Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms
  • C07D213/71—Sulfur atoms to which a second hetero atom is attached

Definitions

• the present invention relates to new substituted 2-phenylpyridines of the formula I.
• R 1 halogen, C-- . - -Halogenalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkyl-thio, -C-C 4 -alkylsulfinyl, C ⁇ -C 4 -alkylsulfonyl, C 1 -C 4 -halogenylthio or cyano;
• R 2 is fluorine or trifluoromethyl
• R 3 is hydrogen or halogen
• R 4 halogen or cyano
• R 6 is hydrogen, an unsubstituted or halogen-substituted -CC 8 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl radical; C 1 -C 4 alkoxy -CC 4 -alkyl, Ci -C 6 -alkoxycarbonyl -C ⁇ -C -alkyl, C 3 -C -alkenyloxycarbonyl -Ci -C 4 -alkyl, C 3 -C 4 - Alkynyloxycarbonyl -CC 4 -alkyl or C 1 -C 4 -alkoxy- (C1-C4-alkoxy) carbonyl -CC 4 -alkyl means;
• R 7 can have the meaning of R 6 or for CH 2 -C0 2 [-C-C 4 alkylene] -C0 2 R 9 and
• R ö is hydrogen, halogen or C 1 -C 4 alkyl
• R 9 represents hydrogen or C 1 -C 4 alkyl, and the agriculturally useful salts of the compounds I.
• the invention also relates to
• the object of the present invention was therefore to provide new herbicidally active compounds which can be used to control undesirable plants better than before.
• the task also extends to the provision of new desiccant / defoliant connections.
• the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
• the invention relates both to the pure enantiomers or diastereomers and to mixtures thereof.
• the salts of such bases come into consideration in which the herbicidal action is not adversely affected in comparison with the free compound I.
• Particularly suitable salts are those of the alkali metals, preferably sodium and potassium salts, of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and ammonium salts, in which the ammonium ion can carry, if desired, one to four C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and tri ethyl- (2-hydroxyethyl) ammonium salts, furthermore phosphonium salts, sulfonium such as preferably tri (C ⁇ -C 4 -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri (C ⁇ -C4-alky
• alkyl, alkylene, haloalkyl, alkoxy, carboxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkenyl and alkynyl used in the definition of the substituents R 1 , R 6 , R 7 , R 8 and R 9 represent - like the meaning of halogen - collective terms for individual enumerations of the individual group members. All alkyl parts can be straight-chain or branched.
• the haloalkyl radical preferably carries one to five identical or different halogen atoms.
• Halogen fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine;
• C 1 -C 4 alkyl methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl;
• Ci-C ⁇ -alkyl -C-C 4 ⁇ alkyl as mentioned above, and n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 -Dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl , 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and l-ethyl -2-methylpropyl;
• Ci-C ⁇ -alkyl -C 6 alkyl as mentioned above, and inter alia n-heptyl, n-octyl;
• - C 3 -C 6 alkenyl C -C 4 alkenyl as mentioned above, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl , 1-methyl-but-l-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl but-1-en-l-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l- yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3-en-l-yl, 1, l-dimethyl prop-2-en-l-yl, 1, 2-dimethyl-prop-1-en-l-yl, 1, 2-dimethyl-prop-2-en-l-yl, 1-ethyl-prop-l- en-2-yl, 1-
• C 3 -C 4 alkynyl prop-1-in-l-yl, prop-2-in-3-yl, n-but-1-in-l-yl, n-but-l-in-4- yl, n-but-2-in-l-yl;
• C 3 -C 6 alkynyl C 3 - C 4 alkynyl as mentioned above, n-pent-1-in-yl, n-pent-1-in-3-yl, n-pent-1-yn -4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2 -in-5 -yl, 3-methyl-but-1-in-1-yl, 3-methyl-but-1-in-3-yl, 3-methyl-but-1-in-4-yl, n-hex-1 -in-l-yl, n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in -6-yl, n-hex-2-in-1-yl, n-hex-2-in-4 -yl, n-
• -C 1 -C 4 haloalkyl -C 4 C 4 -alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, Dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro 2-fluoroethyl, 2, 2, 2-trichloroethyl, pentafluoroethyl and 3-chloropropyl, preferably trifluoromethyl;
• C- L -C-C-haloalkoxy C- L -C 4 -alkoxy as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, Chlorofluoromethoxy, dichlorofluoromethoxy, chlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy and pentafluoroethoxy, preferably C 1 -C 2 haloalkoxy such as trifluoromethoxy;
• C ⁇ -C4-haloalkylthio chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, Chlorfluormethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-Dif luorethylthio, 2, 2, 2-trifluoroethylthio,
• 2-chloro-2-fluoroethylthio 2-chloro-2, 2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, 2, 2, 2-trichloroethylthio and pentafluoroethylthio, preferably C 1 -C 2 haloalkylthio such as Trif luormethylthio; C ⁇ ⁇ C 4 alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methyl-propylsulfonyl, 2-methylpropylsulfonyl and 1, 1-dimethylethylsulfonyl;
• -C-C 4 alkylsulfinyl methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1, 1-dimethylethylsulfinyl;
• C ⁇ -C alkoxy-C 1 -C 4 alkyl by C ⁇ -C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1 -Dimethylethoxy substituted C 1 -C 4 alkyl, e.g.
