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EP1222178A1 - Alkyl-amino-1,3,5-triazines et leur utilisation comme herbicides - Google Patents

Alkyl-amino-1,3,5-triazines et leur utilisation comme herbicides

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Publication number
EP1222178A1
EP1222178A1 EP00962536A EP00962536A EP1222178A1 EP 1222178 A1 EP1222178 A1 EP 1222178A1 EP 00962536 A EP00962536 A EP 00962536A EP 00962536 A EP00962536 A EP 00962536A EP 1222178 A1 EP1222178 A1 EP 1222178A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
radicals
group
substituted
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Withdrawn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
EP00962536A
Other languages
German (de)
English (en)
Inventor
Hartmut Ahrens
Lothar Willms
Klemens Minn
Jürgen Zindel
Jens Hollander
Wolfgang Giencke
Klaus Lorenz
Hermann Bieringer
Thomas Auler
Felix Thürwächter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Aventis CropScience GmbH
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Filing date
Publication date
Application filed by Aventis CropScience GmbH filed Critical Aventis CropScience GmbH
Publication of EP1222178A1 publication Critical patent/EP1222178A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms

Definitions

  • Alkyl-amino-1, 3,5-triazines process for their preparation and use as herbicides and plant growth regulators
  • the invention relates to the technical field of crop protection agents, such as herbicides and plant growth regulators, in particular herbicides for the selective control of harmful plants in crops of useful plants.
  • crop protection agents such as herbicides and plant growth regulators, in particular herbicides for the selective control of harmful plants in crops of useful plants.
  • the known active compounds sometimes have disadvantages when used, be it inadequate herbicidal activity against harmful plants, too little spectrum of the harmful plants which can be combated with an active compound, or insufficient selectivity in crops of useful plants.
  • Other active ingredients cannot be produced economically on an industrial scale because of the difficult to access precursors and reagents, or they have insufficient chemical stability.
  • the present invention relates to compounds of the formula (I) and their salts, wherein
  • A is a group of the formula NR a R, wherein
  • R a and R b independently of one another are hydrogen, formyl or else
  • R 1 is hydroxy or
  • (-C-C- ⁇ o) alkyl which is unsubstituted or by one or more radicals from the group halogen, hydroxy, cyano, nitro, thiocyanato, formyl, also amino, (CC 4 ) alkoxy, (CrC 4 ) haloalkoxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 ) haloalkenyloxy, (C 2 -C 4 ) alkynyloxy, (C 2 -C 4 ) haloalkynyloxy, also N-mono (CrC 4 ) alkylamino, also N, N-Di ( CC 4 ) alkylamino, (CC 4 ) alkylthio, (C 1 -C) alkylsulfinyl, (d- C 4 ) haloalkylsulfinyl, (dd.alkylsulfonyl, (CrC 4
  • R c and R d together straight-chain (C 2 -C 5 ) alkylene, which is unsubstituted or by one or more radicals from the group (d-dJalkyl, (C ⁇ -C 4 ) alkoxy, (C ⁇ -C 4 ) alkoxy- (C ⁇ -C 4 ) alkyl and oxo is substituted, are halogen, CN, NO 2 , SCN or a radical of the formula -X 1 -A 1 , where
  • X 1 is a direct bond or a divalent group of the formula -O-, -S (O) p -, -S (O) p -O-, -O -S (O) p -, -CO-, -O- CO-, -CO-O-, -S-CO-, -CO-S-, -S-CS-, -CS-S-, -O-CO-O-, -NR ° -, -O-NR ° -, -NR ° -O-, -NR ° -CO-, -CO-NR 0 -, -O-CO-NR ° - or -NR ° -CO-O-, where each p is the integer 0 , 1 or 2 and R ° is hydrogen, (d- C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, phenyl,
  • C ⁇ .Cycloalkyl (C 5 -C 6 ) cycloalkenyl, phenyl or heterocyclyl with 3 to 9 ring atoms and 1 to 4 hetero ring atoms from the group N, O and S, each of the 7 latter radicals being unsubstituted or substituted, preferably unsubstituted or by one or more radicals from the group halogen, cyano, hydroxy, (d-dJalkyl, (C 3 -C 6 ) cycloalkyl, (CC 4 ) alkoxy, (dC 4 ) haloalkoxy and (C ⁇ -C 4 ) hydroxyalkoxy and in the case of cyclic Radicals are also substituted (ie haloalkyl, (CrC 4 ) alkoxy- (C 1 -C 4 ) alkyl and (CC 4 ) hydroxyalkyl, and preferably have up to 20 C atoms including substituents, means each of the radicals R 4
  • X 2 is a direct bond or a divalent group of the formula -O-,
  • alkyl (d-CeJHaloalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (CC 6 ) alkoxy, (d-C 6 ) haloalkoxy, [(dC 6 ) alkyl] carbonyl, [(i.e. -CeJAlkoxyj-carbonyl, (d- C 6 ) alkylsulfonyl and (-C-C 6 ) alkylsulfinyl is substituted,
  • R 5 CH 3 or OCH 3 , R 6 CH 3 or OCH 3 and R 4 , R 7 and R 8 each represent H.
