EP1575957A1 - Triazolopyrimidines substituees par un groupe mercapto en position 2, leurs procedes de production, leur utilisation pour lutter contre des champignons nuisibles et agents les contenant - Google Patents

Triazolopyrimidines substituees par un groupe mercapto en position 2, leurs procedes de production, leur utilisation pour lutter contre des champignons nuisibles et agents les contenant

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Publication number
EP1575957A1
EP1575957A1 EP03782202A EP03782202A EP1575957A1 EP 1575957 A1 EP1575957 A1 EP 1575957A1 EP 03782202 A EP03782202 A EP 03782202A EP 03782202 A EP03782202 A EP 03782202A EP 1575957 A1 EP1575957 A1 EP 1575957A1
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European Patent Office
Prior art keywords
formula
compounds
alkyl
group
groups
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP03782202A
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German (de)
English (en)
Inventor
Jordi Tormo I Blasco
Carsten Blettner
Bernd Müller
Markus Gewehr
Wassilios Grammenos
Thomas Grote
Andreas Gypser
Joachim Rheinheimer
Peter Schäfer
Frank Schieweck
Anja Schwögler
Eberhard Ammermann
Siegfried Strathmann
Ulrich Schöfl
Reinhard Stierl
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BASF SE
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BASF SE
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Publication of EP1575957A1 publication Critical patent/EP1575957A1/fr
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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 2-mercapto-substituted triazolopyrimidines of the formula I.
  • A is hydrogen, hydroxy, -CC 8 -alkyl, C 2 -C 8 -alkenyl, CC 8 -alkoxy,
  • R 1 , R 2 independently of one another are hydrogen, CC 8 -alkyl, C Cs-haloalkyl,
  • R 1 and R 2 together with the nitrogen atom to which they are attached can also form a five- or six-membered ring which is interrupted by an atom from the group O, N and S and / or one or more substituents from the group Halogen, CC 6 alkyl, C Ce-haloalkyl and oxy-C ⁇ C 3 - alkyleneoxy can carry or in which an N and an adjacent C atom can be connected by a CrC 4 alkylene chain;
  • R 1 and / or R 2 can be substituted by one to four identical or different groups R a : R a halogen, cyano, nitro, hydroxy, CC 6 alkyl, CC 6 haloalkyl, CC 6 alkylI carbonyl, C 3 -C 6 cycloalkyl, CrC 6 alkoxy, C s haloalkoxy, CrC 6 alkoxy carbonyl, CC 6 -alkylthio, CrC 6 -alkylamino, di-C ⁇ -C 6 -alkylamino, C 2 -C 6 -alkenyl, C 2 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, C 3 -C 6 Cycloalkyl, phenyl, naphthyl, five- to ten-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S,
  • R b 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 containing 1 to 6 carbon atoms and the alkenyl or alkynyl groups mentioned in these radicals containing 2 to 8 carbon atoms;
  • the invention also relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.
  • 6-Phenyl-7-aminotriazolopyrimidines are generally known from EP-A 71 792 and EP-A 550 113.
  • WO 02/088127 discloses 2-thio-triazolopyrimidines.
  • the compounds described in the cited documents are known for combating harmful fungi. However, in many cases their effect is unsatisfactory. Proceeding from this, the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum.
  • the compounds of formula I differ from those from the abovementioned publications by the mercapto group in the 2-position of the triazoiopyrimidine skeleton.
  • the compounds of the formula I have an increased activity against harmful fungi compared to the known compounds.
  • the compounds according to the invention can be obtained in various ways. They are advantageous by reacting sulfoxides of the formula II with trifluoroacetic anhydride (TFA) under those described in J. Fluorine Chem. (1996), 159 and J. Het. Chem. (1988), 1007 known conditions.
  • TFA trifluoroacetic anhydride
  • M y + ) y SH or sulfides (MH-y S, where M stands for a cation from the group of the alkali or alkaline earth metals of the valence y or for an ammonium group NP + (R H or C ⁇ C -alkyl) NaSH x H 2 O, Na 2 S or (NH 4 ) 2 S, in particular NaSH x H 2 O, are used particularly advantageously in this process.
  • the reaction of the thio compounds of the formula IV, in particular of the formula 1V.1, to give compounds of the formula I is carried out, for example, by reduction with alkali metals, in particular with sodium, in general in the presence of a base.
  • Liquid ammonia which also serves as a solvent, is particularly suitable as the base.
  • Other suitable solvents are ethers, such as tetrahydrofuran or alcohols, such as ethanol or butanol or mixtures thereof [cf. J. Chem. Soc. Perkin Trans., Vol. 1, p. 1421 (1977); J. Org. Chem., P.6672 (1991); DE-OS 35 45 124].