• (-CC 6 alkoxy) carbonyl -CC 2 -alkyl for: by (-C 6 -alkoxy) carbonyl such as COOCH 3 , COOC 2 H 5 , n-propoxycarbonyl, COOCH (CH 3 ) 2 , n- Butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl COOC (CH 3 ) 3 n-pentoxycarbonyl, 1-methyl-butoxycarbonyl and n-hexoxycarbonyl substituted C 1 -C 4 alkyl, e.g.
• (C 1 -C 6 -alkoxy) carbonyl -CC 4 -alkyl for: (-C 6 -alkoxy) carbonyl-C 4 -C 6 -alkyl as mentioned above, and 2- (methoxycarbonyl) propyl, 2- (ethoxycarbonyl) propyl, 2- (n-propoxycarbonyl-propyl, 2- (1-methylethoxycarbonyl) propyl, 2- (n-butoxycarbonyl-propyl, 2- (1-methylpropoxycarbonyl) propyl, 2- (2-methyl- propoxycarbonyl) propyl, 2- (1, 1-dimethylethoxycarbonyl) propyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 3- (n-propoxycarbonyl) ropyl, 3- (1-methylethoxycarbonyl) propyl, 3- (n-butoxycarbonyl) propyl, 3- (1-methylpropoxycarbonyl)
• OCH 3 , OC- 2 H 5 , OCH 2 -C 2 H 5 or OCH (CH 3 ) 2 in the C ⁇ -C 3 alkoxy part substituted (-C-C 3 -alkoxy) carbonyl-C ⁇ -C 6 -alkyl such as CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CHCOOC 2 H 5 , CH 2 CH 2 COOCH 2 -C 2 H 5 , CH 2 CH 2 COOCH (CH 3 ) 2 , 2- (COOCH 3 ) propyl, 2- (COOC 2 H 5 ) propyl, 2- (COOCH 2 -C 2 H 5 ) propyl, 2- [COOCH (CH 3 ) 2 ] propyl,
• alkoxy parts can be n-butoxy, sec-butoxy, iso-butoxy or tert-butoxy and 2- (COOCH 3 ) butyl, 2- (COOC 2 H 5 ) butyl, 2- (COOCH 2 -C 2 H 5 ) butyl, 2- [COOCH (CH 3 ) 2 ] butyl, 3- (COOCH 3 ) butyl, 3- (COOC 2 H 5 ) butyl,
• C -C alkylene is e.g. for methylene, 1,1-ethylene, 1,2-ethylene, 1, 1-propylene, 1, 2-propylene, 1, 3-propylene, 2, 2-propylene,
• the substituents and index m preferably have the following meanings, individually or in combination:
• R 2 is fluorine or trifluoromethyl
• R 3 fluorine or chlorine
• R 6 is hydrogen, Ci-Cs-alkyl, C 3 -C -alkenyl, 3-chloroprop-2-ene, C 3 -C 4 -alkynyl, -C-C 3 -alkoxy-C ⁇ -C 2 -alkyl, C x -C 6 -Alkoxycar- carbonyl-C ⁇ -C 2 alkyl, Ci-propargyloxycarbonyl -C 2 - alkyl, C 1 -C 3 - alkoxy C 1 -C 3 - alkoxy carbonyl -C -C - alkyl group;
• R 7 can have the meaning of R 6 or for CH 2 -C0 2 [-C-C 2 -alkylene] C0 2 R 9 and CH [C X -C 2 -
• R 9 represents hydrogen or C 1 -C 4 alkyl
• the substituted 2-phenylpyridines can be obtained in various ways, for example by the processes described in WO 95/02580 and WO 97/11059.
