? W2, W3 or W4, but especially W^
-c — H and wherein Y is preferably -COOH, or an organic or inorganic salt of that acid, o
, but most especially -COOH, or an organic
or inorganic salt of that acid. Of tiiat group, special preference is given to those compounds wherein R12 is hydrogen, halogen, -OCH3 or -COR13, wherein R13 is especially ^alkyl. Preference is also given to tiiose compounds wherein W is W! and
E is nitrogen.
Very especially preferred individual compounds of formula I are listed in die following Tables 1 to 4:
Table 1: Compounds of formula Ia
OH
OH
OCH3
OC2H5
OCH3
CH3O CH3 I II / 3
1.006 O C-F NH-C-C-N I \ cm, CH3 COOC2H5
1.007 O C-F NH-CH
CH2CH2COOC2H5
NH-N(CH3)2 *Brθ
1.008 O CH CH2COOC2H5
1.009 O CH NH- ■α
1.010 O CH NH-CH- C - NH2
C2H5
1.011 O C-F OH Comp. X E R No.
1.012 O C-H -NH-N(CH3)2
1.023 O N -O Comp. X E R No.
1.026 O N -OCH2CH2ON=C(CH3)2
1.027 O C-OCH3 OH
1.029 O C-F OH
1.030 O C-H -NH-N(CH3)2
Table 2: Compounds of formula lb
Comp. X R 23 R 22 No.
2.001 2.002 2.003 2.004 2.005 2.006
Table 3: Compounds of formula Ic
Comp. X R R 21 R. 20 No.
3.001 O OH CH3 CH3
3.002 O OH C2H5 CH3 Table 4: Compounds of formula Id
2
Table 11: Compounds of formula le
^ n66
Comp. No. X R, 66
11.01 O -NHCH(CH3)2 11.02 O -N(CH3)2
11.03 O ■ Cl
In especially preferred compositions according to the invention tiiere are used, a herbicid¬ ally active pyrimidine of formula I, the above-mentioned preferences being given special mention, and as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula Eg
Further safeners of formula Ila that may be given special mention are listed in Table 5:
Table 5: Compounds of formula Ila
Preference is also given to tiiose compositions according to die invention tiiat comprise a herbicide of formula I, special mention being made of the above-mentioned prefeιτed substituents, and a herbicide-antagonistically effective amount of a safener of formula lib wherein R25 is C-i-C^alkyl, especially methyl, R2g is hydrogen or C1-C alkyl, R27 is
hydrogen and A2 is a group , wherein R~ is
preferably hydrogen, Rg is hydrogen, mediyl or methoxy, \ is methyl or methoxy, and R^ R^ and Rf are hydrogen.
Further safeners of formula lib that may be given special mention are listed as compounds of formula lie in Table 6: Table 6: Compounds of formula He
Comp. R 26
No.
Further preferred compositions according to die invention comprise a herbicide of formula I, special mention being made of die above-mentioned preferred substituents, and a herbicide-antagonistically effective amount of a safener of formula He wherein R29 is preferably phenyl or halo-substituted phenyl, R30 is 2-Cl, R32 is^methyl and E is methine.
Further safeners of formula lie that may be given special mention are listed as compounds of formula Hf in Table 7: Table 7: Compounds of formula Hf
Further preferred compositions according to die invention comprise a herbicide of formula I, me above-mentioned preferred substituents being given special mention, and a herbicide-antagonistically effective amount of a safener of formula Ed wherein R33 and
R^ are allyl, or R33 and R^ together are ; or R33 and R34 together are
, wherein either R37 and R38 are each metiiyl and R39 iiss
R37. 38 and R39 ai-- eac^ methyl; or R39 is hydrogen; or R37 and R3g together are
-(CH2)5-; or R33 and , wherein R53, R54 and R55
are preferably methyl and R,^, R50, R51 and R52 are preferably hydrogen.
Further safeners of formula ud tiiat may be given special mention are listed in Table 8:
Table 8: Compounds of formula Ed
Outstanding selective herbicidal compositions according to die invention comprise as herbicide a compound of formula If
wherein a) Y is -COOCH3 and R12 is hydrogen; or b) Y is -COOCH3 and R12 is methylcarbonyl; or c) Y is -COOCH3 and R12 is ethylcarbonyl; or d) Y is -COOH and R12 is hydrogen; or e) Y is -COOH and R12 is fluorine; or f) Y is -COOH and R12 is methoxy; or g) Y is 2-chlorophenylhydrazinoyl and R1 is methoxy; or h) Y is 2-fluorophenylhydrazinoyl and R12 is methoxy; or i) Y is o-tolylhydrazinoyl and R12 is methoxy; or j) Y is -NHNHC(CH3)3 and R12 is hydrogen; or k) Y is 2-phenylhydrazinoyl and R12 is hydrogen; or
1) Y is 2-fluorophenylhydrazinoyl and R12 is hydrogen; m) Y is 2-trifluoromethylphenylhydrazinoyl and R12 is hydrogen; or n) Y is o-tolylhydrazinoyl and R12 is hydrogen; or o) Y is 4-chlorophenylhydrazinoyl and R12 is hydrogen;
o
O
II p) Y is -NH- CH- C - NH2 and R12 is hydrogen; or C2H5
q) Y is and R12 is hydrogen; or
OH r) Y and R12 togetiier are •o- or
CH3
s) Y and R12 together are or
H t) Y and R12 together are o or
(S)
CH3 '
o H u) Y and R12 togetiier are •O- ; or
CH (R) v) Y and R12 together are or w) a compound of formula Ig
and as safener a herbicide-antagonistically effective amount of a compound of formula Ee
wherein A2 is die group and R26 is hydrogen; or of a compound of formula Ee
wherein A2 is die group H and R26 is hydrogen; or of a compound of formula Ee
wherein A2 is the group and R26 is med yl;
or of a compound of formula Ee
wherein A2 is die group and R26 is mediyl.
