EP1697367A1 - 6-(2-halophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances - Google Patents

6-(2-halophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances

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Publication number
EP1697367A1
EP1697367A1 EP04803941A EP04803941A EP1697367A1 EP 1697367 A1 EP1697367 A1 EP 1697367A1 EP 04803941 A EP04803941 A EP 04803941A EP 04803941 A EP04803941 A EP 04803941A EP 1697367 A1 EP1697367 A1 EP 1697367A1
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European Patent Office
Prior art keywords
formula
compounds
hydrogen
cyano
alkyl
Prior art date
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EP04803941A
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German (de)
French (fr)
Inventor
Jordi Tormo I Blasco
Carsten Blettner
Bernd Müller
Markus Gewehr
Wassilios Grammenos
Thomas Grote
Joachim Rheinheimer
Peter Schäfer
Frank Schieweck
Anja Schwögler
Oliver Wagner
Maria Scherer
Siegfried Strathmann
Ulrich Schöfl
Reinhard Stierl
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to substituted triazolopyrimidines of the formula I.
  • R 1, R 2 independently of one another are hydrogen, C 8 alkyl, C r C 8 haloalkyl, C 3 -C 8 - cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 8 alkenyl, C 2 - C 8 haloalkenyl, C 3 -C 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partial unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S,
  • R 1 and R 2 can also form, together with the nitrogen atom to which they are attached, a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and one to three further heteroatoms from the group O, N and S as ring member contain and / or one or more substituents from the group halogen, C r C 6 alkyl, CC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 - haloalkenyl, -C 6 -alkoxy, C 6 Halogeno-alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, C 1 -C 6 -alkylene and oxy-C 3 -C 3 -alkyienoxy;
  • R 1 and / or R 2 may carry one to four identical or different groups R a :
  • R a is halogen, cyano, nitro, hydroxy, CC 6 alkyl, CC 6 haloalkyl, CC 6 - alkylcarbonyl, C 3 -C 6 cycloalkyl, C r C 6 alkoxy, C Ce haloalkoxy, C
  • A is hydrogen, hydroxy, d-C ⁇ -alkyl, C r C 8 alkoxy, CRCE haloalkoxy, CrC ⁇ -alkylamino or di- (CC 8 alkyl) amino;
  • L 3 is hydrogen, halogen, cyano, nitro, C ⁇ -C 4 haloalkyl, CC 6 alkoxy, C r C 6 - alkoxycarbonyl;
  • the invention relates to processes and intermediates for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
  • EP-A 71 792, EP-A 550 113, 5-chloro-6-phenyl-7-amino-triazolopyrimidines are generally known.
  • WO 03/080615 generally proposes 6-phenyltriazolopyrimidines whose phenyl group can carry an alkylamide group in the para position. These compounds are known for controlling harmful fungi.
  • the compounds according to the invention differ from those described in WO 03/080615 by the position of the alkylamide group as substituent of the 6-phenyl ring.
  • the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.
  • the compounds of the invention can be obtained in various ways.
  • they are prepared by reacting 5-aminotriazole of the formula II with correspondingly substituted phenylmalonates of the formula III in which R is alkyl, preferably d-C ⁇ -alkyl, in particular methyl or ethyl.
  • This reaction is usually carried out at temperatures of from 80 ° C. to 250 ° C., preferably from 120 ° C. to 180 ° C., without solvent or in an inert organic solvent in the presence of a base [cf. EP-A 770 615] or in the presence of acetic acid under the conditions described in Adv. Het. Chem. Vol. 57, p. 81ff. (1993) known conditions.
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, Nitriles, ketones, alcohols, and N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide and dimethylacetamide.
  • the reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are generally inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides, and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium.
  • organometallic compounds in particular alkali metal alkyls, alkyl magnesium halides, and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium.
  • organic bases eg tertiary amines such as trimethylamine, triethylamine, tri-isopropylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl-aminopyridine and bicyclic amines into consideration.
  • tertiary amines such as tri-isopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base and the malonate III in an excess based on the triazole.
  • Phenylmalonates of the formula III are advantageously obtained from the reaction of correspondingly substituted bromobenzenes with dialkylmalonates under Cu (I) catalysis [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02788].
  • the dihydroxytriazolopyrimidines of the formula IV are converted under the conditions known from WO-A 94/20501 into the dihalopyrimidines of the formula V in which Y is a halogen atom, preferably a bromine or a chlorine atom, in particular a chlorine atom.
  • the halogenating agent [HAL] used is advantageously a chlorinating agent or a brominating agent such as phosphorus oxybromide or phosphorus oxychloride, optionally in the presence of a solvent.
  • This reaction is usually carried out at 0 ° C to 150 ° C, preferably at 80 ° C to 125 ° C, performed [see. EP-A 770 615].
  • This reaction is advantageously carried out at 0 ° C to 70 ° C, preferably 10 ° C to 35 ° C, preferably in the presence of an inert solvent such as ethers, eg. As dioxane, diethyl ether or especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cp. WO-A 98/46608].
  • ethers eg. As dioxane, diethyl ether or especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cp. WO-A 98/46608].
  • a base such as tertiary amines, for example triethylamine or inorganic bases, such as potassium carbonate is preferred; Excess amine of the formula VI can also serve as a base.
  • the reaction temperature is usually 0 to 120.degree. C., preferably 10 to 40.degree. C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
  • Suitable solvents include ethers, such as dioxane, diethyl ether and, preferably, tetrahydrofuran, alcohols, such as methanol or ethanol, halogenated hydrocarbons, such as dichloromethane, and aromatic hydrocarbons, such as toluene or acetonitrile.
  • ethers such as dioxane, diethyl ether and, preferably, tetrahydrofuran
  • alcohols such as methanol or ethanol
  • halogenated hydrocarbons such as dichloromethane
  • aromatic hydrocarbons such as toluene or acetonitrile.
  • the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IVa are obtained.
  • X 1 is CC 4 -alkyl or C 1 -C 4 -haloalkyl.
  • the 5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained [see. Chem. Pharm. Bull., 9, 801, (1961)].
  • the preparation of the starting compounds IIIa is advantageously carried out under the conditions described in EP-A 10 02 788.
  • the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines thus obtained are reacted with halogenating agents [HAL] under the conditions described above to give the 7-halotriazolopyrimidines of the formula Va in which Y represents a halogen atom.
  • halogenating agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride.
  • the reaction may be carried out neat or in the presence of a solvent. Typical reaction temperatures are from 0 to 150 ° C or preferably from 80 to 125 ° C.
  • compounds of the formula I in which X is C 4 -alkyl may alternatively be prepared from compounds I in which X is halogen, in particular chlorine, and malonates of the formula VIII are prepared.
  • the subsequent saponification of the ester IX is carried out under generally customary conditions, depending on the various structural elements, the alkaline or acidic saponification of the compounds IX may be advantageous. Under the conditions of the ester saponification, the decarboxylation to I can already take place completely or partially.
  • the decarboxylation is usually carried out at temperatures of 20 ° C to 180 ° C, preferably 50 ° C to 120 ° C, in an inert solvent, optionally in the presence of an acid.
  • Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid.
  • Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.
  • M is a valence Y metal ion, such as B, Zn or Sn, and X "is C 1 -C 3 alkyl, for example, by the following methods: J. Chem. Soc., Perkin Trans., 1, 1187 (1994), ibid. 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Vol. 43, 733 (1990); J. Org. Chem., Vol. 43, 358 (1978); Chem. Soc. Chem. Commun., 866 (1979); Tetrahedron Lett, Vol. 34, 8267 (1993); ibid., Vol. 33, 413 (1992).
  • the reaction mixtures are worked up in conventional, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
  • the intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example CC 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1- Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- Methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethyl butylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular CC 2 -haloalkyl such as chloromethyl, bromomethyl , Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 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-trichloroeth
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 -butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl
  • Haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), wherein in these groups, the hydrogen atoms partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be;
  • Alkynyl straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2 Methyl 3-butynyl,
  • Cycloalkyl mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C 3 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; 5- to 10-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S: - 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or an oxygen or sulfur atom or a or two oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isox
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom 5-membered heteroaryl groups which contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members may, for example, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5 Oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl; 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as
  • Alkylene divalent linear chains of 3 to 5 CH 2 groups, eg CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 and CH 2 CH 2 CH 2 CH 2 CH 2 ;
  • Oxyalkylene divalent unbranched chains of 2 to 4 CH 2 groups, wherein a valence is bonded to the skeleton via an oxygen atom, for example OCH 2 CH 2 , OCH 2 CH 2 CH 2 and OCH 2 CH 2 CH 2 CH 2 ;
  • Oxyalkylenoxy divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
  • R 1 is dd-alkyl, C 2 -C 6 -alkenyl or CC 8 -haloalkyl.
  • R 1 is a group A: FF (CH '2,)' q-CHR 3 - AZ 'Z wherein
  • Z 1 is hydrogen, fluorine or C 1 -C 6 -fluoroalkyl
  • Z 2 is hydrogen or fluorine, or Z and Z 2 together form a double bond
  • q is 0 or 1
  • R 3 is hydrogen or methyl
  • R 1 is C 3 -C 6 -cycloalkyl, which may be substituted by CC 4 alkyl.
  • R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with chiral centers, the (S) - isomers are preferred for these groups. In the case of halogen-free alkyl or alkenyl groups with chiral centers in R 1 or R 2 , the (R) -configured isomers are preferred.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thio morpholinyl, in particular a piperidinyl ring which is optionally substituted by one to three halogen, dC 4 -alkyl or dC 4 -haloalkyl.
  • Particularly preferred are the compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring.
  • a further preferred subject of the invention are compounds I in which R and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which is optionally substituted by one or two groups halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkyl.
  • Haloalkyl in particular by 3,5-dimethyl or 3,5-di- (trifluoromethyl) is substituted.
  • R 2 is hydrogen or methyl; or R 1 and R 2 together are - (CH 2 ) 2 CH (CH 3 ) (CH 2 ) 2-, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 - or - (CH 2 ) 2 O (CH2) 2 - mean.
  • X is halogen, CC-alkyl, cyano or C 1 -C 4 -alkoxy, such as chlorine, methyl, cyano, methoxy or ethoxy, especially chlorine or methyl, in particular chlorine.
  • shark is in particular chlorine or fluorine.
  • compounds I are preferred in which L 1 is C 2 -alkoxy, such as methoxy; cyano; Halomethyl, such as trifluoromethyl or dd-alkoxycarbonyl, such as methoxycarbonyl means.
  • L 2 and L 3 particularly preferably mean hydrogen.
  • L 2 CC 2 alkoxy such as methoxy
  • cyano such as cyano
  • Halomethyl such as trifluoromethyl or dC 4 alkoxycarbonyl, such as methoxycarbonyl.
  • L 1 and L 3 are hydrogen.
  • a preferred embodiment of the invention relates to compounds of the formula 1.1:
  • GC 2 -C 6 -alkyl in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and CC 4 -alkoxymethyl, in particular ethoxymethyl, or C 3 -C 6 -cycloalkyl, in particular cyclopentyl or cyclohexyl ;
  • R 2 is hydrogen or methyl;
  • X is chlorine, methyl, cyano, methoxy or ethoxy.
  • a further preferred embodiment of the invention relates to compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and another heteroatom from the group O , N and S as a ring member and / or one or more substituents selected from the group halogen, CC 6 alkyl, d-Ce-haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dC 6 alkoxy CRCE haloalkoxy C_-C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, -C 6 alkylene and oxy-dC 3, - may bear alkyleneoxy.
  • These compounds correspond in particular to formula I.2,
  • D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as ring member and / or one or more substituents from the group halogen, dC 4 - Alkyl, CC 4 alkoxy and dC 2 haloalkyl; and
  • X is chlorine, methyl, cyano, methoxy or ethoxy.
  • Another preferred embodiment of the invention relates to compounds of the formula I.3.
  • Y is hydrogen or C 1 -C 4 -alkyl, in particular methyl and ethyl, and X is chlorine, methyl, cyano, methoxy or ethoxy.
  • Table 84 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 85 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 86 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 87 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 88 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 90 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 91 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 107 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 108 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 109 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 110 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 112 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L z is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 113 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 114 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 130 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 131 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 132 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 133 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 134 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 135 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 136 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 137 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 153 Compounds of the formula I in which X corresponds to chlorine, Hal fluorine, L 1 methoxy, L 2 hydrogen, L 3 cyano and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 154 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 155 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 156 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 157 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 158 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 159 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 160 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 176 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 177 Compounds of the formula I in which X is chlorine, Hal is chlorine, L is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 178 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 180 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 181 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
  • Table 182 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • Table 183 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
  • the compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Bassidiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.
  • the compounds I are also suitable for controlling harmful fungi such as Pecilomyces variotii in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Pecilomyces variotii in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients.
  • the application can be done both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.
  • the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
  • amounts of active ingredient of 1 to 1000 g / 100 kg of seed preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg are used.
  • the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.
  • Suitable solvents / auxiliaries are essentially: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma Butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • aromatic solvents eg Solvesso products, xylene
  • paraffins eg petroleum fractions
  • alcohols eg methanol, butanol, pentanol, benzyl alcohol
  • ketones eg cyclohe
  • solvent mixtures may also be used, - carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (for example, polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants, such as lignin-sulphite liquors and methylcellulose.
  • ground natural minerals for example kaolins, clays, talc, chalk
  • ground synthetic minerals for example finely divided silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (for example, polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates)
  • dispersants such as lignin-sulphite liquors and methylcellulose.