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • Such compounds of the formula (I) contain one or more asymmetrically substituted carbon atoms or else double bonds which are not indicated separately in the general formulas (I).
  • the possible stereoisomers defined by their specific spatial shape, such as enantiomers, diastereomers, including Z and E isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or can also be produced by stereoselective reactions in combination with the use of stereochemically pure or enriched starting materials.
  • stereoisomers which are formed by the asymmetrically substituted carbon atom to which the group R 3 is attached if R 3 is not hydrogen.
  • the isomers R- and S-configured at this center which are enantiomers when no further asymmetrically substituted C atom is contained in the molecule of the formula (I), are thus also a subject of the invention.
  • these R and S isomers have no identical biological effects, but one of the isomers has the higher herbicidal activity or selectivity in individual cases, depending on the harmful plant species and culture.
  • the compounds of the formula (I) can form salts by addition of a suitable inorganic or organic acid, for example HCl, HBr, H 2 SO 4 or HNO 3 , but also oxalic acid or sulfonic acids to a basic group, such as amino or alkylamino.
  • Suitable substituents which are present in deprotonated form such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups which can be protonated, such as amino groups.
  • Salts can also be formed in that, in the case of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, the hydrogen is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines.
  • the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkyithio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched. Unless specifically stated, these residues are the lower carbon skeletons, for example with 1 to 6 C atoms or, in the case of unsaturated groups, with 2 to 6 C atoms, are preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2
  • Cycloalkyl means a carbocyclic, saturated ring system with preferably 3-8 C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • substituents with a double bond on the cycloalkyl radical e.g. B. an alkylidene yeast such as methylidene, are included.
  • multi-cyclic aliphatic systems are also included, such as, for example, bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentan-1-yl, Bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, adamantan-1-yl and adamantan-2-yl.
  • Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system with preferably 4-8 C atoms, for example 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1, 3-cyclohexadienyl or 1, 4-cyclohexadienyl.
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; The same applies to haloalkenyl and other halogen-substituted radicals.
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; unless otherwise defined, it preferably contains one or more, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group N, O, and S; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms.
  • the heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms.
  • heteroaromatic ring with a heteroatom from the group N, O and S for example pyridyl, pyrrolyl, thienyl or furyl; furthermore it is preferably a corresponding heteroaromatic ring with 2 or 3 heteroatoms, e.g. B. pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl and triazolyl.
  • Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo.
  • the oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
  • Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents for example one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino , and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also al
  • cyclic systems are also included with those substituents which are bonded to the ring with a double bond, for. B. are substituted with an alkylidene group such as methylidene or ethylidene.
  • alkylidene group such as methylidene or ethylidene.
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • Substituents from the group halogen e.g.
  • Fluorine and chlorine (d-dJ alkyl, preferably methyl or ethyl, (CrC) haloalkyl, preferably trifluoromethyl, (d-d J alkoxy, preferably methoxy or ethoxy, (i.e. haloalkoxy, nitro and cyano.
  • the substituents methyl, methoxy are particularly preferred , Fluorine and chlorine.
  • Substituted amino such as mono- or disubstituted amino means a radical from the group of substituted amino radicals, which are, for example, by one or two identical or different radicals from the group alkyl, alkoxy, acyl and aryl Are N-substituted; preferably mono- and dialkylamino, mono- and diarylamino, acylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and N-heterocycles; alkyl radicals having 1 to 4 carbon atoms are preferred;
  • Aryl is preferably phenyl or substituted phenyl; the definition given below applies to acyl, preferably (dC) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (dC) alkyl, (C ⁇ -C) alkoxy, (C ⁇ -C 4 ) haloalkyl, ( C ⁇ -d) haloalkoxy and nitro is substituted, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2.4 -, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
  • Acyl means a residue of an organic acid which is formally formed by removing a hydroxyl group on the acid function, the organic residue in the acid also being able to be linked to the acid function via a hetero atom.