Of tiiat group of compositions according to d e invention, special preference is made of tiiose that comprise as herbicide a compound of formula If wherein
a) Y is -COOCH3 and R12 is hydrogen; or b) Y is -COOCH3 and R12 is ethylcarbonyl; or c) Y is -COOH and R12 is hydrogen; or
d) Y and R12 together are or
o OH e) Y and R12 together are ii_o-4-
C2H5 or a compound of formula Ig
and as safener a herbicide-antagonistically effective amount of a compound of formula Ee
wherein A2 is die group and R26 is hydrogen; or of a compound of formula Ee
wherein A2 is the group and R26 is hydrogen;
or of a compound of formula Ee
wherein A2 is the group and R26 is methyl;
or of a compound of formula Ee
wherein A2 is the group and R 6 is mediyl.
The herbicides of formula I can advantageously also be combined wid the safeners mentioned in the following Tables 9 and 10 to form compositions according to the invention:
Table 9: Compounds of formula Eh
Table 10: Compounds of formula Hi
Especially outstanding compositions according to die invention comprise die following herbicide/safener combinations:
The compounds of formulae I, Ila, Eb, He, Ed, Eh and IE are known or they can be prepared analogously to known processes. Compounds of formula I are described, for example, in EP-A-0347 811, 0335 409, 0426476, 0315 889, 0435 170, 0402751, 0459 243, 0409369 and WO 91/05781 -A. Compounds of formula I wherein W is W5 or W6 are described in WO 92/17468.
The quinoline derivatives within die scope of formula Ha and dieir preparation are known or they can be prepared analogously to known processes which are described, for example, in patent specification EP-A-0094349. Compounds of formula Eb are described in EP-A-0365 484 and compounds of formula Ec are described in EP-A-0268 554 and 0 174562. Compounds of formula Ed are known, for example, from USP 4971 618, USP 3 959304, USP 4256481, EP-A-0 149974, EP-A-0304409 and DE-OS-2948 535. Compounds of formula Eh are disclosed in EP-A-0089313 and compounds of formula Ei are disclosed in EP-A-0055 693.
The invention relates also to a method for the selective control of weeds in crops of useful plants, which meti od comprises treating die useful plants, the seeds or seedlings thereof or the cultivated area diereof with a herbicidally effective amount of the pyrimidine of formula I and a herbicide-antagonistically effective amount of a safener of formula Ha, lib, He, πd, Eh or IIi, simultaneously or independendy of one another.
Crop plants that can be protected against die damaging effect of the above-mentioned herbicides by die safeners of formula Ea, lib, Ec, Ed, Eh or Hi are especially those tiiat are important in the food and textile sectors, for example sugar cane and, especially, sorghum, maize, rice and other species of cereal (wheat, rye, barley, oats), most especially wheat and maize. The weeds to be controlled may be bom monocotyledonous and dicotyledonous weeds.
There come into consideration as crop plants or parts of tiiose plants, for example, those mentioned above. Cultivated areas will be understood as meaning areas of land in which the crop plants are already growing or in which the seed of tiiose crop plants has already been sown, and also ground intended for growing those crop plants.
A safener or antidote of formula Ha, Eb, He, Ed, Hh or Hi can, depending on die intended use, be used to pre-treat the seed of die crop plant (dressing die seeds or seedlings) or can be introduced into die soil before or after sowing has taken place. It can, however, also be applied by itself or together witii the herbicide before or after the emergence of die plants. The treatment of the plant or the seed witii die safener can therefore in principle take place independendy of die time of application of die phytotoxic chemical. The plant can, however, also be treated by applying die phytotoxic chemical and the safener simultan¬ eously (tank mixture). Preemergence treatment includes botii treatment of the cultivated area before sowing and treatment of cultivated areas in which seed has been sown but in which die plants have not yet grown.
The rate of application of die safener relative to tiiat of die herbicide depends largely on die mode of application. In die case of field treatment, which is effected either using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, d e ratio of safener to herbicide is generally from 1:100 to 10:1, preferably from 1:20 to 1:1, and especially 1:1. In contrast, in the case of seed dressing, much lower amounts of safener are required relative to die rate of application of herbicide per hectare of cultivated area.
In die case of field treatment, 0.001 to 5.0 kg of safener/ha, preferably 0.01 to 0.5 kg of safener/ha, will usually be applied.
The rate of application of herbicide is generally from 0.001 to 2 kg/ha, but preferably from 0.05 to 1 kg/ha.
In the case of seed-dressing, 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, will generally be applied. If die safener is applied in liquid form by seed soaking shortly before sowing, then it is advantageous to use safener solutions that comprise the active ingredient in a concentration of 1 to 10000 ppm, preferably 100 to 1000 ppm.
For the purpose of application, the compounds of formula H or combinations of compounds of formula Ea, Eb, Ec, Hd, Eh or Ei witii the herbicides of formula I to be antagonised are advantageously used togetiier with die adjuvants conventionally employed in formulation technology, and are dierefore formulated in known manner, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with die nature of die compositions to be used, die methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance witii die intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula E, or a combination of the compound of formula Ha, Eb, Ec, Hd, Eh or Ei with die herbicide of formula I to be antagonised, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding d e active ingredients witii extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably die fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and tiieir ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomediyl or monoethyl etiier, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmoriUonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. Depending on the nature of the compound of formula Ha, Hb, Ec, Hd, Eh or Hi to be formulated and, where appropriate, also on he nature of the herbicide of formula I to be antagonised, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Botii so-called water-soluble soaps and water-soluble syndietic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Fatty acid mediyltaurin salts may also be mentioned.