  • the surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene lenoctylphenolether, ethoxylated isooctylphenol, octylphenol, nonylphenol, Alkylphe- nolpolyglykolet er, Tributyl
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivative
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a compound of the invention 10 parts by weight of a compound of the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.
  • a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%).
  • This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • Agitator ball mill to a fine suspension of active ingredient crushed. Dilution in water results in a stable suspension of the active ingredient.
  • Water-dispersible and Water-soluble Granules 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • WP, SP Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active substance.
  • H dusts (DP) 5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dust.
  • a compound according to the invention 0.5 parts by weight of a compound according to the invention are finely ground and combined with 95.5% excipients. Common methods are the extrusion, the Spray drying or the fluidized bed. This gives granules for direct application.
  • ULV solutions 10 parts by weight of a compound of the invention are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.
  • organic solvent e.g. Xylene dissolved.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring.
  • the forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulgent. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • wetting agents for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • fertilizers When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.
  • Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;
  • Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph;
  • Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl;
  • antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin;
  • Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochlorazole, prothioconazole, tebuconazole, triadimefon, triadimol, triflumizole , Triticonazole;
  • Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;
  • Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;
  • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxaldine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazide, pyrifenox, pyroquilone, Quinoxyfen, silthiofam, thiabenazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine;
  • Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate;
  • Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl;
  • Phenylpyrroles such as fenpiclonil or fludioxonil; • sulfur;
  • fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorotrilone, cyflufenamid, cymoxanil, dazomet, diclomethine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, Fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide; Strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyr
  • Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
  • Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
  • the aqueous phase was extracted with methylene chloride, the aqueous phase was filtered off, the filter residue was dissolved in tetrahydrofuran. Both the combined organic phases were dried and freed from the solvents. The residue obtained was 2.0 g of the title compound as a beige solid, which was used without further purification in the next reaction.
  • the active compounds were separately prepared as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or D SO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
  • Uniperol® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • Paprika seedlings of the cultivar "Neusiedler Ideal Elite” were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well.
  • the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 ⁇ 10 6 spores / ml in a 2% aqueous biomalt solution.
  • the test plants were placed in a climatic chamber at 22 to 24 ° C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.
  • Leaves of potted plants of the "Golden Queen" variety were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. The following day, the leaves were infected with an aqueous spore suspension of Alternana solani in 2% biomalt solution with a density of 0.17 x 10 6 spores / ml. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days the disease had started The untreated but infected control plants developed so strongly that the infestation could be determined visually in%.

Abstract

The invention relates to triazolopyrimidines of formula (I) in which the substituents are defined as follows: R<1>, R<2> represent hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halocycloalkenyl, alkynyl, haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S; R<1> and R<2>, together with the nitrogen atom, to which they are bonded, can also form a five- or six-membered heterocyclyl or heteroaryl, which is bonded via N, can contain an additional heteroatom from the group O, N and S as a ring member and can be substituted according to the description; L<1>, L<2> represent hydrogen, cyano, haloalkyl, alkoxy, alkenyloxy or C(=O)A, whereby at least one group L<1> or L<2> does not represent hydrogen; A represents hydrogen, hydroxy, alkyl, alkoxy, haloalkoxy, C1-C8 alkylamino or dialkylamino; L<3> represents hydrogen, halogen, cyano, nitro, haloalkyl, alkoxy or alkoxycarbonyl; X represents halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy. The invention also relates to methods and intermediate products for producing said compounds, to agents containing the latter and to their use for combating plant-pathogenic fungi.

Description

6-(2-Halogenpheny.)-Triazolopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen sowie sie enthaltende Mittel6- (2-halophenyl) - triazolopyrimidines, process for their preparation and their use for controlling harmful fungi and agents containing them
Beschreibungdescription
Die vorliegende Erfindung betrifft substituierte Triazolopyrimidine der Formel IThe present invention relates to substituted triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meanings:
R1, R2 unabhängig voneinander Wasserstoff, Cι-C8-Alkyl, CrC8-Halogenalkyl, C3-C8- Cycloalkyl, C3-C8-Halogencycloalkyl, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C3-C6- Cycloalkenyl, C3-C6-Halogencycloalkenyl, C2-C8-Alkinyl, C2-C8-Halogenalkinyl oder Phenyl, Naphthyl, oder ein fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S,R 1, R 2 independently of one another are hydrogen, C 8 alkyl, C r C 8 haloalkyl, C 3 -C 8 - cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 8 alkenyl, C 2 - C 8 haloalkenyl, C 3 -C 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partial unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S,
R1 und R2 können auch zusammen mit dem Stickstoff atom, an das sie gebunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein bis drei weitere Heteroatome aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, CrC6-Alkyl, C C6-Halogenalkyl, C2-C6-Alkenyl, C2-C6- Halogenalkenyl, CrC6-Alkoxy, Cι-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6- Halogenalkenyloxy, C^Ce-Alkylen und Oxy-C C3-alkyienoxy tragen kann;R 1 and R 2 can also form, together with the nitrogen atom to which they are attached, a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and one to three further heteroatoms from the group O, N and S as ring member contain and / or one or more substituents from the group halogen, C r C 6 alkyl, CC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 - haloalkenyl, -C 6 -alkoxy, C 6 Halogeno-alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, C 1 -C 6 -alkylene and oxy-C 3 -C 3 -alkyienoxy;
R1 und/oder R2 können eine bis vier gleiche oder verschiedene Gruppen Ra tragen:R 1 and / or R 2 may carry one to four identical or different groups R a :
Ra Halogen, Cyano, Nitro, Hydroxy, C C6-Alkyl, C C6-Halogenalkyl, C C6- Alkylcarbonyl, C3-C6-Cycloalkyl, CrC6-Alkoxy, C Ce-Halogenalkoxy, C|-C6- Alkoxycarbonyl, CrC6-Alkylthio, C-rC.-Alkylamino, Di-d-Ce-alkylamino, C2- C8-Alkenyl, C2-C8-Halogenalkenyl, C3-C8-Cycloalkenyl, C2-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, C2-C6-Alkinyl, C2-C6-Halogenalkinyl, C3-C6-Al- kinyloxy, C3-C6-Halogenalkinyloxy, C3-C6-Cycloalkoxy, C3-C6-Cyclo- alkenoxy, CrCs-Oxyalkylenoxy, Phenyl, Naphthyl, fünf- bis zehngliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthal- tend ein bis vier Heteroatome aus der Gruppe O, N oder S, wobei diese aliphatischen, alicyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein oder eine bis drei Gruppen Rb tragen können: R° Halogen, Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Amino- carbonyl, Aminothiocarbonyl, Alkyl, Haloalkyl, Alkenyl, Alkenyloxy, Al- kinyloxy, Alkoxy, Halogenalkoxy, Alkylthio, Alkylamino, Dialkylamino, Formyl, Alkylcarbonyl, Alkylsulfonyl, Alkylsulfoxyl, Alkoxycarbonyl, Al- kylcarbonyloxy, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkylami- nothiocarbonyl, Dialkylaminothiocarbonyl, wobei die Alkylgruppen in diesen Resten 1 bis 6 Kohlenstoffatome enthalten und die genannten Alkenyl- oder Alkinylgruppen in diesen Resten 2 bis 8 Kohlenstoffatome enthalten; und/oder einen bis drei der folgenden Reste:R a is halogen, cyano, nitro, hydroxy, CC 6 alkyl, CC 6 haloalkyl, CC 6 - alkylcarbonyl, C 3 -C 6 cycloalkyl, C r C 6 alkoxy, C Ce haloalkoxy, C | -C 6 Alkoxycarbonyl, C 1 -C 6 -alkylthio, C-rC . Alkylamino, di-d-Ce-alkylamino, C 2 - C 8 alkenyl, C 2 -C 8 haloalkenyl, C 3 -C 8 cycloalkenyl, C 2 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy , C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 alkynyloxy, C 3 -C 6 haloalkynyloxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 cyclo alkenoxy, C 1 -C 8 -oxyalkyleneoxy, phenyl, naphthyl, five- to ten-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S, these aliphatic, alicyclic or aromatic groups in turn may be partially or fully halogenated or may carry one to three groups R b : R ° halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, amino carbonyl, aminothiocarbonyl, alkyl, haloalkyl, Alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl groups in these radicals 1 to Contain 6 carbon atoms and said alkenyl or alkynyl groups in these radicals contain from 2 to 8 carbon atoms; and / or one to three of the following radicals:
Cycloalkyl, Cycloalkoxy, Heterocyclyl, Heterocyclyloxy, wobei die cyc- lischen Systeme 3 bis 10 Ringglieder enthalten; Aryl, Aryloxy, Arylthio, Aryl-CrC6-alkoxy, Aryl-C Ce-alkyl, Hetaryl, Hetaryloxy, Het- arylthio, wobei die Arylreste vorzugsweise 6 bis 10 Ringglieder, die Hetarylreste 5 oder 6 Ringglieder enthalten, wobei die cyclischen Systeme partiell oder vollständig halogeniert oder durch Alkyl- oder Haloalkylgruppen substituiert sein können;Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems containing 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl-CrC 6 -alkoxy, aryl-C Ce-alkyl, hetaryl, hetaryloxy, Het- arylthio, wherein the aryl radicals preferably 6 to 10 ring members, the hetaryl contain 5 or 6 ring members, wherein the cyclic systems are partially or completely halogenated or substituted by alkyl or haloalkyl groups;
Hai Halogen;Shark halogen;
L1, L2 Wasserstoff, Cyano, CrC4-Halogenalkyl, CrCe-Alkoxy, C3-C6-Alkenyloxy oder C(=O)A, wobei mindestens eine Gruppe L oder L2 ungleich Wasserstoff ist; A Wasserstoff, Hydroxy, d-Cβ-Alkyl, CrC8-Alkoxy, CrCe-Halogenalkoxy, CrCβ-Alkylamino oder Di-(C C8-Alkyl)amino;L 1 , L 2 is hydrogen, cyano, C r C 4 -haloalkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyloxy or C (= O) A, where at least one group L or L 2 is other than hydrogen; A is hydrogen, hydroxy, d-Cβ-alkyl, C r C 8 alkoxy, CRCE haloalkoxy, CrCβ-alkylamino or di- (CC 8 alkyl) amino;
L3 Wasserstoff, Halogen, Cyano, Nitro, Cι-C4-Halogenalkyl, C C6-Alkoxy, CrC6- Alkoxycarbonyl;L 3 is hydrogen, halogen, cyano, nitro, Cι-C 4 haloalkyl, CC 6 alkoxy, C r C 6 - alkoxycarbonyl;
Halogen, Cyano, C C4-Alkyl, C C4-Halogenalkyl, C C4-Alkoxy oder C C2-Halo- genalkoxy. Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung dieser Verbindungen, sie enthaltende Mittel sowie ihre Verwendung zur Bekämpfung von pflanzenpathogenen Schadpilzen.Halogen, cyano, CC 4 -alkyl, CC 4 -haloalkyl, CC 4 -alkoxy or CC 2 -haloalkoxy. Moreover, the invention relates to processes and intermediates for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
Aus EP-A 71 792, EP-A 550 113 sind 5-Chlor-6-phenyl-7-amino-triazolopyrimidine allgemein bekannt. In WO 03/080615 werden 6-Phenyl-Triazolopyrimidine allgemein vorgeschlagen, deren Phenylgruppe in para-Stellung eine Alkylamid-Gruppe tragen kann. Diese Verbindungen sind zur Bekämpfung von Schadpilzen bekannt.From EP-A 71 792, EP-A 550 113, 5-chloro-6-phenyl-7-amino-triazolopyrimidines are generally known. WO 03/080615 generally proposes 6-phenyltriazolopyrimidines whose phenyl group can carry an alkylamide group in the para position. These compounds are known for controlling harmful fungi.
Die erfindungsgemäßen Verbindungen unterscheiden sich von den in WO 03/080615 beschriebenen durch die Stellung der Alkylamid-Gruppe als Substituent des 6-Phenyl- ringes.The compounds according to the invention differ from those described in WO 03/080615 by the position of the alkylamide group as substituent of the 6-phenyl ring.
Die Wirkung der bekannten Verbindungen ist jedoch in vielen Fällen nicht zufrieden- stellend. Davon ausgehend, liegt der vorliegenden Erfindung die Aufgabe zugrunde, Verbindungen mit verbesserter Wirkung und/oder verbreitertem Wirkungsspektrum bereitzustellen.However, the effect of the known compounds is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.
Demgemäss wurden die eingangs definierten Verbindungen gefunden. Des weiteren wurden Verfahren und Zwischenprodukte zu ihrer Herstellung, sie enthaltende Mittel sowie Verfahren zur Bekämpfung von Schadpilzen unter Verwendung der Verbindungen I gefunden.Accordingly, the compounds defined above were found. Furthermore, processes and intermediates for their preparation, agents containing them and methods for controlling harmful fungi using the compounds I have been found.