  • Examples of acyl are the residue -CO-R of a carboxylic acid HO-CO-R and residues of acids derived therefrom such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the rest of carbonic acid monoesters, N-substituted carbamic acid, sulfonic acids, sulfinic acids, N-substituted sulfonamic acids , Phosphonic acids, phosphinic acids.
  • Acyl means, for example, formyl, alkylcarbonyl such as [(Ci-dJAlkylj-carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of organic acids.
  • alkylcarbonyl such as [(Ci-dJAlkylj-carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of organic acids.
  • the residues can each be in the alkyl or Phenyl part can be further substituted, for example in the alkyl part by one or more radicals from the group halogen, alkoxy, phenyl and phenoxy; examples of substituents in the phenyl part are the substituents mentioned generally above for substituted phenyl.
  • Acyl preferably means an acyl radical in the narrower sense, ie a radical of an organic acid in which the acid group is directly connected to the carbon atom of an organic radical, for example formyl, alkylcarbonyl such as acetyl or [(CrC4) alkyl] carbonyl, phenylcarbonyl, alkylsulfonyl, alkylsulfinyl and other residues of organic acids.
  • A is a group of the formula NR a R b , wherein
  • R a and R b independently of one another are hydrogen, formyl or else
  • A represents a group of the formula NR a R b , wherein
  • R a is hydrogen or (CC 4 ) alkyl
  • R is hydrogen or formyl, or aminocarbonyl or
  • (dd) alkoxy is substituted, preferably H, CHO, CO-CH 3 , CO-C 6 H 5 , SO 2 CH 3 or SO 2 C2H5, or
  • R a and R b together (Ci-dJ alkylidene which is unsubstituted or substituted by one or more radicals from the group halogen, cyano, (-C-C 2 ) alkoxy, (CrC 2 ) haloalkoxy and (C ⁇ -C 2 ) alkylthio, mean or
  • NR a R b together form a saturated heterocyclyl radical with 5 or 6 ring atoms, which in addition to the N atom as a hetero ring atom may have 1 to 3 more
  • compounds of the invention are also of interest Formula (I) or its salts, in which
  • R 1 (-C-C6.Alkyl, which is unsubstituted or by one or more radicals from the group halogen, hydroxy, cyano, nitro, thiocyanato, formyl or also amino, (d-dJalkoxy, (dd.haloalkoxy or also N-mono ( d- C) alkylamino or also N, N-di (dC 4 ) alkylamino or (Ci-dJalkylthio, (Cr C 4 ) alkylsulfonyl, (dC 4 ) haloalkylsulfonyl, [(dC 4 ) alkyl] carbonyl, [(CrC 4 ) Haloalkyl] carbonyl, [(CC 4 ) alkoxy] carbonyl, (C 3 -C 9 ) cycloalkyl, phenyl and heterocyclyl, where each of the latter 3 radicals is unsubstituted or substituted
  • (C 3 -C 6 ) cycloalkyl which is unsubstituted or substituted, preferably unsubstituted or by one or more radicals from the group halogen, (CC 4 ) alkyl, (dC 4 ) haloalkyl, (dC 4 ) alkoxy, (CC 4 ) Haloalkoxy and (dC 4 ) alkylthio is substituted.
  • R 1 (dC) alkyl such as. B. like methyl, ethyl, n-propyl and i-propyl, or (-C-C 4 ) haloalkyl, such as. B. 1-fluoroisopropyl, 1-fluoro-ethyl, 1-fluoropropyl, CF 3 and CCI 3 , or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methyl-cyclopropyl, 1-methyl-cyclobutyl, 1-methyl-cyclopentyl , 1-methyl-cyclohexyl or benzyl.
  • R 1 (dC) alkyl such as. B. like methyl, ethyl, n-propyl and i-propyl, or (-C-C 4 ) haloalkyl, such as. B. 1-fluoroisopropyl, 1-fluoro-ethyl, 1-fluoropropy
  • Preferred compounds of the formula (I) or their salts according to the invention are those in which R 2 is hydrogen, formyl, (dC 4 ) alkyl, (dC 4 ) haloalkyl, (Ci-d.alkylsulfonyl, (CC 4 ) haloalkylsulfonyl, (CrC 4 ) Alkoxy, (dd.Haloalkoxy, [(dC 4 ) alkyl] carbonyl, [(dd.Haloalkyljcarbonyl, [(C ⁇ -d) alkoxy] carbonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, phenylcarbonyl or phenylsulfonyl.