More frequendy, however, so-called syndietic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzunidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes die alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise die salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of die phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ediylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro¬ carbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide widi polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol etiier groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpoly ethoxy edianols, castor oil polyglycol ethers, polypropylene/polyethylene ojtide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyetiianol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C 2alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in die form of halides, mediyl sulfates or ethyl sulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in formulation technology are described inter alia in the following publications:
"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood,
New Jersey, 1981.
Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981.
The agrochemical compositions usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula Ea, Eb, He, Ed, Eh or Ei or a mixture of antidote and herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid adjuvant and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
Various methods and techniques are suitable for using compounds of formula Ea, Eb, He, lid, Hh or Ei or compositions comprising them for protecting crop plants against the damaging effects of herbicides of formula I. The following are examples thereof:
i) Seed dressing a) Dressing the seeds with a wettable powder formulation of a compound of formula Ea, lib, He, Ed, Eh or Hi by shaking in a vessel until the formulation is evenly distributed over the surface of die seeds (dry dressing). Approximately 1 to 500 g of a compound of formula Ha, Hb, Ec, Ed, Eh or Ei (4 g to 2 kg of wettable powder) are used per 100 kg of seed.
b) Dressing the seeds witii an emulsifiable concentrate of a compound of formula Ha, Eb, lie, Ed, Hh or IIi according to metiiod a) (wet dressing).
c) Dressing by immersing the seeds in a mixture comprising 100 to 1000 ppm of a compound of formula Ea, Hb, Ec, Ed, Hh or Hi for 1 to 72 hours and, if desired, subsequendy drying die seeds (immersion dressing).
Dressing d e seed or treating die germinated seedling are naturally the preferred mediods of application since the active ingredient treatment is directed wholly at the target crop. Normally 1 to 1000 g of antidote, preferably 5 to 250 g of antidote, are used per 100 kg of seed, aldiough, depending on die mediod employed, which also allows the addition of otiier active ingredients or micronutrients, amounts tiiat exceed or fall short of specified concentration limits may be employed (repeat dressing).
ii) Application from a tank mixture
A liquid formulation of a mixture of antidote and herbicide (ratio of the one to the other from 10:1 to 1:100) is used, die rate of application of herbicide being 0.01 to 5.0 kg per hectare. A tank mixture of this type is applied before or after sowing.
iii) Application to the seed furrow
The antidote is introduced in d e form of an emulsifiable concentrate, wettable powder or granules into the open, sown seed furrow and tiien, after covering the seed furrow, die herbicide is applied preemergence in die normal manner.
iv) Controlled release of active ingredient
A solution of a compound of formula Ea, Hb, Ec, Ed, Hh or Hi is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and allowed to dry. If desired, a coating may be applied (coated granules) that allows the active ingredient to be released in metered amounts over a specific period of time.
Formulation Examples for liquid active ingredients of formula Ea, Eb, Ec, Ed, Eh or Ei or mixtures thereof with a herbicide of formula I (throughout, percentages are by weight)
1. Emulsifiable concentrates compound mixture calcium dodecylbenzenesulfonate castor oil polyethylene glycol etiier (36 moles of ethylene ojride) tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) cyclohexanone xylene mixture 65 %
Emulsions of any desired concentration can be produced from such concentrates by dilution witii water.
2. Solutions a) b) c) d) compound mixture 80 % 10 % 5 % 95 % ediylene glycol monomediyl ether 20 % polyethylene glycol (mol. wt.400) 70 % N-methyl-2-pyrrolidone 20 % epoxidised coconut oil 1 % 5 % petroleum fraction (boiling range 160-190°) 94 % These solutions are suitable for application in the form of micro-drops.
3. Granules compound mixture kaolin highly dispersed silicic acid attapulgite - 90 %
The active ingredient is dissolved in methylene chloride, die solution is sprayed onto die carrier, and die solvent is subsequendy evaporated off in vacuo.
4. Dusts compound mixture highly dispersed silicic acid talcum kaolin - 90 %
Ready-for-use dusts are obtained by intimately mixing die carriers with the active ingredient
Formulation Examples for solid active ingredients of formula Ha, lib, Ec, Hd, Hh or Ei or mixtures thereof with a herbicide of formula I (throughout, percentages are by weight)
5. Wettable powders compound mixture sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphdialene- sulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 moles of ediylene oxide) - 2 % highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 %
The active ingredient is thoroughly mixed widi the adjuvants and die mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
6. Emulsifiable concentrates compound mixture 10 % octylphenol polyethylene glycol etiier (4-5 moles of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether
(35 moles of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 %
Emulsions of any required concentration can be obtained from tiiis concentrate by dilution witii water.
7. Dusts a) b) compound mixture 5 % 8 % talcum 95 % kaolin - 92 %
Ready-for-use dusts arc obtained by mixing the active ingredient witii the carriers and grinding die mixture in a suitable mill.
8. Extruder granules compound mixture 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %
The active ingredient is mixed and ground witii the adjuvants, and die mixture is subsequently moistened witii water. The mixture is extruded and tiien dried in a stream of air.
9. Coated granules compound mixture 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened witii polyethylene glycol. Non-dusty coated granules are obtained in tiiis manner.