Die erfindungsgemäßen Verbindungen können auf verschiedenen Wegen erhalten werden. Vorteilhaft werden sie durch Umsetzung von 5-Aminotriazol der Formel II mit entsprechend substituierten Phenylmalonaten der Formel III, in der R für Alkyl, bevorzugt für d-Cβ-Alkyl, insbesondere für Methyl oder Ethyl steht, dargestellt.The compounds of the invention can be obtained in various ways. Advantageously, they are prepared by reacting 5-aminotriazole of the formula II with correspondingly substituted phenylmalonates of the formula III in which R is alkyl, preferably d-Cβ-alkyl, in particular methyl or ethyl.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von 80°C bis 250°C, vor- zugsweise 120°C bis 180°C, ohne Solvens oder in einem inerten organischen Lösungsmittel in Gegenwart einer Base [vgl. EP-A 770 615] oder in Gegenwart von Essigsäure unter den aus Adv. Het. Chem. Bd. 57, S. 81ff. (1993) bekannten Bedingungen.This reaction is usually carried out at temperatures of from 80 ° C. to 250 ° C., preferably from 120 ° C. to 180 ° C., without solvent or in an inert organic solvent in the presence of a base [cf. EP-A 770 615] or in the presence of acetic acid under the conditions described in Adv. Het. Chem. Vol. 57, p. 81ff. (1993) known conditions.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe, Ether, Nitrile, Ketone, Alkohole, sowie N-Methylpyrrolidon, Dimethylsulfoxid, Dimethylform- amid und Dimethylacetamid. Besonders bevorzugt wird die Umsetzung ohne Lösungsmittel oder in Chlorbenzol, Xylol, Dimethylsulfoxid, N-Methylpyrrolidon durchgeführt. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, Nitriles, ketones, alcohols, and N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide and dimethylacetamide. The reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide, Alkalimetall- und Erdalkalimetalloxide, Alkalimetall- und Erdalkalimetallhydride, Alkalimetallamide, Alkalimetall- und Erdalkalimetallcarbonate sowie Al- kalimetallhydrogencarbonate, metallorganische Verbindungen, insbesondere Alkalime- tallalkyle, Alkylmagnesiumhalogenide sowie Alkalimetall- und Erdalkalimetallalkoholate und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tri-isopropylamin, Tributylamin und N-Methylpiperidin, N- Methylmorpholin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethyl- aminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden tertiä- re Amine wie Tri-isopropylamin, Tributylamin, N-Methylmorpholin oder N-Methylpiperidin.Suitable bases are generally inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides, and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium. also organic bases, eg tertiary amines such as trimethylamine, triethylamine, tri-isopropylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl-aminopyridine and bicyclic amines into consideration. Particularly preferred are tertiary amines such as tri-isopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.
Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuss oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann für die Ausbeute vorteilhaft sein, die Base und das Malonat III in einem Überschuss bezogen auf das Triazol einzusetzen.The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base and the malonate III in an excess based on the triazole.
Phenylmalonate der Formel III werden vorteilhaft aus der Reaktion entsprechend substituierter Brombenzole mit Dialkylmalonaten unter Cu(l)-Katalyse erhalten [vgl. Che- mistry Letters, S. 367-370, 1981; EP-A 10 02788].Phenylmalonates of the formula III are advantageously obtained from the reaction of correspondingly substituted bromobenzenes with dialkylmalonates under Cu (I) catalysis [cf. Chemistry Letters, pp. 367-370, 1981; EP-A 10 02788].
Die Dihydroxytriazolopyrimidine der Formel IV werden unter den aus WO-A 94/20501 bekannten Bedingungen in die Dihalogenpyrimidine der Formel V überführt, in der Y ein Halogenatom, bevorzugt ein Brom oder ein Chloratom, insbesondere ein Chloratom bedeutet. Als Halogenierungsmittel [HAL] wird vorteilhaft ein Chlorierungsmittel oder ein Bromierungsmittel, wie Phosphoroxybromid oder Phosphoroxychlorid, ggf. in An- Wesenheit eines Lösungsmittels, eingesetzt.The dihydroxytriazolopyrimidines of the formula IV are converted under the conditions known from WO-A 94/20501 into the dihalopyrimidines of the formula V in which Y is a halogen atom, preferably a bromine or a chlorine atom, in particular a chlorine atom. The halogenating agent [HAL] used is advantageously a chlorinating agent or a brominating agent such as phosphorus oxybromide or phosphorus oxychloride, optionally in the presence of a solvent.
Diese Umsetzung wird üblicherweise bei 0°C bis 150°C, bevorzugt bei 80°C bis 125°C, durchgeführt [vgl. EP-A 770 615]. This reaction is usually carried out at 0 ° C to 150 ° C, preferably at 80 ° C to 125 ° C, performed [see. EP-A 770 615].
Dihalogenpyrimidine der Formel V werden mit Aminen der Formel VI, + R2^ -H *■ l (X = Halogen) VI in der R1 und R2 wie in Formel I definiert sind, zu Verbindungen der Formel I, in der X für Halogen steht, weiter umgesetzt.Dihalopyrimidines of the formula V are reacted with amines of the formula VI, + R 2 ^ -H * ■ l (X = halogen) VI in which R 1 and R 2 are as defined in formula I, to give compounds of the formula I in which Halogen is, further reacted.
Diese Umsetzung wird vorteilhaft bei 0°C bis 70°C, bevorzugt 10°C bis 35°C durchge- führt, vorzugsweise in Anwesenheit eines inerten Lösungsmittels, wie Ether, z. B. Di- oxan, Diethylether oder insbesondere Tetrahydrofuran, halogenierte Kohlenwasserstoffe, wie Dichlormethan und aromatische Kohlenwasserstoffe, wie beispielsweise Toluol [vgl. WO-A 98/46608].This reaction is advantageously carried out at 0 ° C to 70 ° C, preferably 10 ° C to 35 ° C, preferably in the presence of an inert solvent such as ethers, eg. As dioxane, diethyl ether or especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cp. WO-A 98/46608].
Die Verwendung einer Base, wie tertiäre Amine, beispielsweise Triethylamin oder anorganische Basen, wie Kaliumcarbonat ist bevorzugt; auch überschüssiges Amin der Formel VI kann als Base dienen.The use of a base, such as tertiary amines, for example triethylamine or inorganic bases, such as potassium carbonate is preferred; Excess amine of the formula VI can also serve as a base.
Verbindungen der Formel I, in derX Cyano, d-C6-Alkoxy oder C C2-Halogenalkoxy bedeutet, können vorteilhaft aus der Umsetzung von Verbindungen I, in der X Halogen, bevorzugt Chlor bedeutet, mit Verbindungen M-X' (Formel VII) erhalten werden. Verbindungen VII stellen je nach der Bedeutung der einzuführenden Gruppe X' ein anorganisches Cyanid, ein Alkoxylat oder ein Halogenalkoxylat dar. Die Umsetzung erfolgt vorteilhaft in Anwesenheit eines inerten Lösungsmittels. Das Kation M in Formel VII hat geringe Bedeutung; aus praktischen Gründen sind üblicherweise Ammonium-, Tetraal- kylammonium- oder Alkali- oder Erdalkalimetallsalze bevorzugt. I (X = Halogen) + M-X' *- l (X = X') VIICompounds of the formula I in which X is cyano, C 1 -C 6 -alkoxy or CC 2 -haloalkoxy can advantageously be obtained from the reaction of compounds I in which X is halogen, preferably chlorine, with compounds MX '(formula VII). Depending on the meaning of the group X 'to be introduced, compounds VII represent an inorganic cyanide, an alkoxylate or a haloalkoxylate. The reaction is advantageously carried out in the presence of an inert solvent. The cation M in formula VII has little significance; For practical reasons, ammonium, tetraalkylammonium or alkali or alkaline earth metal salts are usually preferred. I (X = halogen) + MX '* - I (X = X') VII
Üblicherweise liegt die Reaktionstemperatur bei 0 bis 120°C, bevorzugt bei 10 bis 40°C [vgl. J. Heterocycl. Chem., Bd.12, S. 861-863 (1975)].The reaction temperature is usually 0 to 120.degree. C., preferably 10 to 40.degree. C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
Geeignete Lösungsmittel umfassen Ether, wie Dioxan, Diethylether und, bevorzugt Tetrahydrofuran, Alkohole, wie Methanol oder Ethanol, halogenierte Kohlenwasserstoffe wie Dichlormethan und aromatische Kohlenwasserstoffe, wie Toluol oder Acetonitril.Suitable solvents include ethers, such as dioxane, diethyl ether and, preferably, tetrahydrofuran, alcohols, such as methanol or ethanol, halogenated hydrocarbons, such as dichloromethane, and aromatic hydrocarbons, such as toluene or acetonitrile.
Verbindungen der Formel I, in denen X für C C4-Alkyl oder d-C4-Halogenalkyl steht, können vorteilhaft durch folgenden Syntheseweg erhalten werden: Compounds of formula I in which X 4 alkyl or C 4 haloalkyl stands for CC can advantageously be obtained by following synthesis route:
Ausgehend von den Ketoestern lila werden die 5-Alkyl-7-hydroxy-6-phenyltriazolopyri- midine IVa erhalten. In Formeln lila und IVa steht X1 für C C4-Alkyl oder d-C4-Halo- genalkyl. Durch Verwendung der leicht zugänglichen 2-Phenylacetessigestem (lila mit X1=CH3) werden die 5-Methyl-7-hydroxy-6-phenyltriazolopyrimidine erhalten [vgl. Chem. Pharm. Bull., 9, 801 , (1961)]. Die Herstellung der Ausgangsverbindungen lila erfolgt vorteilhaft unter den aus EP-A 10 02 788 beschrieben Bedingungen.Starting from the ketoesters purple, the 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IVa are obtained. In formulas IIIa and IVa, X 1 is CC 4 -alkyl or C 1 -C 4 -haloalkyl. By using the readily available 2-Phenylacetessigestem (purple with X 1 = CH 3 ), the 5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained [see. Chem. Pharm. Bull., 9, 801, (1961)]. The preparation of the starting compounds IIIa is advantageously carried out under the conditions described in EP-A 10 02 788.
Die so erhaltenen 5-Alkyl-7-hydroxy-6-phenyltriazolopyrimidine werden mit Halogenie- rungsmitteln [HAL] unter den weiter oben beschriebenen Bedingungen zu den 7-Halo- genotriazolopyrimidinen der Formel Va umgesetzt, in der Y für ein Halpgenatom steht. Bevorzugt werden Chlorierungs- oder Bromierungsmittel wie Phosphoroxybromid, Phosphoroxychlorid, Thionylchlorid, Thionylbromid oder Sulfurylchlorid eingesetzt. Die Umsetzung kann in Substanz oder in Gegenwart eines Lösungsmittels durchgeführt werden. Übliche Reaktionstemperaturen betragen von 0 bis 150°C oder vorzugsweise von 80 bis 125°C.The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines thus obtained are reacted with halogenating agents [HAL] under the conditions described above to give the 7-halotriazolopyrimidines of the formula Va in which Y represents a halogen atom. Preference is given to using chlorinating or brominating agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride. The reaction may be carried out neat or in the presence of a solvent. Typical reaction temperatures are from 0 to 150 ° C or preferably from 80 to 125 ° C.
VI I (X = Alkyl) VI I (X = alkyl)
Die Umsetzung von Va mit Aminen VI erfolgt unter den weiter oben beschriebenen Bedingungen.The reaction of Va with amines VI takes place under the conditions described above.
Verbindungen der Formel I in der X d-C4-Alkyl bedeutet, können alternativ auch aus Verbindungen I, in der X Halogen, insbesondere Chlor, bedeutet und Malonaten der Formel VIII hergestellt werden. In Formel VIII bedeuten X" Wasserstoff oder C Cs- Alkyl und R C C4-Alkyl. Sie werden zu Verbindungen der Formel IX umgesetzt und zu Verbindungen I decarboxyliert [vgl. US 5,994,360]. Δ / H IX -_*- 1 (X = Crd ,-Alkyl)Alternatively, compounds of the formula I in which X is C 4 -alkyl may alternatively be prepared from compounds I in which X is halogen, in particular chlorine, and malonates of the formula VIII are prepared. In formula VIII, X "is hydrogen or C 1 -C 6 alkyl and RCC 4 alkyl They are converted to compounds of formula IX and decarboxylated to compounds I [see US 5,994,360]. Δ / H IX -_ * - 1 (X = C r d, -alkyl)
Die Malonate VIII sind in der Literatur bekannt [J. Am. Chem. Soc, Bd. 64, 2714 (1942); J. Org. Chem., Bd. 39, 2172 (1974); Helv. Chim. Acta, Bd. 61, 1565 (1978)] oder können gemäß der zitierten Literatur hergestellt werden.Malonates VIII are known in the literature [J. At the. Chem. Soc., Vol. 64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta, Vol. 61, 1565 (1978)] or can be prepared according to the cited literature.
Die anschließende Verseifung des Esters IX erfolgt unter allgemein üblichen Bedingungen, in Abhängigkeit der verschiedenen Strukturelemente kann die alkalische oder die saure Verseifung der Verbindungen IX vorteilhaft sein. Unter den Bedingungen der Esterverseifung kann die Decarboxylierung zu I bereits ganz oder teilweise erfolgen.The subsequent saponification of the ester IX is carried out under generally customary conditions, depending on the various structural elements, the alkaline or acidic saponification of the compounds IX may be advantageous. Under the conditions of the ester saponification, the decarboxylation to I can already take place completely or partially.
Die Decarboxylierung erfolgt üblicherweise bei Temperaturen von 20°C bis 180°C, vorzugsweise 50°C bis 120°C, in einem inerten Lösungsmittel, gegebenenfalls in Gegenwart einer Säure.The decarboxylation is usually carried out at temperatures of 20 ° C to 180 ° C, preferably 50 ° C to 120 ° C, in an inert solvent, optionally in the presence of an acid.
Geeignete Säuren sind Salzsäure, Schwefelsäure, Phosphorsäure, Ameisensäure, Essigsäure, p-Toluolsulfonsäure. Geeignete Lösungsmittel sind Wasser, aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropyl- ether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butyl- methylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol, sowie Dimethylsulfoxid, Dimethylformamid und Dimethylacetamid, be- sonders bevorzugt wird die Reaktion in Salzsäure oder Essigsäure durchgeführt. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid. Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, the reaction is particularly preferably carried out in hydrochloric acid or acetic acid. It is also possible to use mixtures of the solvents mentioned.