  • X 1 is a direct bond or a divalent group of the formula -O-, -S (0) p -, -S (O) p -O-, -O -S (O) p -, -CO-, -O- CO-, -CO-O-, -S-CO-, -CO-S-, -S-CS-, -CS-S-, -O-CO-O-, -NR ° -, -O-NR 0 -, -NR ° -O-, -NR ° -CO-, -CO-NR 0 -, -O-CO-NR ° - or -NR ° -CO-O-, preferably -O-, -S ( O) p -, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NR ° -, -O-NR °
  • Preferred compounds (I) and their salts are those in which R 3 is H, (-CC) alkyl, preferably methyl or ethyl, or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl, each of the 8 last-mentioned radicals being unsubstituted or by one or more radicals from the group comprising halogen and (CrC 2) alkoxy and in the case of cyclic radicals, also (C ⁇ -C 2) alkyl, (CrC 2) is substituted HaloaIkyl and (C ⁇ -C 4) alkoxy (C -C 4) alkyl, means.
  • each of the radicals R 4 , R 5 , R 6 , R 7 and R 8 independently of one another is halogen, nitro, cyano, thiocyanato or a radical of the formula - X 2 -A 2 , where X 2 is a direct bond or a divalent group of the formula -O-,
  • radicals preferably 2 or 3 radicals, in particular 2 radicals from the group R 4 , R 5 , R 6 , R 7 and R 8, are different from hydrogen.
  • each of the radicals R 4 , R 5 , R 6 , R 7 and R 8 independently of one another is hydrogen, halogen, hydroxyl, amino, nitro, formyl, aminocarbonyl, Carboxy, cyano, Thiocyanato or aminosulfonyl or (C-
  • each of the radicals R 4 , R 5 , R 6 , R 7 and R 8 is, independently of one another, hydrogen, halogen, hydroxy, amino, nitro, formyl, carboxy, cyano, (CiC- ⁇ Jalkyl, Halo- (C ⁇ -C4) alkyl, halo- (C-
  • Each of the radicals R 4 , R 5 , R 6 , R 7 and R 8 is more preferably, independently of one another, hydrogen, hydroxy, amino, nitro, formyl, carboxy, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, n -Propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, CF 3 , CHF 2 , CH 2 F, CCI 3 , OCHF 2 , OCF 3 , OCH 2 F, CH 2 NH 2 , CH 2 CH 2 NH 2> CH 2 OH, CH 2 CH 2 OH, CH 2 SH, CH CH 2 SH, OCH 2 CH 2 OH, OCH (CH 3 ) OH, CH 2 OCH 3> CH2OC2H5, CH 2 CH 2 OCH 3 , CH2CH
  • R 1 is (-C-C ⁇ o) alkyl which is unsubstituted or substituted by other substituents according to the invention as halogen.
  • R 5 , R 6 , R 7 and R 8 are each defined differently than (Cr C ⁇ o) alkyl or (C ⁇ -C ⁇ o) alkoxy.
  • R 3 is defined differently from methyl, ie, for example (C 2 -C ⁇ 0 ) alkyl which is unsubstituted or (d-C ⁇ o) alkyl which is substituted or one of the other definitions according to the invention for R 3 .
  • the present invention also relates to processes for the preparation of the compounds of the general formula (I) or their salts, characterized in that a) a compound of the formula (II),
  • Fu is a functional group from the group of carboxylic acid esters, carboxylic acid orthoesters, carboxylic acid chloride, carboxylic acid amide, carboxylic acid anhydride and trichloromethyl, with a biguanidide of the formula (III) or an acid addition salt thereof
  • Z 1 is an exchangeable radical or a leaving group, for example chlorine, trichloromethyl, (-C-C 4 ) alkylsulfonyl and unsubstituted or substituted phenyl- (-C-C 4 ) alkylsulfonyl or (dC 4 ) alkyl-phenylsulfonyl, with a suitable amine of formula (V) or an acid addition salt thereof
  • the reaction of the compounds of the formulas (II) and (III) is preferably base-catalyzed in an inert organic solvent, such as e.g. Tetrahydrofuran (THF), dioxane, acetonitrile, dimethylformamide (DMF), methanol and ethanol, at temperatures between -10 ° C and the boiling point of the solvent, preferably at 20 ° C to 60 ° C; if acid addition salts of the formula (III) are used, these are generally released in situ with the aid of a base.
  • an inert organic solvent such as e.g. Tetrahydrofuran (THF), dioxane, acetonitrile, dimethylformamide (DMF), methanol and ethanol
  • Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicylco [5.4.0] undec-7-ene (DBU).