• a more recent form of coupling pyridine and phenyl components was described in DE No. 196 36995.9, according to which the pyridine sulfoxides Ilb and pyridine sulfones IIc are reacted with Grignard or zinc compounds III and IV to give the end products I according to the invention.
• R 3 to R 5 have the meaning given in claim 1 and X each represents a halogen atom.
• X each represents a halogen atom.
• the thiopyridines II can be prepared in analogy to the procedure described in DE No. 196 36997.5.
• DE note no. 19722661.2 shows a particularly favorable access to thiopyridines II starting from 2 -halopyridines V and thio compounds of the formula VI in the presence of a copper catalyst.
• R 1 and R 2 have the meaning given in claim 1.
• Z represents an unsubstituted or substituted by halogen, C 1 -C 4 -alkoxy-, C 1 -C 4 -alkoxy carbonyl, di- (C 1 -C 4 -alkylamino) carbonyl, cyano or nitro-substituted C 1 -C 0 -alkyl- , C -C 0 - alkenyl or C 2 -C ⁇ 0 alkynyl radical, a C 3 -C 8 cycloalkyl radical or one which is unsubstituted in the phenyl part or by halogen, C ⁇ -C 3 alkyl, C ⁇ -C 3 alkoxy, trifluoromethyl, Cyano or nitro substituted -CC 4 alkylenephenyl, phenyl or naphthyl radical.
• alkyl, alkenyl, alkynyl, alkylene, alkoxy, alkoxycarbonyl, dialkylaminocarbonyl, cycloalkyl used in the definition of the substituent Z are collective terms for individual lists of the individual group members. All alkyl parts can be straight-chain or branched.
• the haloalkyl radical preferably carries one to five identical or different halogen atoms.
• Ci-C ⁇ -alkyl as in the definition of substituents of R 6 and n-nonyl and n-decyl;
• Rl trifluoromethyl, chlorine, methylsulfonyl or cyano
• Z is an unsubstituted or substituted by chlorine or methoxy Ci-Ca alkyl radical, a benzyl or phenyl radical which is unsubstituted in the phenyl part or is substituted by halogen, methyl, C 1 -C 3 alkoxy, trifluoromethyl, cyano or nitro.
• the pyridine thioethers Ila2.001 - IIa2.116 of the formula IIa2 are preferred, which differ from the compounds IIal.001 - Ilal.116 in that a trifluoromethyl group is in the 5-position on the pyridine ring instead of chlorine.
• pyridine thioethers IIa3.001 - IIa3.116 of the formula IIa3 are preferred, which differ from the compounds
• IIal.001 - IIal.116 differ in that there is a methylsulfonyl group in the 5-position on the pyridine ring.
• pyridine thioethers Ila4.001 - IIa4.116 of the formula IIa4 are preferred, which differ from the compounds Ilal.OOl - IIal.116 in that a cyano group is in the 5-position on the pyridine ring instead of chlorine.
• thiopyridines IIbI.001-IIbl.116 of the formula IIbl are preferred, which differ from the compounds Ilal.OOl-IIal.116 in that the corresponding sulfoxides are present.
• thiopyridines IIb2.001 - IIb2.116 of the formula IIb2 are preferred, which differ from the compounds IIa2.001 - IIa2.116 in that the corresponding sulfoxides are present.
• thiopyridines IIb3.001 - IIb3.116 of the formula IIb3 are preferred, which differ from the compounds IIa3.001 - IIa3.116 in that the corresponding sulfoxides are present.
• thiopyridines IIb4.001 - IIb4.116 of the formula IIb4 are preferred, which differ from the compounds IIa4.001 - IIa4.116 in that the corresponding sulfoxides are present.
• thiopyridines IIcI.001 - IIcl.116 of the formula IIcl are preferred, which differ from the compounds Ilal.OOl - IIal.116 in that the corresponding sulfones are present.
• thiopyridines IIc2.001 - IIc2.116 of the formula IIc2 are preferred, which differ from the compounds IIa2.001 - IIa2.116 in that the corresponding sulfones are present.
• thiopyridines IIc3.001 - IIc3.116 of the formula Ilc3 are preferred, which differ from the compounds Ila3.001 - IIa3.116 in that the corresponding sulfones are present.
• thiopyridines IIc4.001 - IIc4.116 of the formula IIc4 are preferred, which differ from the compounds IIa4.001 - IIa4.116 in that the corresponding sulfones are present.