Verbindungen der Formel I, in denen X für C C -Alkyl steht, können auch durch Kupplung von 5-Halogentriazolopyrimidinen der Formel I, in der X Halogen bedeutet, mit metallorganischen Reagenzien der Formel X erhalten werden. In einer Ausführungsform dieses Verfahrens erfolgt die Umsetzung unter Übergangsmetallkatalyse, wie Ni- oder Pd-Katalyse. 1 (X = Hai) + My(-X")y 1 (X = C1-C4-Alkyl) XCompounds of the formula I in which X is C 1 -C 4 -alkyl can also be obtained by coupling of 5-halotriazolopyrimidines of the formula I in which X is halogen with organometallic reagents of the formula X. In one embodiment of this process, the reaction is carried out under transition metal catalysis, such as Ni or Pd catalysis. 1 (X = Hal) + My (-X ") y 1 (X = C 1 -C 4 -alkyl) X
In Formel X steht M für ein Metallion der Wertigkeit Y, wie beispielsweise B, Zn oder Sn und X" für d-C3-Alkyl. Diese Reaktion kann beispielsweise analog folgender Methoden durchgeführt werden: J. Chem. Soc. Perkin Trans. 1, 1187 (1994), ebenda 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Bd. 43, 733 (1990); J. Org. Chem., Bd. 43, 358 (1978); J. Chem. Soc. Chem. Commun. 866 (1979); Tetrahedron Lett, Bd. 34, 8267 (1993); ebenda, Bd. 33, 413 (1992).In formula X, M is a valence Y metal ion, such as B, Zn or Sn, and X "is C 1 -C 3 alkyl, for example, by the following methods: J. Chem. Soc., Perkin Trans., 1, 1187 (1994), ibid. 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Vol. 43, 733 (1990); J. Org. Chem., Vol. 43, 358 (1978); Chem. Soc. Chem. Commun., 866 (1979); Tetrahedron Lett, Vol. 34, 8267 (1993); ibid., Vol. 33, 413 (1992).
Die Reaktionsgemische werden in üblicherweise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräunlicher, zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The reaction mixtures are worked up in conventional, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
Sofern einzelne Verbindungen I nicht auf den voranstehend beschriebenen Wegen zugänglich sind, können sie durch Derivatisierung anderer Verbindungen I hergestellt werden.If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.
Sofern bei der Synthese Isomerengemische anfallen, ist im allgemeinen jedoch eine Trennung nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säureoder Baseneinwirkung) ineinander umwandeln können. Entsprechende Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen in der behandelten Pflanze oder im zu bekämpfenden Schadpilz erfolgen.However, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for use or in use (e.g., under light, acid, or base action). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
Bei den in den vorstehenden Formeln angegebenen Definitionen der Symbole wurden Sammelbegriffe verwendet, die allgemein repräsentativ für die folgenden Substituenten stehen:In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:
Halogen: Fluor, Chlor, Brom und Jod;Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4, 6 oder 8 Kohlenstoffatomen, z.B. C C6-Alkyl wie Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Me- thylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyl, 1-Ethylpropyl, Hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methyl pentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dime- thylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Tri- methylpropyl, 1-Ethyl-1-methylpropyl und 1-Ethyl-2-methylpropyl;Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example CC 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1- Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- Methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethyl butylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Halogenalkyl: geradkettige oder verzweigte Alkylgruppen mit 1 bis 2, 4 oder 6 Kohlen- Stoffatomen (wie vorstehend genannt), wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können: insbesondere C C2-Halogenalkyl wie Chlormethyl, Brommethyl, Dichlor- methyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Chlorethyl, 1-Bromethyl, 1-Fluorethyl, 2-Fluor- ethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl oder 1,1,1-Trifluorprop-2-yl;Haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular CC 2 -haloalkyl such as chloromethyl, bromomethyl , Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 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 or 1,1,1-trifluoroprop-2-yl ;
Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 4, 6 oder 8 Kohlenstoffatomen und einer oder zwei Doppelbindungen in beliebiger Positi- on, z.B. C2-C6-Alkenyl wie Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-1-propenyl, 2-Methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1 -Methyl- 1-but- enyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl- Ipropenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hex- enyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pent- enyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pent- enyl, 1-Methyl-3-pentenyl, 2-Methyl-3pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pent- enyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pent- enyl, 1 ,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Di- methyl-2-butenyl, 1 ,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1-butenyl, 1,3-Dimethyl-2-bu- tenyl, 1 ,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Di- methyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-bu- tenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl- 2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl und 1-Ethyl-2-methyl-2-propenyl;Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 -butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl 1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-ippropenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hex-enyl , 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pent-enyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl , 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pe ntenyl, 4-methyl-3-pent-enyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pent-enyl, 1, 1 Dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1,3-dimethyl-2-butyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1 butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl 2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Halogenalkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 8 Kohlenstoffatomen und einer oder zwei Doppelbindungen in beliebiger Position (wie vorstehend genannt), wobei in diesen Gruppen die Wasserstoffatome teilweise oder vollständig gegen Halogenatome wie vorstehend genannt, insbesondere Fluor, Chlor und Brom, ersetzt sein können; Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 4, 6 oder 8 Kohlenstoffatomen und einer oder zwei Dreifachbindungen in beliebiger Position, z.B. C2-C6-Alkinyl wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Me- thyl-2-propinyl, 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Me- thyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1 -butinyl, 1,1-Dimethyl-2-propinyI, 1-Ethyl-2- propinyl, 1-Hexinyi, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyi, 3-Methyl-1-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2-pentinyl, 1 ,1-Dimethyl-2-butinyl, 1,1-Dimethyl-3-butinyl, 1 ,2-Dimethyl-3-butinyl, 2,2-Dimethyl-3- butinyl, 3,3-Dimethyl-1 -butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl-3-butinyl und 1 -Ethyl-1 -methyl-2-propinyl;Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 8 carbon atoms and one or two double bonds in any position (as mentioned above), wherein in these groups, the hydrogen atoms partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be; Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl , 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2 Methyl 3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propylene, 1-ethyl-2-propynyl, 1-hexynedi, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5 Hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl , 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1, 2-dimethyl 3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1 Ethyl-1-methyl-2-propynyl;
Cycloalkyl: mono- oder bicyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis 6 oder 8 Kohlenstoffringgliedern, z.B. C3-C8-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyc- lopentyl, Cyclohexyl, Cycloheptyl und Cyclooctyl; fünf- bis zehngliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S: - 5- oder 6-gliedriges Heterocyclyl, enthaltend ein bis drei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome, z.B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-lsoxazolidinyl, 4-lsoxazolidinyl, 5-lsoxazolidinyl, 3-lsothiazolidinyl, 4-lsothiazolidinyl, 5-lsothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thia- zolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-lmidazolidinyl, 4-lmidazolidinyl, 2-Pyrrolin-2- yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperi- dinyl, 1 ,3-Dioxan-5-yl, 2-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydrothi- - enyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl und 2-Piperazinyl;Cycloalkyl: mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C 3 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; 5- to 10-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S: - 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or an oxygen or sulfur atom or a or two oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothi-enyl, 3-hexahydropyridazinyl, 4-hexahydropyridazi nyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stick- stoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, 4-Pyrazo- lyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazo- lyl, 2-lmidazolyl, 4-lmidazolyl, und 1,3,4-Triazol-2-yl; 6-gliedriges Heteroaryl, enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoffatome als Ringglieder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4- Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl und 2-Pyrazinyl;5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups which contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members may, for example, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5 Oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl; 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl , 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
Alkylen: divalente unverzweigte Ketten aus 3 bis 5 CH2-Gruppen, z.B. CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2 und CH2CH2CH2CH2CH2;Alkylene: divalent linear chains of 3 to 5 CH 2 groups, eg CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 and CH 2 CH 2 CH 2 CH 2 CH 2 ;
Oxyalkylen: divalente unverzweigte Ketten aus 2 bis 4 CH2-Gruppen, wobei eine Valenz über ein Sauerstoffatom an das Gerüst gebunden ist, z.B. OCH2CH2, OCH2CH2CH2 und OCH2CH2CH2CH2;Oxyalkylene: divalent unbranched chains of 2 to 4 CH 2 groups, wherein a valence is bonded to the skeleton via an oxygen atom, for example OCH 2 CH 2 , OCH 2 CH 2 CH 2 and OCH 2 CH 2 CH 2 CH 2 ;
Oxyalkylenoxy: divalente unverzweigte Ketten aus 1 bis 3 CH2-Gruppen, wobei beide Valenzen über ein Sauerstoffatom an das Gerüst gebunden ist, z.B. OCH2O, OCH2CH2O und OCH2CH2CH2O;Oxyalkylenoxy: divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
In dem Umfang der vorliegenden Erfindung sind die (R)- und (S)-Isomere und die Ra- zemate von Verbindungen der Formel I eingeschlossen, die chirale Zentren aufweisen.Included within the scope of the present invention are the (R) and (S) isomers and the racemates of compounds of formula I having chiral centers.
Die besonders bevorzugten Ausführungsformen der Zwischenprodukte in Bezug auf die Variablen entsprechen denen der Reste L und R3 der Formel I.The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the radicals L and R 3 of the formula I.
Im Hinblick auf ihre bestimmungsgemäße Verwendung der Triazolopyrimidine der Formel I sind die folgenden Bedeutungen der Substituenten, und zwar jeweils für sich allein oder in Kombination, besonders bevorzugt:With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:
Verbindungen der Formel I werden bevorzugt, in denen R1 nicht Wasserstoff bedeutet.Compounds of the formula I are preferred in which R 1 is not hydrogen.
Verbindungen I werden besonders bevorzugt, in denen R1 für d-d-Alky!, C2-C6-Alkenyl oder C C8-Halogenalkyl steht.Compounds I are particularly preferred in which R 1 is dd-alkyl, C 2 -C 6 -alkenyl or CC 8 -haloalkyl.
Verbindungen I sind bevorzugt, in denen R1 für eine Gruppe A steht: F F (CH '2,)'q-CHR3— A Z' Z worinCompounds I are preferred in which R 1 is a group A: FF (CH '2,)' q-CHR 3 - AZ 'Z wherein
Z1 Wasserstoff, Fluor oder CrC6-Fluoroalkyl, Z2 Wasserstoff oder Fluor, oder Z und Z2 bilden gemeinsam eine Doppelbindung; q 0 oder 1 ist; und R3 Wasserstoff oder Methyl bedeuten.Z 1 is hydrogen, fluorine or C 1 -C 6 -fluoroalkyl, Z 2 is hydrogen or fluorine, or Z and Z 2 together form a double bond; q is 0 or 1; and R 3 is hydrogen or methyl.
Außerdem werden Verbindungen I bevorzugt, in denen R1 für C3-C6-Cycloalkyl steht, welches durch C C4-Alkyl substituiert sein kann.In addition, compounds I are preferred in which R 1 is C 3 -C 6 -cycloalkyl, which may be substituted by CC 4 alkyl.
Insbesondere werden Verbindungen I bevorzugt, in denen R2 Wasserstoff bedeutet.In particular, compounds I are preferred in which R 2 is hydrogen.
Gleichermaßen bevorzugt sind Verbindungen I, in denen R2 für Methyl oder Ethyl steht.Equally preferred are compounds I in which R 2 is methyl or ethyl.
Sofern R1 und/oder R2 Halogenalkyl oder Halogenalkenylgruppen mit Chiralitäts- zentrum beinhalten, sind für diese Gruppen die (S)- Isomere bevorzugt. Im Fall halogenfreier Alkyl oder Alkenylgruppen mit Chiralitätszentrum in R1 oder R2 sind die (R)- konfigurierten Isomere bevorzugt.If R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with chiral centers, the (S) - isomers are preferred for these groups. In the case of halogen-free alkyl or alkenyl groups with chiral centers in R 1 or R 2 , the (R) -configured isomers are preferred.
Weiterhin werden Verbindungen I bevorzugt, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Piperidinyl-, Morpholinyl- oder Thio- morpholinylring bilden, insbesondere einen Piperidinylring, der ggf. durch eine bis drei Gruppen Halogen, d-C4-A!kyl oder d-C4-Halogenalkyl substituiert ist. Besonders bevorzugt sind die Verbindungen, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 4-Methylpiperidinring bilden.Furthermore, compounds I are preferred in which R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thio morpholinyl, in particular a piperidinyl ring which is optionally substituted by one to three halogen, dC 4 -alkyl or dC 4 -haloalkyl. Particularly preferred are the compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring.
Ein weiterer bevorzugter Gegenstand der Erfindung sind Verbindungen I, in denen R und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Pyrazol- ring bilden, der ggf. durch eine oder zwei Gruppen Halogen, d-C4-Alkyl oder d-C - Halogenalkyl, insbesondere durch 3,5-Dimethyl oder 3,5-Di-(trifluormethyl) substituiert ist.A further preferred subject of the invention are compounds I in which R and R 2 together with the nitrogen atom to which they are attached form a pyrazole ring which is optionally substituted by one or two groups halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkyl. Haloalkyl, in particular by 3,5-dimethyl or 3,5-di- (trifluoromethyl) is substituted.