  • the respective base is used, for example, in the range from 0.1 to 3 molar equivalents based on the compound of the formula (III).
  • the compound of formula (II) can be used in relation to the compound of formula (III), for example in equimolar amounts or with an excess of up to 2 molar equivalents.
  • the reaction of the compounds of the formula (IV) and (V) is preferably carried out in a base-catalyzed manner in an inert organic solvent, such as, for example, THF, dioxane, acetonitrile, DMF, methanol and ethanol, at temperatures between -10 ° C. and the boiling point of the particular solvent or Solvent mixture, preferably at 20 ° C to 160 ° C, in particular 30 ° C to 80 ° C, the Compound (V), if used as the acid addition salt, is optionally released in situ with a base.
  • an inert organic solvent such as, for example, THF, dioxane, acetonitrile, DMF, methanol and ethanol
  • Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicylco [5.4.0] undec-7-ene (DBU).
  • the respective base is generally used in the range from 1 to 3 molar equivalents, based on the compound of the formula (IV), the compound of the formula (IV) can, for example, be equimolar to the compound of the formula (V) or with up to 2 molar equivalents of excess be used.
  • the starting materials of the formulas (II), (III), (IV) and (V) are either commercially available or can be prepared by or analogously to processes known from the literature. Some of the compounds of formula (III) are new and also a subject of the invention. The compounds can also be produced, for example, by one of the processes described below.
  • the compound of formula (IV), or a direct precursor thereof, can be prepared, for example, as follows:
  • R 1 is as defined in formula (I) with an N-cyanodithioiminocarbonate of the formula (VIII),
  • NC-N C (SZ 3 ) 2 (VIII)
  • R 1 is as defined in formula (I), compounds of formula (X),
  • the substituted phenylalkylamines of the formula (V) required as starting materials are known and / or can be prepared by processes known per se.
  • the corresponding aromatic ketone can be reductively aminated directly to the amine, for example by means of a reaction with sodium cyanoborohydride and ammonium acetate or with a mixture of ammonium formate and formic acid with subsequent amide cleavage, or the ketone is converted into an advantageous derivative, for example an oxime, which is then reduced to the amine (cf. JP 11035536; JP 11043470; J. Am. Chem. Soc. 1983, 105, 1578; Synthesis 1980, 695).
  • the reaction of the carboxylic acid derivatives of the formula (II) with the amidinothiourea derivatives of the formula (VI) is preferably carried out under base catalysis in an organic solvent, such as e.g. Acetone, THF, dioxane, acetonitrile, DMF, methanol, ethanol, at temperatures from -10 ° C to the boiling point of the solvent, preferably at 0 ° C to 20 ° C.
  • the reaction can also be carried out in water or in aqueous solvent mixtures with one or more of the above-mentioned organic solvents. If (VI) is used as the acid addition salt, it can optionally be released in situ with a base.
  • Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicylco [5.4.0] undec-7-ene (DBU).
  • the respective base is e.g. used in the range of 1 to 3 molar equivalents based on the compound of formula (VI).
  • Compounds of the formula (II) and (VI) can be used, for example, in equimolar amounts or with up to 2 molar equivalents of excess of the compound of the formula (II).
  • the corresponding processes are known from the literature (see: H. Eilingsfeld, H. Scheuermann, Chem. Ber .; 1967, 100, 1874), the corresponding intermediates of formula (IV) are new.
  • the reaction of the amidines of the formula (VII) with the N-cyanodithioiminocarbonates of the formula (VIII) is preferably base-catalyzed in an inert organic solvent, such as, for example, acetonitrile, DMF, dimethylacetamide (DMA), N-methylpyrrolidone (NMP), methanol and ethanol, at temperatures from -10 ° C to the boiling point of the solvent, preferably at 20 ° C to 80 ° C. If (VII) is used as the acid addition salt, it can optionally be used in situ with a Base to be released.
  • an inert organic solvent such as, for example, acetonitrile, DMF, dimethylacetamide (DMA), N-methylpyrrolidone (NMP), methanol and ethanol
  • Suitable bases or basic catalysts are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal carbonates or organic bases such as triethylamine or 1,8-diazabicylco [5.4.0] undec-7-ene (DBU).
  • the respective base is z. B. in the range of 1 to 3 molar equivalents based on the compound of formula (VIII), compounds of formula (VII) and (VIII) can generally be used in equimolar amounts or with 2 molar equivalents of excess compound of formula (II).