The finely ground active ingredient is intimately mixed with die adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution witii water.
Biological Examples
Example Bl: Safener action on maize:
Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 1.004 by itself and die mixtures of the herbicide widi the safeners are applied to the test plants. The test compounds are applied in die form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B 1 and die rate of application of die safener test compounds is 125 g/ha. 18 days after application die test is evaluated according to a scale of percentages. 100 % denotes that die test plant has died, 0 % denotes no phytoto.dc action. The results in Table Bl show tiiat d e safener test compounds clearly reduce die damage to maize caused by die herbicide. Table Bl:
Safener phytotoxicity to maize in % concentration of herbicide in g/ha
500 250 125 60 30
6.001 6.003 6.004
Example B2: Safener action on maize:
Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 1.004 by itself and die mixtures of the herbicide witii the safeners are applied to die test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B2 and die rate of application of die safener test compounds is 125 g ha. 11 days after application die test is evaluated according to a scale of percentages. 100 % denotes that die test plant has died, 0 % denotes no phytotoxic action. The results in Table B2 show that die safener test compounds clearly reduce the damage to maize caused by the herbicide.
Table B2:
Safener phytotoxicity to maize in % concentration of herbicide in g/ha
250 125
8 . 007 9 . 02
Example B3: Safener action on maize and wheat:
Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the three- leaf stage. At that stage, herbicide No. 1.002 by itself and the mixtures of the herbicide witii the safeners are applied to die test plants. The test compounds are applied in die form of an aqueous suspension in 500 1 of water/ha. The rates of application for the herbicide are given in Table B3 and die rate of application of die safener test compounds is 125 g/ha. 22 days after application die test is evaluated according to a scale of percentages. 100 % denotes that die test plant has died, 0 % denotes no phytotoxic action. The results in Table B3 show that the safener test compounds clearly reduce die damage to maize and wheat caused by die herbicide.
Table B3: phytotoxicity to:
Safener maize wheat in % concentration of herbicide in g ha
80 40 20 80 40 20
5 . 001 5 . 004 8 . 005 9. 02
Example B4: Safener action on maize:
Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 2.001 by itself and die mixtures of die herbicide with die safeners are applied to die test plants. The test compounds are applied in die form of an aqueous suspension in 5001 of water/ha. The rates of application for die herbicide are given in Table B4 and die rate of application of the safener test compounds is 125 g/ha. 18 days after application the test is evaluated according to a scale of percentages. 100 % denotes that die test plant has died, 0 % denotes no phytotoxic action. The results in Table B4 show that die safener test compounds clearly reduce die damage to maize caused by the herbicide. Table B4:
Safener phytotoxicity to maize in % concentration of herbicide in g/ha
250 125 60 30 15
6.001 6.003 6.004
Example B5: Safener action on wheat, barley and rice:
Under greenhouse conditions, in plastics pots, wheat, barley and rice are grown to die two- to three-leaf stage. At that stage, herbicide No.2.003 by itself and d e mixtures of die herbicide witii die safeners are applied to die test plants. The test compounds are applied in die form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are 30 and 60 g ha and die rate of application of die safener test compounds is 60 g/ha. Rice is evaluated according to a scale of percentages 15 days after application, wheat and barley 28 days after application. 100 % denotes tiiat the test plant has died, 0 % denotes no phytotoxic action. The results in Table B5 show that the safener test compounds clearly reduce die damage to wheat, barley and rice caused by die herbicide.
Table B5:
Herbicide concentration 30 g ha:
phytotoxicity to: Safener wheat barley rice in %
85 50 20
5.001 30 20 0
6.001 - - 0
6.002 - 0 6.004 - - 5 7.001 25 15 Herbicide concentration 60 g/ha:
phytotoxicity to:
Safener wheat barley rice in %
98 70 35
5 . 001 70 45 10 6. 001 10 6 . 002 10 6 . 004 5 7 . 001 85 25
Example B6: Safener action on maize and wheat:
Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the tiiree-leaf stage. At that stage, herbicides Nos. 3.001 and 3.002 by diemselves and the mixtures of the herbicide widi the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water ha. The rates of application for the herbicide are given in Table B6 and the rate of application of die safener test compounds is 125 g ha. 22 days after application the test is evaluated according to a scale of percentages. 100 % denotes that die test plant has died, 0 % denotes no phytotoxic action. The results in Table B6 show that the safener test compounds clearly reduce die damage to maize and wheat caused by the herbicide.
Table B6: Herbicide No. 3.001:
phytotoxicity to
Safener wheat in % concentration of herbicide in g/ha
1500 800 400 200
5.001 5.004 8.005 9.02 Herbicide No. 3.002:
phytotoxicity to:
Safener maize wheat in % concentration of herbicide in g ha
1500 800 400 200 1500 800 400 200
5.001 5. 004 8 . 005 9. 02
Example B7: Safener action on maize and wheat:
Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the dirce-leaf stage. At that stage, herbicide No. 1.011 by itself and die mixtures of the herbicide with the safeners arc applied to die test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide arc 30 and 15 g/ha and d e rates of application of die safener test compounds are 60 and 125 g ha. Maize is evaluated according to a scale of percentages 20 days after application and wheat 21 days after application. 100 % denotes that die test plant has died, 0 % denotes no phytotoxic action. The results in Table B7 show tiiat die safener test compounds clearly reduce die damage to maize and wheat caused by die herbicide.