Daneben sind auch Verbindungen der Formel I besonders bevorzugt, in denen R1 CH(CH3)-CH2CH3 , CH(CH3)-CH(CH3)2 , CH(CH3)-C(CH3)3 , CH(CH3)-CF3 , CH2C(CH3)=CH2 ,CH2CH=CH2 , Cyclopentyl oder Cyclohexyl; R2 Wasserstoff oder Methyl; oder R1 und R2 gemeinsam -(CH2)2CH(CH3)(CH2)2-, -(CH2)2CH(CF3)(CH2)2- oder -(CH2)2O(CH2)2- bedeuten.In addition, compounds of the formula I are particularly preferred in which R 1 is CH (CH 3 ) -CH 2 CH 3 , CH (CH 3 ) -CH (CH 3 ) 2 , CH (CH 3 ) -C (CH 3 ) 3 , CH (CH 3 ) -CF 3 , CH 2 C (CH 3 ) = CH 2 , CH 2 CH = CH 2 , cyclopentyl or cyclohexyl; R 2 is hydrogen or methyl; or R 1 and R 2 together are - (CH 2 ) 2 CH (CH 3 ) (CH 2 ) 2-, - (CH 2 ) 2 CH (CF 3 ) (CH 2 ) 2 - or - (CH 2 ) 2 O (CH2) 2 - mean.
Verbindungen I werden bevorzugt, in denen X Halogen, C C -Alkyl, Cyano oder d- C4-Alkoxy, wie Chlor, Methyl, Cyano, Methoxy oder Ethoxy, besonders Chlor oder Methyl, insbesondere Chlor bedeutet.Compounds I are preferred in which X is halogen, CC-alkyl, cyano or C 1 -C 4 -alkoxy, such as chlorine, methyl, cyano, methoxy or ethoxy, especially chlorine or methyl, in particular chlorine.
In Formel I bedeutet Hai insbesondere Chlor oder Fluor. Weiterhin sind Verbindungen I bevorzugt, in denen L1 C C2-Alkoxy, wie Methoxy; Cyano; Halogenmethyl, wie Trifluormethyl oder d-d-Alkoxycarbonyl, wie Methoxycarbo- nyl bedeutet. Besonders bevorzugt bedeuten in diesen Verbindungen L2 und L3 Was- serstoff.In formula I, shark is in particular chlorine or fluorine. Furthermore, compounds I are preferred in which L 1 is C 2 -alkoxy, such as methoxy; cyano; Halomethyl, such as trifluoromethyl or dd-alkoxycarbonyl, such as methoxycarbonyl means. In these compounds, L 2 and L 3 particularly preferably mean hydrogen.
Gleichsam sind Verbindungen I bevorzugt, in denen L2 C C2-Alkoxy, wie Methoxy; Cyano; Halogenmethyl, wie Trifluormethyl oder d-C4-Alkoxycarbonyl, wie Methoxy- carbonyl bedeutet. Besonders bevorzugt bedeuten in diesen Verbindungen L1 und L3 Wasserstoff.Similarly, compounds I are preferred in which L 2 CC 2 alkoxy, such as methoxy; cyano; Halomethyl, such as trifluoromethyl or dC 4 alkoxycarbonyl, such as methoxycarbonyl. Particularly preferred in these compounds L 1 and L 3 are hydrogen.
Daneben sind Verbindungen I bevorzugt, in denen L3 Wasserstoff bedeutet.In addition, compounds I are preferred in which L 3 is hydrogen.
Eine bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel 1.1:A preferred embodiment of the invention relates to compounds of the formula 1.1:
in der in the
G C2-C6-Alkyl, insbesondere Ethyl, n- und i-Propyl, n-, sek-, tert- Butyl, und C C4-Alkoxymethyl, insbesondere Ethoxymethyl, oder C3-C6-Cycloalkyl, insbesondere Cyclopentyl oder Cyclohexyl; R2 Wasserstoff oder Methyl; undGC 2 -C 6 -alkyl, in particular ethyl, n- and i-propyl, n-, sec-, tert-butyl, and CC 4 -alkoxymethyl, in particular ethoxymethyl, or C 3 -C 6 -cycloalkyl, in particular cyclopentyl or cyclohexyl ; R 2 is hydrogen or methyl; and
X Chlor, Methyl, Cyano, Methoxy oder Ethoxy bedeuten.X is chlorine, methyl, cyano, methoxy or ethoxy.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft Verbindungen, in denen R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, C C6-Alkyl, d-Ce-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, d-C6-Alkoxy, CrCe-Halogenalkoxy, C_-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, CrC6-Alkylen und Oxy-d-C3- alkylenoxy tragen kann. Diese Verbindungen entsprechen insbesondere Formel I.2,A further preferred embodiment of the invention relates to compounds in which R 1 and R 2 together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and another heteroatom from the group O , N and S as a ring member and / or one or more substituents selected from the group halogen, CC 6 alkyl, d-Ce-haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, dC 6 alkoxy CRCE haloalkoxy C_-C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, -C 6 alkylene and oxy-dC 3, - may bear alkyleneoxy. These compounds correspond in particular to formula I.2,
in der in the
D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bildet, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, d-C4-Alkyl, C C4-Alkoxy und d-C2-HalogenalkyI tragen kann; undD together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as ring member and / or one or more substituents from the group halogen, dC 4 - Alkyl, CC 4 alkoxy and dC 2 haloalkyl; and
X Chlor, Methyl, Cyano, Methoxy oder Ethoxy bedeuten.X is chlorine, methyl, cyano, methoxy or ethoxy.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft Verbindungen der Formel I.3.Another preferred embodiment of the invention relates to compounds of the formula I.3.
in der Y für Wasserstoff oder d-C -Alkyl, insbesondere für Methyl und Ethyl, und X für Chlor, Methyl, Cyano, Methoxy oder Ethoxy steht. in which Y is hydrogen or C 1 -C 4 -alkyl, in particular methyl and ethyl, and X is chlorine, methyl, cyano, methoxy or ethoxy.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen I bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet, unabhängig von der Kombination, in der sie genannt sind, eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar.In particular, with regard to their use, the compounds I compiled in the following tables are preferred. The groups mentioned in the tables for a substituent are also considered individually, regardless of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
Tabelle 1Table 1
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 methoxy, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 2Table 2
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 3Table 3
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 4Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 4
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 5Table 5
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 6Table 6
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluor, L 1 cyano, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 7Table 7
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 8Table 8
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluor, L 1 cyano, L 2 and L 3 is hydrogen and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 9Table 9
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 is trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 10Table 10
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle nTable n
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 12Compounds of the formula I in which X is methyl, Hal fluorine, L 1 is trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 12
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 13Table 13
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, fluorine, L 1 is methoxycarbonyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 14Table 14
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxycarbonyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 15Table 15
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxycarbonyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 16Table 16
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxycarbonyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 17Table 17
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal is chlorine, L 1 is methoxy, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 18Table 18
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 19Table 19
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 20Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxy, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 20
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 21Table 21
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal is chlorine, L 1 is cyano, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 22Table 22
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 23Table 23
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 24Table 24
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 25Table 25
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal is chlorine, L 1 is trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 26Table 26
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is trifluoromethyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 27Table 27
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 28Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is trifluoromethyl, L 2 and L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 28
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Trifluormethyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is trifluoromethyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 29Table 29
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal is chlorine, L is methoxycarbonyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 30Table 30
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxycarbonyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 31Table 31
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxycarbonyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 32Table 32
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxycarbonyl, L2 und L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxycarbonyl, L 2 and L 3 are hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 33Table 33
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 34Table 34
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 35Table 35
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 36Compounds of the formula I in which X is methyl, Hal fluorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 36
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 37Table 37
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 38Table 38
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 39Table 39
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 40Table 40
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 41Table 41
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 42Table 42
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 43Table 43
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 44Compounds of the formula I in which X is methyl, Hal fluorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 44
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 45Table 45
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 46Table 46
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 47Table 47
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is fluorine, L is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 48Table 48
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is fluorine, L is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 49Table 49
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 50Table 50
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 51Table 51
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 52Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 52
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Wasserstoff, L2 Methoxy, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is hydrogen, L 2 is methoxy, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 53Table 53
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 54Table 54
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 55Table 55
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 56Table 56
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Wasserstoff, L2 Cyano, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is hydrogen, L 2 is cyano, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 57Table 57
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 58Table 58
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 59Table 59
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 60Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 60
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Wasserstoff, L2 Trifluormethyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is hydrogen, L 2 is trifluoromethyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 61Table 61
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 62Table 62
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 63Table 63
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 64Table 64
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Wasserstoff, L2 Methoxycarbonyl, L3 Wasserstoff und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is hydrogen, L 2 is methoxycarbonyl, L 3 is hydrogen and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 65Table 65
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 66Table 66
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 67Table 67
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 68Compounds of the formula I in which X is methyl, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 68
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 69Table 69
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 70Table 70
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 und L2 Wasserstoff , L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 71Table 71
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 72Table 72
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 73Table 73
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 74Table 74
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 75Table 75
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 76Compounds of the formula I in which X is methyl, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 76
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 77Table 77
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 78Table 78
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 79Table 79
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 und L2 Wasserstoff , L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 80Table 80
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 81Table 81
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 82Table 82
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 83Table 83
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 and L 2 are hydrogen, L 3 Methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 84 Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 84 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 85 Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 85 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 86 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 86 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 87 Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 87 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 88 Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 und L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 88 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 89 Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 89 Compounds of the formula I in which X is chlorine, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 90 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 91Table 90 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 91
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 92Table 92
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 und L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 93Table 93
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 and L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 94Table 94
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 and L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 95Table 95
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 96Table 96
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 und L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 97Table 97
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 and L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 98Table 98
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 99Compounds of the formula I in which X is cyano, Hal, chlorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 99
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 100Table 100
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 101Table 101
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 102Table 102
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal, chlorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 103Table 103
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 104Table 104
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 und L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 and L 2 are hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 105Table 105
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 106Table 106
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 Fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 107 Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 107 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 108 Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 108 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 109 Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 109 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 110 Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 110 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 111 Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable III Compounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 112 Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, Lz Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 112 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L z is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 113 Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 114Table 113 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 114
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 115Table 115
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 116Table 116
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluor, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 117Table 117
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, fluorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 118Table 118
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 119Table 119
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 120Table 120
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 121Table 121
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 122Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 122
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Cyano, L2 Wasserstoff , L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 123Table 123
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 124Table 124
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 125Table 125
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 126Table 126
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 127Table 127
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 128Table 128
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 129Table 129
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 Chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 130 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 130 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 131 Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 131 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 132 Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 132 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 133 Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 133 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 134 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 134 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 135 Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 135 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 136 Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 137Table 136 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 137
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 138Table 138
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 139Table 139
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 140Table 140
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 141Table 141
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 142Table 142
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Cyano, L2 Wasserstoff , L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 143Table 143
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 144Table 144
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Cyano, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 145Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is cyano, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 145
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, fluorine, L 1 is methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 146Table 146
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 147Table 147
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 148Table 148
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 149Table 149
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 150Table 150
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 151Table 151
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 152Table 152
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 Wasser- Stoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 hydrogen Substance, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 153 Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 153 Compounds of the formula I in which X corresponds to chlorine, Hal fluorine, L 1 methoxy, L 2 hydrogen, L 3 cyano and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 154 Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 154 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 155 Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 155 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 156 Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 156 Compounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 157 Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 157 Compounds of the formula I in which X is chlorine, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 158 Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 158 Compounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 159 Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 160Table 159 Compounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R and R 2 for a compound corresponds in each case to one row of Table A. Table 160
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 161Table 161
Verbindungen der Formel I, in denen X Chlor, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 162Table 162
Verbindungen der Formel I, in denen X Cyano, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 163Table 163
Verbindungen der Formel I, in denen X Methyl, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 164Table 164
Verbindungen der Formel I, in denen X Methoxy, Hai Fluor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal fluorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 165Table 165
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 166Table 166
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy,, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 167Table 167
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 168Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A. Table 168
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Fluor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is fluorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 169Table 169
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 170Table 170
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 171Table 171
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 172Table 172
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Chlor und die Kombination von R1 und R2 für eine Verbindung.jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is chlorine and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 173Table 173
Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is chlorine, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 174Table 174
Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 175Table 175
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 cyano and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 176 Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Cyano und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 176 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is cyano and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 177 Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 177 Compounds of the formula I in which X is chlorine, Hal is chlorine, L is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 178 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 178 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 179 Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 179 Compounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 180 Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxy und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 180 Compounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxy and the combination of R 1 and R 2 for each compound corresponds to one row of Table A.
Tabelle 181 Verbindungen der Formel I, in denen X Chlor, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 181 Compounds of the formula I in which X is chlorine, Hal chlorine, L 1 methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 182 Verbindungen der Formel I, in denen X Cyano, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 183Table 182 Compounds of the formula I in which X is cyano, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for each compound corresponds to one row of Table A. Table 183
Verbindungen der Formel I, in denen X Methyl, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methyl, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle 184Table 184
Verbindungen der Formel I, in denen X Methoxy, Hai Chlor, L1 Methoxy, L2 Wasserstoff, L3 Methoxycarbonyl und die Kombination von R1 und R2 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is methoxy, Hal is chlorine, L 1 is methoxy, L 2 is hydrogen, L 3 is methoxycarbonyl and the combination of R 1 and R 2 for a compound corresponds in each case to one row of Table A.