• peracetic acid sodium hypochlorite or chlorine and bromine can also be used analogously according to the above scheme.
• reaction of the 2 -halopyridines V with a thiol VI is advantageously carried out in the presence of a solvent at temperatures in the range from 80-250 ° C., preferably 120-200 ° C., particularly preferably 140-180 ° C.
• the solvents used for these reactions are hydrocarbons such as toluene, xylene, chlorinated hydrocarbons such as 1,2-dichloroethane, 1, 1, 2, 2-tetrachloroethane, chlorobenzene, 1,2- 1,3- or 1,4-dichlorobenzene, ether such as 1,4 dioxane, anisole, glycol ethers such as dimethyl glycol ether, diethyl glycol ether, diethylene glycol dimethyl ether, esters such as ethyl acetate, propyl acetate, methyl isobutyrate, isobutyl acetate, carboxylic acid amides such as DMF, N-methylpyrrolidone, nitro hydrocarbons 5 such as nitrobenzene, tetrabutyl tetrabutyl ether urea, dimethylethylene urea, dimethyl propylene urea, sulfoxides such as dimethyl sulfoxide
• the molar ratios in which the starting compounds are reacted with one another are generally 0.9-1.4, preferably 0.95-1.1, particularly preferably 0.98-1.04, for the ratio of thiol to 2 -Halogen pyridine V.
• the concentration of the starting materials in the solvent is 0.1-5 mol / 1, preferably 0.2-0.2 mol / 1.
• Suitable catalysts are copper oxide, salts such as copper (II) chloride, copper sulfate, copper nitrate, copper acetate,
• the molar amount of catalyst based on the 2-halopyridine V is 0.001-10, preferably 0.001-1, particularly preferably 0.001-0.1 mol%.
• the reaction can also be carried out in the presence of an organic base, such as. B. triethylamine, tri-n-propylamine, N-ethyldiisopropylamine, pyridine, ⁇ -, ß-, ⁇ -picoline, 2, 4 -, 2, 6 -lutidine, n-methylpyrrolidine, triethylenediamine, dimethylaniline, N, N-dimethylcyclohexylamine ,
• the reaction is preferably carried out under acidic conditions, in which the hydrogen halide split off in the reaction is discharged from the reaction mixture by means of an inert gas, for example nitrogen, or is allowed to escape into a washing device under autogenous pressure.
• an inert gas for example nitrogen
• the 2 -halopyridine V is advantageously added for 10 to 60 min. to a mixture of the thiol VI and the catalyst at 45 20-80 ° C and then stirred to complete the reaction 0.5 to 12 hours, preferably 1 to 8 hours at 140-180 ° C after.
• thiol VI can also be added to a mixture of 2-halopyridine V and catalyst and the reaction can then be completed as above.
• reaction can also be carried out in an autoclave.
• the higher-boiling component can be introduced together with the catalyst and the low-boiling component - depending on its consumption - directly at the reaction temperature of preferably 120-200 ° C., particularly preferably 140-180 ° C or gas.
• the reaction can be carried out under pressure or under pressure, continuously or batchwise.
• the oxidation of the pyridine thioethers of the formula Ha to the pyridine sulfoxides IIb and pyridine sulfones IIc can advantageously be carried out using hydrogen peroxide, the pyridine sulfoxides IIb being obtained with approximately equivalent amounts of oxidant and the pyridine sulfones IIc being obtained with approximately double molar amounts.
• the reaction can also be catalyzed by adding stronger acids such as trifluoroacetic acid or perchloric acid.
• metal compounds are also suitable as catalysts, e.g. B. transition metal oxides such as vanadium pentoxide, sodium tungstate, potassium dichromate, iron oxide tungstate, sodium tungstate, molybdic acid, osmic acid, titanium trichloride, selenium dioxide, phenylene selenic acid, oxovanadinyl -2, 4-pentanedioate.
• the catalysts are generally used in an amount of 0.5 to 10%, but because of the easy filterability and recovery of the inorganic catalysts, stoichiometric amounts can also be used.
• Another preferred oxidizing agent is peracetic acid or hydrogen peroxide / acetic anhydride, optionally also the peracetic acid present in equilibrium in a hydrogen peroxide / acetic acid mixture.
• a preferred oxidizing agent is also pertrifluoroacetic acid or the mixture of hydrogen peroxide / trifluoroacetic acid or the mixture of hydrogen peroxide / trifluoroacetic anhydride.
• Oxidation with water peroxide in glacial acetic acid is generally very selective, but is often slow.