  • the corresponding processes are known from the literature (cf. TA Riley, WJ Henney, NK Dalley, BE Wilson, RK Robins; J. Heterocyclic Chem .; 1986, 23 (6), 1706-1714), the corresponding intermediates of the formula (IV ) are new.
  • the reaction components are, for example, acid-catalyzed in an inert organic solvent such as toluene, chlorobenzene, chlorinated hydrocarbons at temperatures between -10 ° C and the boiling point of the solvent, preferably at 20 ° C to 80 ° C, with the intermediates formed in situ with a suitable chlorination reagent such as phosphorus oxychloride.
  • Suitable acids are, for example, hydrohalic acids, such as HCl, or Lewis acids, such as, for example, AICI 3 or BF 3 (cf. US-A-5095113, DuPont).
  • the reaction components are, for example, acid-catalyzed in an inert organic solvent such as toluene, chlorobenzene, chlorinated hydrocarbons at temperatures between -40 ° C and the boiling point of the solvent, preferably at -10 ° C to 30 ° C.
  • Suitable acids are, for example, hydrohalic acids such as HCl or Lewis acids such as AICI 3 or BF 3 (cf. EP-A-130939, Ciba Geigy).
  • hydrohalic acids such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid Salicylic acid, sorbic acid or lactic acid, and sulfonic acids such as p-toluenesulfonic acid or 1, 5-naphthalene disulfonic acid.
  • hydrohalic acids such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids
  • acetic acid maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid Salicylic acid, sorbic acid or lactic acid
  • sulfonic acids such as p-toluenesulfonic acid or 1, 5-naphthalen
  • the acid addition compounds of the formula (I) can be prepared in a simple manner by the customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable organic solvent such as methanol, acetone, methylene chloride or gasoline and adding the acid at temperatures from 0 to 100 ° C can be obtained and isolated in a known manner, for example by filtering, and optionally cleaned by washing with an inert organic solvent.
  • a suitable organic solvent such as methanol, acetone, methylene chloride or gasoline
  • the base addition salts of the compounds of formula (I) are preferably in inert polar solvents such as e.g. Water, methanol or acetone at temperatures from 0 to 100 ° C.
  • Suitable bases for the preparation of the salts according to the invention are, for example, alkali carbonates, such as potassium carbonate, alkali and alkaline earth metal hydroxides, e.g. NaOH or KOH, alkali and alkaline earth hydrides, e.g. NaH, alkali and alkaline alcoholates, e.g. Sodium methoxide, potassium tert-butoxide, or ammonia or ethanolamine.
  • inert solvents mean in each case solvents which are inert under the respective reaction conditions but do not have to be inert under any reaction conditions.
  • a collection of compounds (I) which can be synthesized according to the above-mentioned methods can additionally be produced in a parallelized manner, which can be done in a manual, partially automated or fully automated manner. It is possible to automate the implementation of the reaction, the processing or the cleaning of the products or intermediate stages. Overall, this is understood to be a procedure as described, for example, by S. H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Volume 1, Escom Verlag, 1997, pages 69 to 77.
  • a number of commercially available devices can be used for parallelized reaction execution and processing, for example those offered by Stern Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE, England or H + P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleissheim, Germany become.
  • Chromatography apparatuses are available, for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
  • the equipment listed enables a modular procedure in which the individual work steps are automated, but manual operations must be carried out between the work steps. This can be avoided by using partially or fully integrated automation systems in which the respective automation modules are operated by robots, for example. Automation systems of this type can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
  • compounds (I) can be prepared completely or partially by methods supported by solid phases.
  • solid phases For this purpose, individual intermediate stages or all intermediate stages of the synthesis or a synthesis adapted for the corresponding procedure are bound to a synthetic resin.
  • Solid phase-supported synthesis methods are adequately described in the specialist literature, e.g. For example: Barry A. Bunin in "The Combinatorial Index", Academic Press, 1998.
  • the preparation according to the processes described here provides compounds (I) in the form of substance collections or libraries.
  • the present invention therefore also relates to libraries of the compounds (I) which contain at least two compounds (I) and their precursors.
  • invention compounds of formula (I) have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants.
  • Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It does not matter whether the substances are applied by pre-sowing, pre-emergence or post-emergence.
  • Galium Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea,
  • the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
  • the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crop plants of economically important crops such as e.g. Wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesirable plant growth in agricultural crops.
  • the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene in the plant's metabolism in a regulating manner and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.