Tabelle ATable A
Die Verbindungen I eignen sich als Fungizide. Sie zeichnen sich aus durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromyceten, Oomyceten und Ba- sidiomyceten. Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Blatt- und Bodenfungizide eingesetzt werden.The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Bassidiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Ba- nanen, Baumwolle, Soja, Kaffee, Zuckerrohr, Wein, Obst- und Zierpflanzen und Gemüsepflanzen wie Gurken, Bohnen, Tomaten, Kartoffeln und Kürbisgewächsen, sowie an den Samen dieser Pflanzen. Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten: Alternaria-Arten an Gemüse und Obst, Bipolaris- und Drechslera-Arten an Getreide, Reis und Rasen, Blumeria graminis (echter Mehltau) an Getreide, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Fusarium- und Verticiliium-Arten an verschiedenen Pflanzen, Mycosphaerella-Aύen an Getreide, Bananen und Erdnüssen, Phytophthora infestans an Kartoffeln und Tomaten, Plasmopara viticola an Reben, Podosphaera leucotricha an Äpfeln, Pseudocercosporella herpotrichoides an Weizen und Gerste, Pseudoperonospora-Aύen an Hopfen und Gurken, Puccinia-Arien an Getreide, Pyricularia oryzae an Reis, Rhizoctonia-Aύe an Baumwolle, Reis und Rasen, Septoria tritici und Stagonospora nodorum an Weizen, Uncinula necator an Reben, Ustilago-Arten an Getreide und Zuckerrohr, sowie Ven.t/r/a-Arten (Schorf) an Äpfeln und Birnen.They are particularly important for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants. Specifically, they are suitable for controlling the following plant diseases: Alternaria species on vegetables and fruits, Bipolaris and Drechslera species on cereals, rice and turf, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Fusarium and Verticiliium species on various plants, Mycosphaerella cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora on hops and cucumbers, Puccinia on cereals, Pyricularia oryzae on rice, Rhizoctonia on cotton, rice and turf, Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines, Ustilago species on cereals and sugar cane, as well as Ven.t / r / a species (scab) on apples and pears.
Die Verbindungen I eignen sich außerdem zur Bekämpfung von Schadpilzen wie Pae- cilomyces variotii im Materialschutz (z.B. Holz, Papier, Dispersionen für den Anstrich, Fasern bzw. Gewebe) und im Vorratsschutz.The compounds I are also suitable for controlling harmful fungi such as Pecilomyces variotii in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
Die Verbindungen I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung kann sowohl vor als auch nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze erfolgen.The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.
Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.-% Wirkstoff.The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.
Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 1 bis 1000 g/100 kg Saatgut, vorzugsweise 1 bis 200 g/100 kg, insbesondere 5 bis 100 g/100 kg verwendet.The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha. In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg of seed, preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg are used.
Bei der Anwendung im Material- bzw. Vorratsschutz richtet sich die Aufwandmenge an Wirkstoff nach der Art des Einsatzgebietes und des gewünschten Effekts. Übliche Aufwandmengen sind im Materialschutz beispielsweise 0,001 g bis 2 kg, vorzugsweise 0,005 g bis 1 kg Wirkstoff pro Kubikmeter behandelten Materials.When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
Die Verbindungen I können in die üblichen Formulierungen überführt werden, z.B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung gewährleisten.The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln. Als Lösungsmittel / Hilfsstoffe kommen dafür im wesentlichen in Betracht: - Wasser, aromatische Lösungsmittel (z.B. Solvesso Produkte, Xylol), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol, Pentanol, Benzylalko- hol), Ketone (z.B. Cyclohexanon, gamma-Butryolacton), Pyrrolidone (NMP, NOP), Acetate (Glykoldiacetat), Glykole, Dimethylfettsäureamide, Fettsäuren und Fettsäureester. Grundsätzlich können auch Lösungsmittelgemische ver- wendet werden, - Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyo- xyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergier- mittel wie Lignin-Sulfitablaugen und Methylcellulose.The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma Butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used, - carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (for example, polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants, such as lignin-sulphite liquors and methylcellulose.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate, Fettsäuren und sulfa- tierte Fettalkoholglykolether zum Einsatz, ferner Kondensationsprodukte von sulfonier- tem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethy- lenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphe- nolpolyglykolet er, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Alkohol- und Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpoly- glykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene lenoctylphenolether, ethoxylated isooctylphenol, octylphenol, nonylphenol, Alkylphe- nolpolyglykolet er, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, alcohol and Fettalkoholethylenoxid condensates, ethoxylated Castor oil, polyoxyethylene alkyl, ethoxylated polyoxypropylene, Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Öldis- persionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kero- sin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xy- lol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Isophoron, stark polare Lösungsmittel, z.B. Dimethylsulfoxid, N-Methylpyrrolidon oder Wasser in Betracht.For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver und andere feste Trägerstoffe.Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.-%, vorzugs- weise zwischen 0,1 und 90 Gew.-% des Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
Beispiele für Formulierungen sind: 1. Produkte zur Verdünnung in WasserExamples of formulations are: 1. Products for dilution in water
A Wasserlösliche Konzentrate (SL)A Water Soluble Concentrates (SL)
10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff.10 parts by weight of a compound of the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.
B Dispergierbare Konzentrate (DC)B Dispersible Concentrates (DC)
20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Cyclohexanon unter Zusatz eines Dispergiermittels z.B. Polyvinylpyrrolidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. C Emulgierbare Konzentrate (EG)20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant, for example polyvinylpyrrolidone. Dilution in water gives a dispersion. C Emulsifiable Concentrates (EC)
15 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Xylol unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 %) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emulsion.15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Dilution in water results in an emulsion.
D Emulsionen (EW, EO)D emulsions (EW, EO)
40 Gew.-Teile einer erfindungsgemäßen Verbindung werden in Xylol unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 %) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (Ultraturax) in Wasser eingebracht und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion.40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
E Suspensionen (SC, OD)E suspensions (SC, OD)
20 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln und Wasser oder einem organischen Lösungsmittel in einer20 parts by weight of a compound according to the invention are mixed with the addition of dispersants and wetting agents and water or an organic solvent in a
Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs.Agitator ball mill to a fine suspension of active ingredient crushed. Dilution in water results in a stable suspension of the active ingredient.
F Wasserdispergierbare und wasserlösliche Granulate (WG, SG) 50 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs.F Water-dispersible and Water-soluble Granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
G Wasserdispergierbare und wasserlösliche Pulver (WP, SP) 75 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von Disper- gier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirk- Stoffs.G Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active substance.
2. Produkte für die Direktapplikation2. Products for direct application
H Stäube (DP) 5 Gew.Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95 % feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel.H dusts (DP) 5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dust.
I Granulate (GR, FG, GG, MG)I Granules (GR, FG, GG, MG)
0.5 Gew-Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95.5 % Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation.0.5 parts by weight of a compound according to the invention are finely ground and combined with 95.5% excipients. Common methods are the extrusion, the Spray drying or the fluidized bed. This gives granules for direct application.
J ULV- Lösungen (UL) 10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einem organischen Lösungsmittel z.B. Xylol gelöst. Dadurch erhält man ein Produkt für die Direktapplikation.ULV solutions (UL) 10 parts by weight of a compound of the invention are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus berei- teten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfin- dungsgemäßen Wirkstoffe gewährleisten.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Sub- stanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emuigiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulgent. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1%.The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.-% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
Zu den Wirkstoffen können Öle verschiedenen Typs, Netzmittel, Adjuvants, Herbizide, Fungizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel können zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1:10 bis 10:1 zugemischt werden. Die erfindungsgemäßen Mittel können in der Anwendungsform als Fungizide auch zusammen mit anderen Wirkstoffen vorliegen, der z.B. mit Herbiziden, Insektiziden, Wachstumsregulatoren, Fungiziden oder auch mit Düngemitteln. Beim Vermischen der Verbindungen I bzw. der sie enthaltenden Mittel in der Anwendungsform als Fungizide mit anderen Fungiziden erhält man in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums.To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the inventive compositions in a weight ratio of 1:10 to 10: 1. The agents according to the invention can also be present in the application form as fungicides together with other active substances, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.
Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken:The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.
• Acylalanine wie Benalaxyl, Metalaxyl, Ofurace, Oxadixyl;Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;
• Aminderivate wie Aldimorph, Dodine, Dodemorph, Fenpropimorph, Fenpropidin, Guazatine, Iminoctadine, Spiroxamin, Tridemorph; • Anilinopyrimidine wie Pyrimethanil, Mepanipyrim oder Cyrodinyl;Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph; Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl;
• Antibiotika wie Cycloheximid, Griseofulvin, Kasugamycin, Natamycin, Polyoxin oder Streptomycin;• antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin;
• Azole wie Bitertanol, Bromoconazol, Cyproconazol, Difenoconazole, Dinitrocona- zol, Enilconazol, Epoxiconazol, Fenbuconazol, Fluquiconazol, Flusilazol, Flutriafol, Hexaconazol, Imazalil, Metconazol, Myclobutanil, Penconazol, Propiconazol, Prochloraz, Prothioconazol, Tebuconazol, Triadimefon, Triadimenol, Triflumizol, Triticonazol;• Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochlorazole, prothioconazole, tebuconazole, triadimefon, triadimol, triflumizole , Triticonazole;
• Dicarboximide wie Iprodion, Myclozolin, Procymidon, Vinclozolin;Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;
• Dithiocarbamate wie Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propi- neb, Polycarbamat, Thiram, Ziram, Zineb;Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;
• Heterocylische Verbindungen wie Anilazin, Benomyl, Boscalid, Carbendazim, Car- boxin, Oxycarboxin, Cyazofamid, Dazomet, Dithianon, Famoxadon, Fenamidon, Fenarimol, Fuberidazol, Flutolanil, Furametpyr, Isoprothiolan, Mepronil, Nuarimol, Probenazol, Proquinazid, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam, Thiaben- dazol, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazol, Triforine;Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxaldine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazide, pyrifenox, pyroquilone, Quinoxyfen, silthiofam, thiabenazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine;
• Kupferfungizide wie Bordeaux Brühe, Kupferacetat, Kupferoxychlorid, basisches Kupfersulfat;Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate;
• Nitrophenylderivate, wie Binapacryl, Dinocap, Dinobuton, Nitrophthal-isopropyl;Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl;
• Phenylpyrrole wie Fenpiclonil oder Fludioxonil; • Schwefel;Phenylpyrroles such as fenpiclonil or fludioxonil; • sulfur;
• Sonstige Fungizide wie Acibenzolar-S-methyl, Benthiavalicarb, Carpropamid, Chlo- rothalonil, Cyflufenamid, Cymoxanil, Dazomet, Diclomezin, Diclocymet, Diethofen- carb, Edifenphos, Ethaboxam, Fenhexamid, Fentin-Acetat, Fenoxanil, Ferimzone, Fluazinam, Fosetyl, Fosetyl-Aluminium, Iprovalicarb, Hexachlorbenzol, Metrafenon, Pencycuron, Propamocarb, Phthalid, Toloclofos-methyl, Quintozene, Zoxamid; • Strobilurine wie Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin oderTrifloxystrobin;Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorotrilone, cyflufenamid, cymoxanil, dazomet, diclomethine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, Fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide; Strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin;
• Sulfensäurederivate wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid;Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
• Zimtsäureamide und Analoge wie Dimethomorph, Flumetover oder Flumorph.Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
Synthesebeispielesynthesis Examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in der anschließenden Tabelle mit physikalischen Angaben aufgeführt.The instructions given in the Synthesis Examples below were used with appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the following table with physical data.
Beispiel 1 : Herstellung von 5-Chlor-6-(2-fluor,3-trifluormethyl-phenyl)-7-(4-methyl- piperidinyl)-1 ,2,4-triazolo[1 ,5a]pyrimidinExample 1: Preparation of 5-chloro-6- (2-fluoro, 3-trifluoromethylphenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a] pyrimidine
a) 2-(2-Fluor,3-trifluormethyl-phenyl)-malonsäuredimethylestera) 2- (2-fluoro, 3-trifluoromethyl-phenyl) -malonate
Eine Mischung aus 5,1 g (0,03 mol) Kalium-dimethylmalonat und 1 g Kupferbromid in 40 ml Diethylenglykoldimethylether wurden ca. 1 Std. bei 100° gerührt. Anschließend gab man 2,43 g (0,01 mol) 2-Fluor-3-trifluorphenyl-brombenzol hinzu und rührte ca. 3 Std. bei 100°C weiter. Nach Zugabe von weiteren 3 g Kalium-dimethylmalonat wurden noch 3 Std. bei 110°C gerührt.A mixture of 5.1 g (0.03 mol) of potassium dimethylmalonate and 1 g of copper bromide in 40 ml of diethylene glycol dimethyl ether was stirred for about 1 hour at 100 °. Subsequently, 2.43 g (0.01 mol) of 2-fluoro-3-trifluorophenyl bromobenzene were added and the mixture was stirred for about 3 hours at 100 ° C on. After addition of a further 3 g of potassium dimethylmalonate, stirring was continued for 3 hours at 110.degree.
Dann wurde die Reaktionsmischung mit konz. Salzsäure angesäuert und mit Methyl-t- butylether (MTBE) extrahiert. Die vereinigten organischen Phasen wurden getrocknet und vom Lösungsmittel befreit. Der erhaltene Rückstand wurde mit Cyclohexan/Essig- ester-Gemischen aufgenommen und über Kieselgel abfiltriert. Das Eluat wurde vom Lösungsmittel befreit, der Rückstand getrocknet. Als Rückstand wurden 2,7 g der Titelverbindung erhalten.Then the reaction mixture was treated with conc. Hydrochloric acid and extracted with methyl t-butyl ether (MTBE). The combined organic phases were dried and freed from the solvent. The residue obtained was taken up in cyclohexane / ethyl acetate mixtures and filtered through silica gel. The eluate was freed from the solvent, the residue was dried. As a residue, 2.7 g of the title compound were obtained.