• the reaction time can generally be shortened by adding trifluoroacetic acid.
• Oxidation with hydrogen superoxide in pure trifluoroacetic acid often leads, as also described in Chimia 29 (1975) 466, to the formation of the corresponding N-oxides.
• a rapid and selective oxidation of the pyridine thioethers Ha to the corresponding sulfoxides Ilb and sulfones IIc is possible with solutions of hydrogen superoxide in mixtures of acetic acid and trifluoroacetic acid in a volume ratio of 10: 1 to 1: 1, in particular 6: 1 to 4: 1. These mixtures are therefore particularly preferred as solvent.
• Petroleum ether the abovementioned solvents and the catalysts listed above can also be used as solvents.
• perbenzoic acid In addition to peracetic acid and pertrifluoroacetic acid, perbenzoic acid, monoperphthalic acid or 3-chloroperbenzoic acid can also advantageously be used in chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane.
• Chlorine and bromine are also very suitable for the oxidation of the thiols to sulfoxides or sulfones.
• Favorable solvents are water, acentontril, dioxane, two-phase systems such as aqueous potassium hydrogen carbonate solution / dichloromethane and, in the case of pyridine alkyl thioether, also acetic acid.
• active halogen can also tert. -Butyl hypochlorite, hypochlorous and bromonic acid, the salts thereof, and also H-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
• oxidation are also dinitrogen tetroxide z. B. in the process engineering simple variant with air / nitrogen dioxide or trioxide and, for example, osmium (VII) oxide as a catalyst.
• the oxidation can also be carried out directly with Acid are carried out, with acetic anhydride, acetic acid as additional solvents and copper (I) and (II) bromide and chloride as catalysts.
• Photosensitized oxygen transfer is also suitable for the oxidation, chlorophyll, protoporphyrin, Rose Bengal or methylene blue being recommended as photosensitizers.
• inert solvents are hydrocarbons such as pentane, hexane, heptane, cyclohexane, chlorinated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 1, 2, 2, tetrachloroethane, alcohols such as methanol, ethanol, n-propanol or isopropanol, ketones such as Acetone, methyl ethyl ketone, polar aprotic solvents such as acetonitrile, propionitrile or aromatic hydrocarbons such as benzene, toluene, chlorobenzene or xylene are suitable.
• oxygen it is also possible to use ozone in the abovementioned solvents, in addition to ether, 1,4-dioxan
• catalysts are also recommended for oxygen oxidation.
• B oxides and sulfides of nickel, copper, aluminum, tungsten, chromium, vanadium, ruthenium, titanium, manganese, molybdenum, magnesium and iron.
• pyridine sulfoxides Ilb or their pyridine sulfones IIc are obtained.
• the molar ratios in which the starting compounds are reacted with one another are generally 0.9-1.8, preferably 1.05-1.3 for the ratio of pyridine thioether Ha to oxidizing agent in the case of oxidation to pyridine sulfoxide IIb and generally 1 , 9 - 3.5, preferably 2.05 - 2.9 in the case of oxidation to pyridine sulfone IIc.
• the concentration of the starting materials in the solvent is generally 0.1-5 mol / 1, preferably 0.2-2 mol / 1.
• the pyridine thioether or the pyridine sulfoxide if appropriate with one of the abovementioned catalysts, is initially introduced into one of the abovementioned solvents, and the oxidizing agent is then added over the course of 0.25-20 hours while stirring.
• the addition and reaction temperature depends on the optimal efficiency of the respective oxidizing agent and the avoidance of side reactions. If photosensitized oxygen is used, the process is generally carried out at from -20 to 80 ° C., but is generally metal-catalyzed at from 50 to 140 ° C. and, when using ozone, generally at from -78 to 60 ° C.
• Reaction mixture are gasified until the oxidation is completed on the sulfoxide or sulfone stage. If air / nitrogen dioxide or trioxide is used, work is preferably carried out at 15-150 ° C. for 1-15 hours.
• Liquid or 5 easily soluble oxidizing agents such as hydrogen superoxide, the peracetic acid formed together with acetic anhydride or in equilibrium with acetic acid or trifluoroacetic acid or pertrifluoroacetic acid, hypochlorous or bromonic acid, tert. -Butylhy- pochlorite, chlorine or bromine, N-chlorine, or N-bromosuccinimide or
• 10 nitric acid can be added to the reaction mixture of the pyridine thioether or sulfoxide in a shorter period of time from 0.25 to 6 hours in order to bring the reaction to a conclusion after a further 1 to 60 hours.