Table B7:
Herbicide concentration 30 g/ha:
phytotoxicity to:
Safener concentration in g/ha maize wheat in %
95 98 45 35 45
35 65 45 55 25 50
Herbicide concentration 15 g ha:
phytotoxicity to:
Safener concentration in g/ha maize wheat in %
80 90 30 15 15
30 40 40 40 20 25

Claims

What is claimed is:
1. A composition for the selective control of weeds in crops of useful plants, which, in addition to inert carriers and additives, comprises as active ingredient a mixture comprising a) a herbicidally effective amount of a pyrimidine of formula I
wherein
X is oxygen or sulfur or, when W is W5, may also be NH, NC(O)H or NC(O)R62; is -COOH, or an organic or inorganic salt of that acid,
or , or the possible salts of these groups;
R is -ORn;
R1 is one of the groups (a), (b) and (c)
R2 is hydrogen, methyl or the group Q"
wherein
Q1 is hydrogen, methyl or, together with Q4, is -(CH2)2-, -(CH2)3-, -CH2CH(OH)CH2- or -CH2SCH2-;
Q2 is hydrogen or methyl;
Q3 is hydrogen, trifluoromethyl, ethynyl, vinyl, phenyl, cyano or C1 -4alkoxycarbonyl, C1 -4alkyl, or C1 -4alkyl substituted by hydroxy, C1 -4alkoxy, mercapto, C1 -4alkylmercapto, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxycarbonyl, C1 -4alkoxycarbonyl, 2-propenyloxycarbonyl, cyano or by carbamoyl; and Q4 is hydrogen, methyl, hydroxymethyl, formyl or cyano;
or R2 together with R7 is -(CH2)p-, -CH2SCH2- or -CH2CHOHCH2-;
R3 is hydrogen, C1 -4alkyl, phenyl, or phenyl mono- or di- substituted by fluorine,
chlorine, bromine, methyl, trifluoromethyl, methoxy or by nitro;
R4 is hydrogen or methyl;
R5 is C1 -4alkyl, C1 -6haloalkyl, phenyl, benzyl, or phenyl substituted by fluorine,
chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro, cyano, carboxy or by C1 -3alkoxy carbonyl ;
R6 is hydrogen, hydroxymethyl, formyl, cyano, hydroxyimino, C1 -4alkoxyimino,
phosphono, phosphino, methylphosphino or a group COX1;
R7 is hydrogen; C1 -4alkyl or C1 -4alkyl substimted by hydroxy, C1 -4alkoxy, mercapto, acylmercapto, C1 -4alkylthio, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl,
3-indolyl, hydroxycarbonyl, C1 -4alkoxycarbonyl, 2-propenyloxycarbonyl, cyano, carbamoyl, methylphosphino or by methylsulfoximino; trifluoromethyl; ethynyl; vinyl or vinyl substituted by chlorine or by methoxy; phenyl or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl or by methoxy; or cyano or C1 -4alkoxycarbonyl;
R8 is hydrogen or methyl;
A is oxygen, sulfur or -NH-;
m is 1, 2 or 3;
n is O, 1, 2 or 3;
p is 2 or 3;
X1 is hydroxy, C1 -4alkoxy, C3-4alkenyloxy, mercapto, C1 -4alkylthio, amino, C1 -4alkyl amino, C1 -4dialkylamino or C1 -4alkoxyamino; or C1 -4alkoxy, C3 -4alkenyloxy, mercapto, C1 -4alkylthio, amino, C1 -4alkylamino, C2 -4dialkylamino or C1 -4alkoxyamino each substituted by phenyl, benzyloxy or by C1 -2alkoxy, or is one of the groups (d), (e) and (f)
wherein
A1 is oxygen, sulfur or -NH-;
R9 is hydrogen, C1 -4alkyl or benzyl;
R10 is hydroxymethyl, cyano or a group COQ';
Q is hydroxy, C1 -4alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d); and
Q' is hydroxy, C1 -4alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);
R1 1 is hydrogen, C1-C10alkyl, C1-C4alkoxy- C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, diC1-C4alkylamino-C1-C4alkyl, halo- C1-C8alkyl, C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C8alkylcarbonyl,
C1-C4alkylcarbonyloxy-C1-C2alkyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, haloC1-C4alkoxy and C1-C6alkoxy; or is furoyl or thienyl; or C1-C4alkyl substituted by phenyl, halophenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C6alkylthiocarbonyl, C3-C8alkenyldιiocarbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, mono-C1-C4alkylaminocarbonyl, di-C1-C4alkylaminocarbonyl, tri-C1-C6alkylsilyl or by
di-C1-C6alkyl-phenylsilyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy or is monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; oxetan-3-yl or dioxan-2-yl that are unsubstituted or substituted by one or two C1-C4alkyl radicals; or C1-C4alkyl that is substituted by cyano, nitro, carboxy or by C1-C6alkylthio-C1-C6alkoxycarbonyl; or the groups -N=C(CH3)2 or -CH2CH2ON=C(CH3)2; W is
or W and Y together form a group W4
or W and Y together form a group W5
or W and Y together form a group W6
E is nitrogen or -CR12;
R12 is hydrogen, halogen, hydroxy, C1-C4alkoxy, phenyl or benzyl; or phenyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or by halogen; benzyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or by halogen; -COR13, -C-R14 ,
N-R15
-S(O)qR16, (4,6-Dimethoxy-pyrimidin-2-yl)-oxy; C1-C4alkyl that is unsubstituted or substituted by halogen; ethenyl that is unsubstinited or substituted by C1-C4alkyl, phenyl, halogen, cyano or C1-C4alkoxycarbonyl; ethynyl that is unsubstituted or substituted by halogen, C1-C4alkyl or phenyl, phenoxy or phenylthio that arc unsubstituted or substimted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or halogen; R13 is C1-C4alkyl, halo- C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl; amino, C1-C4alkylamino, di-C1-C4alkylamino, C2-C4haloalkylamino, di-C2-C4haloalkylamino, C1-C4alkoxyalkylamino, di-C1-C4alkoxyalkylamino, C3-C4alkenylamino, diallylamino,