1H-NMR (CDCI3l δ in ppm): 7,75 (t, 1H); 7,6 (t, 1H); 7,3 (t, 1H); 5,1 (s, 1H); 3,8 (s, 6H). 1 H-NMR (CDCl 3 Iδ in ppm): 7.75 (t, 1H); 7.6 (t, 1H); 7.3 (t, 1H); 5.1 (s, 1H); 3.8 (s, 6H).
b) 5,7-Dihydroxy-6-(2-fluor,3-trifluormethyl-phenyl)-1 ,2,4-triazolo[1 ,5a]pyrimidinb) 5,7-Dihydroxy-6- (2-fluoro, 3-trifluoromethyl-phenyl) -1,2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 2,7 g (9,2 mmo!) 2-(2-Fluor,3-trifluormethyl-phenyl)-malonsäure- dimethylester (aus Bsp. 1a) und 0,8 g (9,5 mmol) Aminotriazol in 2,1 g Tributylamin wurden ca. 3 Std. bei etwa 170°C gerührt, wobei Methanol abdestillierte. Anschließend wurde die Reaktionsmischung auf ca. 80-100°C abgekühlt und mit 20 %iger Natronlauge versetzt. Man extrahierte die wässrige Phase mit MTBE und säuerte sie mit konz. Salzsäure an. Die wässrige Phase wurde mit Methylenchlord extrahiert, die wässrige Phase wurde abfiltriert, der Filterrückstand wurde in Tetrahydrofuran gelöst. Sowohl die vereinigten organischen Phasen wurden getrocknet und von den Lösungsmitteln befreit. Als Rückstand erhielt man 2,0 g der Titelverbindung als beigen Festkörper, der ohne weitere Reinigung in die nächste Reaktion eingesetzt wurde.A solution of 2.7 g (9.2 mmol) of 2- (2-fluoro, 3-trifluoromethyl-phenyl) -malonic acid dimethyl ester (from Ex. 1a) and 0.8 g (9.5 mmol) of aminotriazole in 2.1 g of tributylamine were stirred for about 3 hours at about 170 ° C, with methanol distilled off. Subsequently, the reaction mixture was cooled to about 80-100 ° C and treated with 20% sodium hydroxide solution. The aqueous phase was extracted with MTBE and acidified with conc. Hydrochloric acid on. The aqueous phase was extracted with methylene chloride, the aqueous phase was filtered off, the filter residue was dissolved in tetrahydrofuran. Both the combined organic phases were dried and freed from the solvents. The residue obtained was 2.0 g of the title compound as a beige solid, which was used without further purification in the next reaction.
c) 5,7-Dichlor-6-(2-fluor,3-trifluormethyl-phenyl)-1 ,2,4-triazolo[1 ,5a]pyrimidinc) 5,7-dichloro-6- (2-fluoro, 3-trifluoromethylphenyl) -1,2,4-triazolo [1,5a] pyrimidine
Eine Lösung von 2,0 g (6,7 mmol) 5,7-Dihydroxy-6-(2-fluor,3-trifluormethyl-phenyl)- 1,2,4-triazolo[1,5a]pyrimidin (aus Beispiel 1b) in 30 ml Phosphoroxychlorid wurden ca. 5 Std. bei 100°C gerührt. Anschließend destillierte man das überschüssige Phosphoroxychlorid ab, nahm den Rückstand mit Methylenchlorid und Wasser auf und neutralisierte diese Mischung mit NaHCO3. Anschließend wurden die Phasen getrennt und die wässrige mit Methylenchlorid extrahiert. Dann trocknete man die vereinigten organischen Phasen und destillierte das Lösungsmittel ab. Nach Chromatographie an Kiesel- gel mit Cyclohexan/Essigester-Gemischen wurden 0,9 g der Titelverbindung erhalten.A solution of 2.0 g (6.7 mmol) of 5,7-dihydroxy-6- (2-fluoro, 3-trifluoromethylphenyl) -1,2,4-triazolo [1,5a] pyrimidine (from Example 1b ) in 30 ml of phosphorus oxychloride were stirred at 100 ° C for about 5 hrs. The excess phosphorus oxychloride was then distilled off, the residue was taken up in methylene chloride and water, and this mixture was neutralized with NaHCO 3 . Subsequently, the phases were separated and the aqueous extracted with methylene chloride. Then the combined organic phases were dried and the solvent was distilled off. Chromatography on silica gel with cyclohexane / ethyl acetate mixtures gave 0.9 g of the title compound.
1H-NMR (CDCI3l δ in ppm): 8,65 (s, 1H); 8,4 (t, 1H); 7,6 (t, 1H); 7,5 (t, 1H). 1 H-NMR (CDCl 3 I δ in ppm): 8.65 (s, 1H); 8.4 (t, 1H); 7.6 (t, 1H); 7.5 (t, 1H).
1 d) 5-Chlor-6-(2-fluor,3-trifluormethyl-phenyl)-7-(4-methylpiperidinyl)-1 ,2,4-tri- azolo[1 ,5ajpyrimidin1 d) 5-Chloro-6- (2-fluoro, 3-trifluoromethylphenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5-pyrimidine
Eine Lösung von 0,25 g (0,7 mmol) 5,7-Dichlor-6-(2-fluor,3-trifluormethyl-phenyl)-1,2,4- triazolo[1 ,5a]pyrimidin (aus Beispiel 1c), 0,106 g (146 μl, 1,05 mmol) Triethylamin und 0,104 g 4-Methylpiperidin (als 0,8 m Lösung in Methylenchlorid) in 4 ml Methylenchlorid wurden 5 Std. bei 35°C und 15 Stunden bei 20-25°C gerührt. Die Reaktionsmischung wurde mit verd. Salzsäure und Kochsalz-Lösung extrahiert. Die organische Phase wurde getrocknet und vom Lösungsmittel befreit. Es blieben 0,156 g der Titelverbindung als blasse Kristallmasse vom Fp. 166-170°C zurück.A solution of 0.25 g (0.7 mmol) of 5,7-dichloro-6- (2-fluoro, 3-trifluoromethyl-phenyl) -1,2,4-triazolo [1, 5a] pyrimidine (from Example 1c ), 0.106 g (146 μL, 1.05 mmol) of triethylamine and 0.104 g of 4-methylpiperidine (as a 0.8 M solution in methylene chloride) in 4 mL of methylene chloride were stirred at 35 ° C for 5 h and at 20-25 ° C for 15 h C stirred. The reaction mixture was extracted with dil. Hydrochloric acid and brine. The organic phase was dried and freed from the solvent. There remained 0.156 g of the title compound as a pale crystal mass, mp. 166-170 ° C back.
HPLC/MS: Rt=3,929 min; m/z=414 (M++H)HPLC / MS: R t = 3.929 min; m / z = 414 (M + + H)
HPLC-Säule: RP-18 Säule (Chromolith Speed ROD von Merck KgaA, Deutschland) Eluent: Acetonitril + 0,1% Trifuoressigsäure (TFA)/ Wasser + 0,1% TFA (Gradient von 5:95 bis 95:5 in 5 min), 40°C. MS: Quadrupol Elektrospray Ionisation, 80 V (positiv Modus) Tabelle I - Verbindungen der FormelHPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany) eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA (gradient from 5:95 to 95: 5 in 5 min), 40 ° C. MS: Quadrupole electrospray ionization, 80 V (positive mode) Table I - Compounds of the formula
Beispiele für die Wirkung gegen SchadpilzeExamples of the effect against harmful fungi
Die fungizide Wirkung der Verbindungen der Formel I ließ sich durch die folgenden Versuche zeigen:The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:
Die Wirkstoffe wurden getrennt als eine Stammlösung aufbereitet mit 25 mg Wirkstoff, welcher mit einem Gemisch aus Aceton und/oder D SO und dem Emulgator Unipe- rol® EL (Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) im Volumen-Verhältnis Lösungsmittel-Emulgator von 99 zu 1 ad 10 ml aufgefüllt wurde. Anschließend wurde ad 100 ml mit Wasser aufgefüllt. Diese Stammlösung wurde mit dem beschriebenen Lösungsmittel-Emulgator-Wasser Gemisch zu der unten angegebenen Wirkstoffkonzentration verdünnt.The active compounds were separately prepared as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or D SO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
Anwendungsbeispiel 1 - Wirksamkeit gegen den Grauschimmel an Paprikablättern verursacht durch Botrytis cinerea bei protektiver AnwendungUse Example 1 - Anti-gray pepper efficacy caused by Botrytis cinerea in protective application
Paprikasämlinge der Sorte "Neusiedler Ideal Elite" wurden, nachdem sich 2 - 3 Blätter gut entwickelt hatten, mit einer wässrigen Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am nächsten Tag wurden die behandelten Pflanzen mit einer Sporensuspension von Botrytis cinerea, die 1 ,7 x 106 Sporen/ml in einer 2 %igen wässrigen Biomalzlösung enthielt, inokuliert. Anschließend wurden die Versuchspflanzen in eine Klimakammer mit 22 bis 24°C, Dunkelheit und hoher Luftfeuchtigkeit gestellt. Nach 5 Tagen konnte das Ausmaß des Pilzbefalls auf den Blättern visuell in % ermittelt werden.Paprika seedlings of the cultivar "Neusiedler Ideal Elite" were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 × 10 6 spores / ml in a 2% aqueous biomalt solution. Subsequently, the test plants were placed in a climatic chamber at 22 to 24 ° C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.
In diesem Test zeigten die mit 63 ppm der Wirkstoffe I-3, 1-4, 1-7, 1-13 bis 1-16, 1-18 bis I-22, I-24 bis I-26, 1-28, 1-30 bis I-32, 1-34, 1-38, 1-40, 1-42, 1-45, 1-47 bis I-49, 1-52, 1-54 bis I-57, I-88, 1-99, 1-1061-114, 1-116, 1-121, 1-136, 1-137, 1-140, 1-144, 1-149, 1-159, 1-167, 1-172, 1-174, 1-176, 1-179, 1-180, 1-182 bis 1-185, 1-190, 1-191, 1-193, 1-199, I-202, I-207 bis I-209, bzw. 1-215 behandelten Pflanzen nicht über 30 % Befall, während die unbehandelten Pflanzen zu 85 % befallen waren.In this test, those containing 63 ppm of the active ingredients I-3, 1-4, 1-7, 1-13 to 1-16, 1-18 to I-22, I-24 to I-26, 1-28, 1-30 to I-32, 1-34, 1-38, 1-40, 1-42, 1-45, 1-47 to I-49, 1-52, 1-54 to I-57, I- 88, 1-99, 1-1061-114, 1-116, 1-121, 1-136, 1-137, 1-140, 1-144, 1-149, 1-159, 1-167, 1- 172, 1-174, 1-176, 1-179, 1-180, 1-182 to 1-185, 1-190, 1-191, 1-193, 1-199, I-202, I-207 to I-209, or 1-215 treated plants did not exceed 30% infestation, while untreated plants were 85% infected.
Anwendungsbeispiel 2: Wirksamkeit gegen die Dürrfleckenkrankheit der Tomate verursacht durch Alternaria solaniUse Example 2: Efficacy against tomato blight caused by Alternaria solani
Blätter von Topfpflanzen der Sorte "Goldene Königin" wurden mit einer wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am folgenden Tag wurden die Blätter mit einer wässrigen Sporenaufschwemmung von Alternana solani in 2 % Biomalzlösung mit einer Dichte von 0,17 x 106 Sporen/ml infiziert. Anschließend wurden die Pflanzen in einer wasserdampf-gesättigten Kammer bei Temperaturen zwischen 20 und 22°C aufgestellt. Nach 5 Tagen hatte sich die Krankheit auf den unbehandelten, jedoch infizierten Kontrollpflanzen so stark entwickelt, dass der Befall visuell in % ermittelt werden konnte.Leaves of potted plants of the "Golden Queen" variety were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. The following day, the leaves were infected with an aqueous spore suspension of Alternana solani in 2% biomalt solution with a density of 0.17 x 10 6 spores / ml. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days the disease had started The untreated but infected control plants developed so strongly that the infestation could be determined visually in%.
In diesem Test zeigten die mit 63 ppm der Wirkstoffe 1-14, 1-20, 1-22, 1-24, 1-26, 1-28, I-30, 1-33, I-34, I-36, I-45, I-47, I-54, I-60, 1-61, I-98, 1-103, 1-105, 1-107, 1-114, 1-159, 1-167, bzw. 1-182 behandelten Pflanzen nicht über 30 % Befall, während die unbehandelten Pflanzen zu 90 % befallen waren. In this test, those containing 63 ppm of drugs 1-14, 1-20, 1-22, 1-24, 1-26, 1-28, I-30, 1-33, I-34, I-36, I-45, I-47, I-54, I-60, 1-61, I-98, 1-103, 1-105, 1-107, 1-114, 1-159, 1-167, and 1-182 treated plants did not exceed 30% infestation, while untreated plants were 90% infected.