• a staggered addition of the liquid is also preferred
• the oxidations can be operated without pressure or under pressure, continuously or batchwise.
• the multistage reaction can advantageously also be carried out as a one-pot process, the thioethers Ha obtained in the first synthesis step in the reaction of the 2 -halopyridines V with the thiols VI being added directly without isolation and purification
• reaction product Ha is optionally cooled to 90 to 120 ° C, optionally a solvent, for.
• Hydrogen superoxide especially sodium hypochlorite, are preferred as oxidizing agents.
• the intermediates Ila-c are taken up in a water-immiscible solvent, acidic impurities or oxidizing agents are extracted with dilute alkali or water, dried and the solvent is removed under reduced pressure.
• the substituted 2-phenylpyridines I can normally be prepared after 45 by one of the synthesis methods mentioned above. For economic or procedural reasons, however, it may be more convenient to use some compounds I from similar ones 2-Phenylpyridinen, but differ in the meaning of a residue.
• reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase towards the product.
• the substituted 2-phenylpyridines of the formula I can contain one or more centers of chirality and are then usually obtained as mixtures of enantiomers or diastereomers. If desired, the mixtures can be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.
• Salts of I can be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
• the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
• the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
• the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
• the following crops are considered, for example: Allium cepa, pineapple co osus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var.
• the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
• substituted 2-phenylpyridines I are also suitable for the desiccation and / or defoliation of plants.
• desiccants are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
• the compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules , Dusting, scattering or pouring.
• the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.
• mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin
• aliphatic, cyclic and aromatic hydrocarbons e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes
• Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• the 2-phenylpyridines I as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
• concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
• the surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenyl glycolphenyl, alkylphen -
• Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
• Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
• the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
• the compounds I according to the invention can be formulated, for example, as follows:
• Example No. 9 I 20 parts by weight of the active ingredient Example No. 9 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of Addition product of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
• Example No. 8 20 parts by weight of the active ingredient Example No. 8 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of
• Mixture in 20,000 parts by weight of water contains a spray mixture which contains 0.1% by weight of the active ingredient.
• V 3 parts by weight of the active ingredient Example No. 14 are mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.
• Example No. 6 1 part by weight of the active ingredient Example No. 6 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
• the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers, that the leaves of the sensitive crop plants are not hit, if possible, while the active ingredients get onto the leaves of unwanted plants growing underneath or the uncovered floor area (post-directed, lay-by).
• the active compound application rates are 0.0005 to 3.0, preferably 0.0005 to 1.0 kg / ha of active substance (as described above)
• the 2-phenylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
• 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl come as mixing partners -l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazines, dichloropropionic acid and their derivatives for dihydrobenes , Dihydrofuran-3-
• Propargyl alcohol was added at 20-29 ° C. with stirring to a solution of 0.5 g (0.00125 mol) of the compound from Example 11 in 10 ml of 1,2-dichloroethane and stirred at 23 ° C. for 1 hour.
• the reaction mixture was partitioned between methylene chloride and water and the organic phase was dried. After concentration in vacuo, 0.5 g (95.3% of theory) of the title compound was obtained as a colorless resin.
• Plastic pots with loamy sand with about 3.0% humus served as the culture vessels.
• the seeds of the test plants were sown separately according to species.
• the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
• the vessels were lightly sprinkled to promote germination and growth, and then covered with clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
• test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• the application rate for post-emergence treatment was 1.9 and 0.9 g / ha a. S.
• the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
• the trial period lasted 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
• Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
• the plants used in the greenhouse experiments are composed of the following types:
• Table C Comparison of compounds for determining the herbicidal activity in greenhouse tests using the post-emergence method
• the young cotton plants were drip-treated with aqueous preparations of the active ingredients (with the addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac® LF 700, based on the spray mixture).
• the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

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• Chemical & Material Sciences (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
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• 1998
  • 1998-05-15 EP EP98929325A patent/EP0984933A1/de not_active Withdrawn
  • 1998-05-15 AU AU79130/98A patent/AU7913098A/en not_active Abandoned
  • 1998-05-15 WO PCT/EP1998/002878 patent/WO1998054137A1/de not_active Application Discontinuation
  • 1998-05-15 CA CA002291446A patent/CA2291446A1/en not_active Abandoned
  • 1998-05-15 US US09/423,971 patent/US6420314B1/en not_active Expired - Fee Related
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