-N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperidazino, -O-N=C(CH3)-CH3 or -O-CH2-CH2-O-N=C(CH3)-CH3;
R14 is hydrogen, C1-C10alkyl that is unsubstituted or substimted by acyl or by cyano;
C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylsulfonylC1-C4alkyl, C1-C4alkylsulfinyl-C1-C4alkyl, or phenyl that is unsubstituted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and
C1-C4alkoxy;
R15 is hydroxy, C1-C10alkyl that is unsubstimted or substimted by halogen; C1-C6alkoxy that is unsubstimted or substimted by halogen, benzyloxy, C1-C6alkoxycarbonyl, C3-C6Cycloalkyl, acyl, di-C1-C4alkylamino or by C1-C6alkoxy; phenyl, phenoxy or benzyloxy each of which is unsubstimted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C4alkyl, haloC1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy; C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C4alkoxyamino,
C1-C4alkylamino, phenylamino, -OSi(CH3)3, C2-C8alkenyloxy or C3-C8alkynyloxy; q is the number 0, 1 or 2;
R16 is C1-C10alkyl that is unsubstituted or substimted by halogen; phenyl that is
unsubstituted or substimted by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy; C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl or halo- C3-C7cycloalkyl;
R17 is hydrogen, C1 -6alkyl, C3-6cycloalkyl, C1 -6alkyl that is monosubstimted by chlorine or mono- to hexa-substituted by fluorine; phenyl or thienyl, or phenyl mono- or di- substituted by fluorine, chlorine, methyl.or by methoxy;
R18 is hydrogen, methyl or, together with R17, is -(CH2)2-, -(CH2)3-, -(CH2)4- or
-(CH2)5- ;
R19 is hydrogen, methyl, fluorine, chlorine, bromine, C1 -4alkoxy, C3-6alkenyloxy,
C3-6alkynyloxy, C3-4cycloalkyl-C1-2alkoxy, C4-6cycloalkoxy, or C1 -4alkoxy that is monosubstituted by cyano, C1 -4alkoxy or by chlorine or is mono- to hexa-substituted by fluorine; C1 -6alkylthio or cyano;
R20 is hydrogen, C1 -4alkyl, C1-3alkylthio or, together with R21, is -(CH2)4-, -(CH2)5-, -S(CH2)2S- or -S(CH2)3S- ;
R21 is C1 -6alkyl, C2-6alkenyl, C3-6cycloalkyl, C1 -6haloalkyl, C1 -3alkoxy, C1 -4alkylthio, formyl, C1 -5alkylcarbonyl, carboxy, C1 -4alkoxycarbonyl, phenyl, or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or by nitro, or is 2-, 3- or 4-pyridyl, 2- or 3-furyl or 2- or 3-ttienyl; R22 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl, C1-C6haloalkyl, C3-C6alkenyl,
C3-C6alkynyl, C3-C6haloalkenyl, C3-C6haloalkynyl, phenyl or benzyl, or phenyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or by halogen; benzyl substimted by C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or by halogen; halogen, hydroxy, -CHO, -COOH, phenoxy, cyano, phenylthio, -CONH2, -OCHO,
C2-C5alkanoyloxy, C2-C5alkoxycarbonyloxy, C2-C3alkylcarbamoyloxy,
di(C1-C2alkyl)carbamoyloxy or di(C1-C2alkoxy)phosphonyl;
R23 is hydrogen, C1-C6alkyl or CF3;
r is 0, 1, 2 or 3;
s is 0, 1, 2 or 3;
m is 0, 1 or 2;
R57 is hydrogen, hydroxy, C1-C6alkoxy, C1-C6alkoxyalkoxy, C1-C6acyloxyalkoxy, trimethylsilyledioxy, C1-C6alkylsulfonylamino, C1-C6alkylthio, imidazolyl, benzyloxy, phenoxy or diiophenoxy, or benzyloxy, phenoxy or diiophenoxy;
R58 is halogen, C1-C6haloalkyl, C1-C6alkyl, acylamino, C3-C6cycloalkyl, halosubstimted C3-C6cycloalkyl, C2-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkoxycarbonyl, C1-C6alkoxy, Cj-Qalkylamino, di-C1-C6alkylamino, C1-C6alkoxyiminoalkyl, acyl, C1-C6alkylthio, phenyl, benzyl, phenylamino or benzylamino;
R59 is halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6alkylamino, di-C1-C6alkylamino,
C1-C6haloalkyl, C1-C6haloalkoxy, nitro, hydroxy, cyano, C1-C6alkoxyalkoxy, C1-C6alkoxycaτbonylalkoxy, C1-C6alkylthioalkoxy, C1-C6alkylthio, C1-C6alkoxyalkyl, C2-C6alkenyl, C3-C6alkynyl, benzyloxy or phenoxy;
R60 is halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, halo-substituted
C3-C6cycloalkyl, C2-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkoxycarbonyl, C1-C6alkoxy, C1-C6alkylamino, di-C1-C6alkylamino, phenyl, benzyl, C1-C6alkoxyiminoalkyl, acyl, C1-C6alkylthio, phenylamino or benzylamino;
R61 is hydrogen, hydroxy, C1-C6alkoxy, C1-C6alkoxyalkoxy, C1-C6acyloxyalkoxy, trimethylsilyledioxy, C1-C6alkylsulfonylamino, C1-C6alkylthio, imidazolyl, benzyloxy, phenoxy or diiophenoxy, or benzyloxy, phenoxy or thiophenoxy;
R62 is C1-C6alkyl or C1-C6alkoxy;
R66 is C1-C6alkyl, or C1-C6alkyl which is substimted by up to 3 fluorine atoms, 1
chlorine atom, 1 C1-C4a&oxy group, 1 C1-C4alkoxycarbonyl group, 1
dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ediynyl group or 1 phenyl group which is unsubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or NR67R68; or OR69;
R67 is hydrogen or C1-C4alkyl;