Claims

Patentansprücheclaims
1. Triazolopyrimidine der Formel I1. Triazolopyrimidines of the formula I.
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meanings:
R1, R2 unabhängig voneinander CrC8-Alkyl, C C8-Halogenalkyl, C3-C8-Cyc- loalkyl, C3-C8-Halogencycloalkyl, C2-C8-Alkenyl, C2-C8-Halogenalkenyi, C3-C6-Cycloalkenyl, C3-C6-Halogencycloalkenyl, C2-C8-Alkinyl, C2-C8- Halogenalkinyl oder Phenyl, Naphthyl, oder ein fünf- oder sechsgliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Heteroatome aus der Gruppe O, N oder S,R 1, R 2 are independently C r C 8 alkyl, CC 8 -haloalkyl, C 3 -C 8 loalkyl -Cyc-, C 3 -C 8 halocycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 -Halogenalkenyi, C 3 -C 6 cycloalkenyl, C 3 -C 6 halocycloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 - haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S,
R und R2 können auch zusammen mit dem Stickstoffatom, an das sie ge- bunden sind, ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bilden, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, Cι-C6-Alkyl, CrC6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, CrC6-Alkoxy, CrCe-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, CrC6-Alkylen und Oxy-CrC3- alkylenoxy tragen kann;R and R 2 may also together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as ring member and / or one or more substituents from the group halogen, Cι-C6 alkyl, -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, -C 6 alkoxy, CRCE haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, -C 6 alkylene and oxy-C r C 3 - may bear alkyleneoxy;
R1 und/oder R2 können eine bis vier gleiche oder verschiedene Gruppen Ra tragen:R 1 and / or R 2 may carry one to four identical or different groups R a :
Ra Halogen, Cyano, Nitro, Hydroxy, C C6-Alkyl, C C6-Halogenalkyl, CrC6-Alkylcarbonyl, C3-C6-Cycloalkyl, CrCrAlkoxy, C C6-Halogen- alkoxy, CrC6-Alkoxycarbonyl, CrC6-Alkylthio, CrC6 jAlkylamino, Di- CrC6-alkylamino, C2-C8-Alkenyl, C2-C8-Halogenalkenyl, C3-C8-Cyclo- alkenyl, C2-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, C2-C6-Alkinyl, C2-C6-Halogenalkinyl, C3-C6-Alkinyloxy, C3-C6-Halogenalkinyloxy, C3-C6-Cycloalkoxy, C3-C6-Cycloalkenoxy, CrC3-Oxyalkylenoxy, Phenyl, Naphthyl, fünf- bis zehngliedriger gesättigter, partiell ungesättigter oder aromatischer Heterocyclus, enthaltend ein bis vier Hetero- atome aus der Gruppe O, N oder S, wobei diese aliphatischen, alicyclischen oder aromatischen Gruppen ihrerseits partiell oder vollständig halogeniert sein oder eine bis drei Gruppen Rb tragen können: Rb Halogen, Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Alkyl, Haloalkyl, Alkenyl, Alkenyloxy, Alkinyloxy, Alkoxy, Halogenalkoxy, Alkylthio, Alkyl- amino, Dialkylamino, Formyl, Alkylcarbonyl, Alkylsulfonyl, Alkyl- sulfoxyl, Alkoxycarbonyl, Alkylcarbonyloxy, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkylaminothiocarbonyl, Dialkylamino- thiocarbonyl, wobei die Alkylgruppen in diesen Resten 1 bis 6 Kohlenstoffatome enthalten und die genannten Alkenyl- oder Alkinylgruppen in diesen Resten 2 bis 8 Kohlenstoffatome enthalten; und/oder einen bis drei der folgenden Reste:R a is halogen, cyano, nitro, hydroxy, CC 6 alkyl, CC 6 haloalkyl, -C 6 alkylcarbonyl, C 3 -C 6 cycloalkyl, CrCrAlkoxy, CC 6-halo-alkoxy, -C 6 -alkoxycarbonyl, CrC 6 - Alkylthio, CrC 6 j alkylamino, di-CrC 6 -alkylamino, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 3 -C 8 -cycloalkenyl, C 2 -C 6 -alkenyloxy, C 3 -C 6 -haloalkenyloxy, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -alkynyloxy, C 3 -C 6 -haloalkynyloxy, C 3 -C 6 -cycloalkoxy, C 3 -C 6- cycloalkenoxy, C 1 -C 3 -oxyalkyleneoxy, phenyl, naphthyl, five to ten membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S, these aliphatic, alicyclic or aromatic groups in turn may be partially or fully halogenated or may carry one to three groups R b : R b is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, Alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups in these radicals having 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these radicals contain from 2 to 8 carbon atoms; and / or one to three of the following radicals:
Cycloalkyl, Cycloalkoxy, Heterocyclyl, Heterocyclyloxy, wobei die cyclischen Systeme 3 bis 10 Ringglieder enthalten; Aryl, Aryloxy, Arylthio, Aryl-C C6-alkoxy, Aryl-CrC6-alkyI, Hetaryl, Hetaryloxy, Hetarylthio, wobei die Arylreste vorzugsweise 6 bis 10 Ringglieder, die Hetarylreste 5 oder 6 Ringglieder enthalten, wobei die cyclischen Systeme partiell oder vollständig halogeniert oder durch Alkyl- oder Haloalkylgruppen substituiert sein können;Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3 to 10 ring members; Aryl, aryloxy, arylthio, aryl-C C 6 -alkoxy, aryl-CrC 6 -alkyI, hetaryl, hetaryloxy, hetarylthio, wherein the aryl radicals preferably contain 6 to 10 ring members, the hetaryl 5 or 6 ring members, wherein the cyclic systems partially or completely halogenated or substituted by alkyl or haloalkyl groups;
Hai Halogen;Shark halogen;
L1, L2 Wasserstoff, Cyano, CrC4-Halogenalkyl, CrC6-Alkoxy, C3-C6-AlkenyIoxy oder C(=O)A, wobei mindestens eine Gruppe L1 oder L2 ungleich Wasserstoff ist; R C, C 3 -C 6 -AlkenyIoxy or C (= O) A, wherein at least one group L 1 or L 2 is L 1, L 2 is hydrogen, cyano, -C 4 haloalkyl, C 6 alkoxy not hydrogen;
A Wasserstoff, Hydroxy, CrC8-Alkyl, C C8-Alkoxy, CrCe-Halogenalkoxy, d-Cs-Alkylamino oder Di-(CrC8-Alkyl)amino;A is hydrogen, hydroxy, -C 8 alkyl, CC 8 alkoxy, CRCE-haloalkoxy, d-Cs-alkylamino or di- (C r C 8 alkyl) amino;
L3 Wasserstoff, Halogen, Cyano, Nitro, C C4-Halogenalkyl, CrC6-Alkoxy, C Ce-Alkoxycarbonyl;L 3 is hydrogen, halogen, cyano, nitro, CC 4 -haloalkyl, C 1 -C 6 -alkoxy, C 6 -alkoxycarbonyl;
X Halogen, Cyano, C C4-Alkyl, C C4-Halogenalkyl, C C4-Alkoxy oder d-C2- Halogenalkoxy. X is halogen, cyano, CC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy or dC 2 haloalkoxy.
2. Verbindungen der Formel I gemäß Anspruch 1 , in der R1 nicht Wasserstoff bedeutet.2. Compounds of formula I according to claim 1, in which R 1 is not hydrogen.
3. Verbindungen der Formel 1.1,3. Compounds of the formula 1.1,
in der G C2-C6-Alkyl, CrC4-Alkoxymethyl, oder C3-C6-Cycloalkyl; R2 Wasserstoff oder Methyl; und X Chlor, Methyl, Cyano, Methoxy oder Ethoxy bedeuten und L1 bis L3 und Hai gemäß Anspruch 1 definiert sind. in the C 2 -C 6 alkyl, C 1 -C 4 alkoxymethyl, or C 3 -C 6 cycloalkyl; R 2 is hydrogen or methyl; and X is chlorine, methyl, cyano, methoxy or ethoxy and L 1 to L 3 and shark are defined according to claim 1.
Verbindungen der Formel I.2,Compounds of the formula I.2,
in der D zusammen mit dem Stickstoffatom ein fünf- oder sechsgliedriges Heterocyclyl oder Heteroaryl bildet, welches über N gebunden ist und ein weiteres Heteroatom aus der Gruppe O, N und S als Ringglied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, CrC -Alkyl, C C4-Alkoxy und CrC2-Halogenalkyl tragen kann; X Chlor, Methyl, Cyano, Methoxy oder Ethoxy bedeuten und L1 bis L3 und Hai gemäß Anspruch 1 definiert sind. in which D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and contains a further heteroatom from the group O, N and S as ring member and / or one or more substituents from the group halogen, CrC Alkyl, CC 4 alkoxy and CrC 2 haloalkyl; X is chlorine, methyl, cyano, methoxy or ethoxy and L 1 to L 3 and shark are defined according to claim 1.
5. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1 , in der X für Halogen, Cyano, CrC -Alkyl, CrC -Alkoxy oder CrC2-Halogenalkoxy steht, durch Umsetzung von 5-Aminotriazol der Formel II mit Phenymalonaten der Formel III, in der R für Alkyl steht, zu Dihydroxytriazolopyrimidinen der Formel IV,5. A process for preparing the compounds of formula I according to claim 1, in which X is halogen, cyano, CrC alkyl, CrC alkoxy or -C 2 -haloalkoxy, by reaction of 5-aminotriazole of the formula II with phenymalonates of the formula III, in which R is alkyl, to dihydroxytriazolopyrimidines of the formula IV,
Halogenierung zu den Dihalogenverbindungen der Formel V,Halogenation to the dihalogen compounds of the formula V,
in der Y für Halogen steht und Umsetzung von V mit Aminen der Formel VI R R2 -H VI zu Verbindungen der Formel I, in der X für Halogen steht, gewünschtenfalls zu Herstellung von Verbindungen I, in denen X für Cyano, C C4-Alkoxy oder C C2- Halogenalkoxy steht, Umsetzung von Verbindungen l, in denen X Halogen bedeutet, mit Verbindungen der Formel VII, M-X' VII die, je nach der einzuführenden Gruppe X', ein anorganisches Cyanid, ein Alk- oxylat oder ein Halogenalkoxylat darstellen und in der M für ein Ammonium-, Tetraalkylammonium-, Alkali- oder Erdalkalimetallkation steht und, gewünschtenfalls, zur Herstellung von Verbindungen der Formel I gemäß Anspruch 1 , in der X für Alkyl steht, durch Umsetzung der Verbindungen I, in denen X für Halogen steht, mit Malonaten der Formel VIII, in which Y is halogen and reaction of V with amines of the formula VI R R2 -H VI to compounds of the formula I in which X is halogen, if desired to prepare compounds I in which X is cyano, CC 4 alkoxy or CC 2 - haloalkoxy, reaction of compounds I, in which X is halogen, with compounds of formula VII, MX 'VII which, depending on the introduced group X', an inorganic cyanide, an alk oxylate or a haloalkoxylate and represent in which M is an ammonium, tetraalkylammonium, alkali or alkaline earth metal cation and, if desired, for the preparation of compounds of the formula I according to claim 1, in which X is alkyl, by reacting the compounds I in which X is halogen , with malonates of the formula VIII,
in der X" Wasserstoff oder C C3-Alkyl und R C C4-Alkyl bedeuten, zu Verbin düngen der Formel IX und Decarboxylierung zu Verbindungen I, in denen X für Alkyl steht. in which X "is hydrogen or CC 3 -alkyl and RCC 4 -alkyl, to Verbin fertilize the formula IX and decarboxylation to compounds I in which X is alkyl.
Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1 , in der X für C C -AIkyl oder C C4-HaIogenalkyl steht, durch Umsetzung von 5-Aminotriazol der Formel II gemäß Anspruch 5 mit Ketoestern der Formel lila,A process for the preparation of the compounds of the formula I according to claim 1, in which X represents CC-alkyl or CC 4 -haloalkyl, by reacting 5-aminotriazole of the formula II according to claim 5 with ketoesters of the formula IIIa,
in der X1 für CrC -Alkyl oder d-d-Halogenalkyl und R für CrC -Alkyl steht, zu 5-Alkyl-7-hydroxy-6-phenyltriazolopyrimidinen der Formel IVa, in which X 1 is C 1 -C 4 -alkyl or d-haloalkyl and R 2 is C 1 -C 4 -alkyl, to give 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines of the formula IVa,
Halogenierung von IVa zu 7-Halogenotriazolopyrimidinen der Formel Va, Halogenation of IVa to 7-halotriazolopyrimidines of the formula Va,
in der Y für Halogen steht und Umsetzung von Va mit Aminen der Formel VI gemäß Anspruch 5 zu Verbindungen I, in denen X für CrC4-Alkyl oder d-C4-Halo- genalkyl steht. in which Y is halogen and reaction of Va with amines of the formula VI according to claim 5 to compounds I in which X is C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl.
7. Verbindungen der Formeln IV, IVa, V und Va gemäß Ansprüchen 5 und 6.7. Compounds of the formulas IV, IVa, V and Va according to claims 5 and 6.
8. Fungizides Mittel, enthaltend einen festen oder flüssigen Träger und eine Verbin- düng der Formel I gemäß Anspruch 1 8. A fungicidal composition containing a solid or liquid carrier and a compound of the formula I according to claim 1
9. Saatgut, enthaltend 1 bis 1000 g einer Verbindung der Formel I gemäß Anspruch 1 pro 100 kg.9. Seed containing 1 to 1000 g of a compound of formula I according to claim 1 per 100 kg.
10. Verfahren zur Bekämpfung von pflanzenpathogenen Schadpilzen, dadurch gekennzeichnet, dass man die Pilze, oder die vor Pilzbefall zu schützenden Materialien, Pflanzen, den Boden oder Saatgüter mit einer wirksamen Menge einer Verbindung der Formel I gemäß Anspruch 1 behandelt. 10. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected against fungal infection, materials, plants, the soil or seeds with an effective amount of a compound of formula I according to claim 1.
EP04803941A 2003-12-18 2004-12-16 6-(2-halophenyl)-triazolopyrimidines, method for their production and their use for combating pathogenic fungi, in addition to agents containing said substances Withdrawn EP1697367A1 (en)

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