  • the active compounds can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties concern e.g. B. the crop in terms of quantity, quality, storability, composition and special ingredients. So are transgenic plants with increased starch content or changed starch quality or known with a different fatty acid composition of the crop.
  • B. of cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the compounds of the formula (I) can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
  • new plants which have modified properties in comparison to previously occurring plants are, for example, classic breeding methods and the generation of mutants.
  • new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624).
  • genetic engineering changes in crop plants have been described in order to modify the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827,
  • Glufosinate see e.g. EP-A-0242236, EP-A-242246) or glyphosate
  • Bacillus thuringiensis toxins (Bt toxins) which the
  • nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of the above standard procedures such. B. base exchanges, partial sequences removed or natural or synthetic sequences added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments.
  • the production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme which specifically cleaves transcripts of the gene product mentioned above.
  • DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
  • the synthesized protein When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any compartment of the plant cell. However, in order to achieve localization in a particular compartment, z. B. the coding region can be linked to DNA sequences that localize in guarantee a certain compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991).
  • the transgenic plant cells can be regenerated into whole plants using known techniques.
  • the transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.
  • the compounds (I) according to the invention can preferably be used in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium or analogous active compounds.
  • the active compounds according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic culture, for example a changed or specially expanded weed spectrum which can be controlled changed Application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the invention therefore also relates to the use of the compounds (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
  • the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and Adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powder
  • EC emulsifiable concentrates
  • EW emulsions
  • combinations with other pesticidally active substances e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.
  • pesticidally active substances e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g.
  • the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers).
  • organic solvent for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents.
  • ionic and / or nonionic surfactants emulsifiers
  • emulsifiers may be used, for example: calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan fatty acid such as Polyoxethylensorbitanester. Dusts are obtained by grinding the active ingredient with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • talc natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as those e.g. already listed above for the other types of formulation.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other formulation types.
  • EW Oil-in-water emulsions
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • adhesives e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils
  • Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • spray drying fluidized bed granulation
  • plate granulation mixing with high-speed mixers and extrusion without solid inert material.
  • spray granules see e.g. Procedure in "Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration”, Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook,” 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
  • the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active ingredient of the formula (I).
  • the active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight.
  • Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
  • the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
  • the compounds of formula (I) or their salts can be used as such or in the form of their preparations (formulations) with other pesticidally active substances, such as. B. insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and / or growth regulators can be used in combination, for. B. as a finished formulation or as a tank mix.
  • active ingredients such as those described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 10th edition, The British Crop Protection Council, can be used as combination partners for the active ingredients according to the invention in mixture formulations or in the tank mix and the Royal Soc. of Chemistry, 1994 and the literature cited therein.
  • Known herbicides or plant growth regulators that work with the compounds of Formula (I) can be combined, for example the following active substances are suitable; the compounds are referred to below either with the "common name" (usually according to the English spelling) according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a customary code number: acetochlor; acifluorfen (-sodium); aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim (-sodium); ametryn; amidochlor, amidosulfuron; amitrol; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azafenidin, azim
  • the selective control of harmful plants in crops of useful and ornamental plants is of particular interest.
  • the compounds (I) according to the invention already have very good to sufficient selectivity in many crops, phytotoxicity can occur on the crop plants in principle in some crops and especially in the case of mixtures with other herbicides which are less selective.
  • combinations are more inventive Compounds (I) of particular interest which contain the compounds (I) or their combinations with other herbicides or pesticides and safeners.
  • the safeners which are used in an antidotically effective content, reduce the phytotoxic side effects of the herbicides / pesticides used, eg. B.
  • cereals wheat, barley, rye, corn, rice, millet
  • sugar beet sugar cane
  • rapeseed cotton and soybeans
  • cotton and soybeans preferably cereals.
  • safeners for the compounds (I) and their combinations with other pesticides are suitable, for example, as safeners for the compounds (I) and their combinations with other pesticides:
  • Active substances of the phenoxyacetic or propionic acid derivative or aromatic carboxylic acid type such as, for example, 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methylphenoxy-propionester (mecoprop) , MCPA or 3,6-dichloro-2-methoxy-benzoic acid (ester) (Dicamba).
  • Active substances of the pyrimidine type which are used as soil-active safeners in rice, such as, for. B.
  • Safeners known for pretilachlor in sown rice are i) active substances of the dichloroacetamide type, often used as pre-emergence safeners
  • PPG-1292 N-allyl-N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide from the
  • Cyanomethoxyimino (phenyl) acetonitrile which is known as a seed dressing safener for millet against damage to metolachlor, I) active substances of the thiazole carboxylic acid ester type, which are known as seed dressings, such as, for. B.