R68 is hydrogen, C1-C6alkyl, phenyl, pyridyl, or phenyl which is monosubstimted to trisubstituted or pyridyl which is monosubstituted by C1-C4alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is C1-C6alkylcarbonyl, trifluoromethylcarbonyl, C3-C6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or diiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, medioxy or nitro; or C1-C4alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminodiiocarbonyl, or aminocarbonyl or aminodiiocarbonyl each of which is monosubstimted to disubstituted by phenyl or C1-C4alkyl, it being possible for the phenyl group to be substimted by fluorine, chlorine, methyl or methoxy; and
R69 is hydrogen, C1-C6alkyl or C2-C6alkenyl, or C2-C6alkenyl which is substimted by halogen or phenyl, or C1-C4alkoxycarbonyl-C1-C4alkyl or C1-C4alkylthiocarbonyl- C1-C4alkyl; and b) as safener, a herbicide-antagonistically effective amount of a quinoline derivative of formula IIa
wherein
R24 is hydrogen or C1-C6alkyl and
X2 is hydrogen or chlorine;
or of an N-acylsulfamoylphenylurea of formula IIb wherein
A2 is a group
R25 and R26, independently of one another, are hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, , or C1-C4alkyl substituted by
C1-C4alkoxy or by
or R1 and R2 together form a C4-C6alkylene bridge that can be interrupted by oxygen, sulfur, SO, SO2, NH or by -N(C1-C4alkyl)-;
R27 is hydrogen or C1-C4alkyl;
Ra is hydrogen, halogen, cyano, trifluoromethyl, nitro, C1-C4alkyl, C1-C4alkoxy,
C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm,
-CORn, -SO2NRkRm or -OSO2-C1-C4alkyl;
Rg is hydrogen, halogen, cyano, nitro, C1-C6alkyl, C1-C4haloalkyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm,
-OSO2-C1-C4alkyl, C1-C6alkoxy, or C1-C6alkoxy substimted by C1-C4alkoxy or by halogen; C3-C6alkenyloxy, or C3-C6alkenyloxy substimted by halogen; or
C3-C6alkynyloxy; or Ra and Rb together form a C3-C4alkylene bridge that can be substituted by halogen or by C1-C6alkyl, or a C3-C4alkenylene bridge that can be substimted by halogen or by C1-C4alkyl, or a C4alkadienylene bridge that can be substimted by halogen or by C1-C6alkyl;
Rb and Rh, independendy of one another, are hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C6alkoxy, C1-C6alkylthio or -COORj-,
Rc is hydrogen, halogen, nitro, C1-C4alkyl or methoxy;
Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj or CONRkRm;
Re is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy;
or Rd and Re together form a C3-C4alkylene bridge;
Rf is hydrogen, halogen or C1-C4alkyl;
Rx and Ry, independendy of one another, are hydrogen, halogen, C1-C4alkyl,
C1-C4alkoxy, C1-C4alkylthio, -COOR28, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm, independently of one another, are hydrogen or C1-C4alkyl; or
Rk and Rm together form a C4-C6alkylene bridge that can be interrupted by oxygen, NH or by -N(C1-C4alkyl)-;
Rn is C1-C4alkyl, phenyl, or phenyl substimted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl;
R28 is hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, diC1-C4alkylamino-C1-C4alkyl, halo-C1-C8alkyl, C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C8alkylcarbonyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl that is unsubstimted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy; or is furoyl or thienyl; or C1-C4alkyl substimted by phenyl, halophenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C6alkylthiocarbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynyldιiocarbonyl, carbamoyl, mono-C1-C4alkylaminocarbonyl or by di-C1-C4alkylaminocarbonyl; or phenylaminocarbonyl that is unsubstituted or substimted at the phenyl by up to three identical or different substituents selected from halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy or monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; or dioxan-2-yl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; or C1-C4alkyl substituted by cyano, nitro, carboxy or by C1-C8alkylthio-C1-C8alkoxycarbonyl;
or of a 1-phenylazole-3-carboxylic acid derivative of formula IIc
wherein
E2 is nitrogen or methine;
R29 is -CCl3, phenyl or halo-substituted phenyl;
R30 and R31, independendy of one another, are hydrogen or halogen; and
R32 is C1-C4alkyl;
or of a chloroacetamide of formula IId
wherein
R33 and R34, independendy of one another, are C1-C6alkyl or C1-C6alkenyl;
or R33 and R34 together are ; wherein
R35 and R36, independently of one another, are hydrogen or C1-C6alkyl; or R33 and R34 together are ; wherein
R37 and R38, independendy of one another, are C1-C4alkyl;
or R37 and R38 together are -(CH2)5-;
R39 is hydrogen, C1-C4alkyl or
»
or R33 and R34 together are wherein
R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54 and R55, independendy of one another, are hydrogen or C1-C4alkyl;
or of an oxime of formula IIh
wherein
R63 is hydrogen or chlorine and
R66 is cyano or trifluoromethyl;
or of a phenylpyrimidine of formula IIi
wherein
R65 is hydrogen or methyl.
2. A composition according to claim 1, wherein W is W1, W2, W3 or W4.
3. A composition according to claim 1, wherein W is W1.
4. A composition according to claim 3, wherein Y is -COOH, or an organic or inorganic salt of that acid, , or
5. A composition according to claim 4, wherein R12 is hydrogen, halogen -OCH3 or -COR13.
6. A composition according to claim 5, wherein R13 is C1-C4alkyl.
7. A composition according to claim 3, wherein E is nitrogen.
8. A composition according to claim 3, wherein Y is -COOH, or an organic or inorganic salt of that acid.
9. A composition according to any one of claims 1 to 8, wherein there is used as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula IIg
10. A composition according to any one of claims 1 to 8, wherein there is used a safener of formula IIb wherein R25 is C1-C4alkyl, R26 is hydrogen or C1-C4alkyl, R27 is hydrogen
and A2 is a group or
11. A composition according to claim 10, wherein R25 is methyl, Rg is hydrogen, methyl or medioxy, Rh is methyl or methoxy and Rd, Re and Rf are hydrogen.
12. A composition according to any one of claims 1 to 8, wherein there is used a safener of formula IIc wherein R29 is phenyl or halo-substituted phenyl, R30 is 2-Cl, R32 is methyl and E2 is methine.
13. A composition according to any one of claims 1 to 8, wherein there is used a safener of
formula IId wherein R33 and R34 are allyl, or R33 and R34 together are
or R33 and R34 together are ; wherein either R37 and R38 are each methyl and R39 is ; or R37, R38 and R39 are each methyl; or R39 is hydrogen; or R37
and R38 together arc -(CH2)5- ; or R33 and R34 together are ;
wherein R53, R54 and R55 are preferably methyl and R49, R50, R51 and R52 are preferably hydrogen.
14. A composition according to claim 1, wherein there are used as herbicide a compound of formula If
wherein
Y is -COOCH3 and R12 is hydrogen; or
Y is -COOCH3 and R12 is methylcarbonyl; or
Y is -COOCH3 and R12 is ethylcarbonyl; or
Y is -COOH and R12 is hydrogen; or
Y is -COOH and R12 is fluorine; or
Y is -COOH and R12 is methoxy; or
Y is 2-chlorophenylhydrazinoyl and R12 is methoxy; or
Y is 2-fluorophenylhydrazinoyl and R12 is methoxy; or
Y is o-tolylhydrazinoyl and R12 is methoxy; or
Y is -NHNHC(CH3)3 and R12 is hydrogen; or
Y is 2-phenylhydrazinoyl and R12 is hydrogen; or Y is 2-fluorophenylhydrazinoyl and R12 is hydrogen; or
Y is 2-trifluoromedιylphenylhydrazinoyl and R12 is hydrogen; or
Y is o-tolylhydrazinoyl and R12 is hydrogen; or
Y is 4-chlorophenylhydrazinoyl and R12 is hydrogen;
Y is and R12 is hydrogen; or
Y is and R12 is hydrogen; or
Y and R12 together are ; or
Y and R12 together are ; or
Y and R12 together are ; or
Y and R12 together are ; or
Y and R12 together are ; or
a compound of formula Ig
and as safener a herbicide-antagonistically effective amount of a compound of formula IIe
wherein A2 is the group and R26 is hydrogen;
or of a compound of formula IIe
wherein A2 is the group and R26 is hydrogen;
or of a compound of formula IIe wherein A2 is the group and R26 is methyl;
or of a compound of formula IIe
wherein A2 is the group and R26 is methyl.
15. A composition according to claim 1, wherein there are used as herbicide a compound of formula If according to claim 14, wherein
Y is -COOCH3 and R12 is hydrogen; or
Y is -COOCH3 and R12 is ethylcarbonyl; or
Y is -COOH and R12 is hydrogen; or
Y and R12 together are ; or
Y and R12 together are
or a compound of formula Ig
and as safener a herbicide-antagonistically effective amount of a compound of formula IIe
wherein A2 is the group and R26 is hydrogen;
or of a compound of formula IIe
wherein A2 is the group and R26 is hydrogen;
or of a compound of formula IIe
wherein A2 is the group and R26 is methyl;
or of a compound of formula IIe wherein A2 is the group and R26 is methyl.
16. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the crops, the seeds thereof or the cultivated area thereof with an effective amount of a herbicide of formula I according to claim 1 and a herbicide-antagonistically effective amount of a safener of formula IIa, IIb, IIc, IId, IIh or IIi according to claim 1, simultaneously or independently of one another.
17. A method according to claim 16, which comprises treating crop plants or cultivated areas intended for crop plants with 0.05 to 2 kg/ha of a compound of formula I according to claim 1 and an amount of 0.01 to 0.5 kg/ha of a compound of formula IIa, IIb, IIc, IId, IIh or IIi according to claim 1.
18. A method according to claim 16 for the selective control of weeds and grasses in maize and cereal crops.
EP93915750A 1992-07-08 1993-06-30 Selective herbicidal composition Withdrawn EP0671880A1 (en)

Applications Claiming Priority (7)

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CH2148/92 1992-07-08
CH214892 1992-07-08
CH300792 1992-09-25
CH3007/92 1992-09-25
CH423/93 1993-02-11
CH42393 1993-02-11
PCT/EP1993/001683 WO1994000987A2 (en) 1992-07-08 1993-06-30 Selective herbicidal composition

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