  • Seed dressings are known, such as. B.
  • Naphthalenedicarboxylic anhydride which acts as a seed dressing safener against corn
  • n active substances of the chromanacetic acid derivative type, such as. B.
  • the weight ratio of herbicide (mixture) to safener generally depends on the amount of herbicide applied and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20.
  • the safeners can be analogous to the compounds (I) or mixtures thereof with others
  • Herbicides / pesticides are formulated and provided and used as a ready formulation or tank mix with the herbicides.
  • the herbicide or herbicide safener formulations present in commercially available form are optionally diluted in the customary manner, for example for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water.
  • Preparations in the form of dust, ground granules or scattering granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate of the compounds of formula (I) varies. It can fluctuate within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, but it is preferably between 0.005 and 5 kg / ha, in particular between 0.01 and 1 kg / ha of active substance.
  • the contents were taken up in water and the aqueous phase was extracted twice with ethyl acetate.
  • the aqueous phase was alkalized with 5 M potassium hydroxide solution while cooling with ice and extracted again twice with ethyl acetate.
  • the two last separated organic phases were combined, dried over magnesium sulfate and the filtrate was freed from the solvent on a rotary evaporator. 7.25 g (76% yield) of the desired product were obtained as an oil.
  • Phys. Data physical data; if a number is given, it means the melting point in ° C; “Resin” or “oil” refers to the consistency of the non-crystalline compound obtained.
  • a dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl taurine as a wetting and dispersing agent and grind in a pin mill.
  • a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether ( ® Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight.
  • Parts of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) and ground in a friction ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
  • Water-dispersible granules are also obtained by adding 25 parts by weight of a compound of the formula (I), 5 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants are placed in sandy loam in plastic pots and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates are then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.
  • the pots After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants have emerged, the optical damage to the plants or the emergence damage is assessed after a test period of 3 to 4 weeks in comparison to untreated controls. As the test results show, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds. For example, Examples Nos.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds are placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants are treated at the three-leaf stage.
  • the compounds according to the invention formulated as wettable powder or as emulsion concentrates are sprayed onto the green parts of the plant in various dosages with an amount of water converted from 600 to 800 l / ha. After the test plants have stood in the greenhouse for about 3 to 4 weeks under optimal growth conditions, the effect of the preparations is assessed visually in comparison with untreated controls.
  • the agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence.
  • Transplanted and sown rice as well as typical rice weeds and weeds are grown in the greenhouse up to the three-leaf stage (Echinochloa crus-galli 1, 5-leaf) under paddy rice conditions (accumulation height of the water: 2 - 3 cm) in closed plastic pots.
  • the treatment with the compounds according to the invention is then carried out.
  • the formulated active ingredients are suspended in water, dissolved or emulsified and, by means of pouring, applied to the test plants' ramewater in different dosages. After the treatment has been carried out in this way, the test plants are placed in the greenhouse under optimal growth conditions and are kept this way throughout the test period.
  • the compounds according to the invention have very good herbicidal activity against harmful plants.

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Abstract

L'invention concerne des alkylamino-1,3,5-triazines, leur procédé de production et leur utilisation comme herbicides et régulateurs de croissance de plantes. Les composés de la formule (I), R?1, R2, R3, R4, R5, R6, R7, R8¿ et A ayant la définition donnée dans la revendication n° 1, et leurs sels conviennent comme herbicides et régulateurs de croissance des plantes. Les composés (I) sont produits d'après le procédé selon la revendication n° 8.
EP00962536A 1999-10-08 2000-09-27 Alkyl-amino-1,3,5-triazines et leur utilisation comme herbicides Withdrawn EP1222178A1 (fr)

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DE1999148450 DE19948450A1 (de) 1999-10-08 1999-10-08 Alkyl-amino-1,3,5-triazine, Verfahren zur Herstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren
DE19948450 1999-10-08
PCT/EP2000/009419 WO2001027093A1 (fr) 1999-10-08 2000-09-27 Alkyl-amino-1,3,5-triazines et leur utilisation comme herbicides

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AU7422100A (en) 2001-04-23
AR025963A1 (es) 2002-12-26
DE19948450A1 (de) 2001-04-12
CA2386800A1 (fr) 2001-04-19
BR0014853A (pt) 2002-07-02
CO5231183A1 (es) 2002-12-27
WO2001027093A1 (fr) 2001-04-19

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