  • the protective group can be cleaved from IV, in particular from IV.1, also with HF in solvents, such as Anisole [see: Bull. Chem. Soc. Jpn., P.2164 (1967)].
  • the protective group can be split off from IV, in particular from IV.2, advantageously under basic conditions, in particular with alkali metal or alkaline earth metal hydroxides, such as NaOH, [see: J. Org. Chem. (1978), 1197].
  • the protective group from IV, in particular from IV.3, is advantageously cleaved off with the 2-chlorosulfonyl-3-nitropyridine / Bu 3 P system [cf. Tetrahedron (2001), 1897].
  • the reaction temperature is usually from 0 to 120 ° C., preferably from 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
  • Suitable solvents include ethers such as dioxane, diethyl ether and, preferably tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene.
  • the compounds IV.B are converted to compounds IB under the reaction conditions described above for the compounds IV (in particular IV.1 to IV.3).
  • Compounds I in which X represents CC-alkyl or dC -haloalkyl (formula IC) can advantageously be prepared starting from starting materials of the formula IV.A via the compounds IV.C on the routes outlined below.
  • Compounds of the formula IC in which XC f is C -alkyl can be obtained by coupling 5-halotriazolopyrimidines of the formula IV.A with organometallic reagents of the formula VI.
  • the reaction takes place using transition metal catalysis, such as Ni or Pd catalysis.
  • X stands for a CC 4 alkyl and M for a metal ion of the valence Y, such as B, Zn or Sn.
  • This reaction can be carried out, for example, analogously to the following methods: J. Chem. Soc. Perkin Trans. 1, 1187 (1994), ibid. 1, 2345 (1996); WO 99/41255; Aust. J. Chem., Vol. 43, p.733 (1990); J. Org. Chem., Vol. 43, p.358 (1978); J. Chem. Soc. Chem. Commun. S.866 (1979); Tetrahedron Lett., Vol. 34, S.8267 (1993); ibid., Vol. 33, P.413 (1992).
  • Chlorination or bromination agents such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride are preferably used.
  • the reaction can be carried out in bulk or in the presence of a solvent. Usual reaction temperatures are from 0 to 150 ° C or preferably from 80 to 125 ° C.
  • reaction of X with amines XI 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 ether, e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene [cf. WO 98/46608].
  • ether e.g. B. dioxane, diethyl ether or in particular tetrahydrofuran
  • halogenated hydrocarbons such as dichloromethane
  • aromatic hydrocarbons such as toluene [cf. WO 98/46608].
  • a base such as tertiary amines, for example triethylamine or inorganic amines, such as potassium carbonate, is preferred; Excess amine of the formula XI can also serve as the base.
  • the malonates XII 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 literature cited.
  • the decarboxylation is usually carried out at temperatures from 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.
  • the oxidation of the compounds IV.B or IV.C to the sulfoxides of the formula II, or the sulfones of the formula III, in which X is cyano, -CC 4 alkoxy or dC 2 haloalkoxy (formulas II . B, or III.B.) or CC 4 alkyl or C 4 -haloalkyl (formulas II. C or III.C), is usually carried out at temperatures of from -40 ° C to 60 ° C, preferably -40 ° C to 40 ° C, in an inert organic solvent [cf. Synth. Commun., Vol. 16, pp. 233ff. (1986); WO 02/088127].
  • Suitable oxidizing agents are inorganic peroxides, such as hydrogen peroxide or peroxocarboxylic acids, such as peracetic acid or perbenzoic acids, in particular meta-chloroperbenzoic acid.
  • the reaction mixtures are usually worked up, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products chromatographically.
  • the intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are freed or purified from volatile components under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting. If individual compounds I are not accessible in the ways described above, they can be prepared by derivatizing other compounds I.
  • isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). 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.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example dC 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-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethyl
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 2, 4 or 6 carbon atoms (as mentioned above), in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above: in particular dC 2 haloalkyl such as chloromethyl, bromomethyl, dichloro - methyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlorine -2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichlor
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 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-l-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 with 2 to 10 carbon atoms and one or two double bonds in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely against halogen atoms as mentioned above, in particular fluorine, chlorine and bromine , can be replaced;
  • Alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6, 8 or 10 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 -Butinyl, 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-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pent
  • Cycloalkyl mono- or bicyclic, saturated hydrocarbon groups with 3 to 6 or 8 carbon ring members, for example C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; five- to ten-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S:
  • Sulfur atoms e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazothiazolidinyl, 4-isothiazolidiazolidinyl, 4 zolidinyl, 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-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidropinyl piperazinyl;
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom
  • 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members can, e.g.
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
  • Alkylene divalent unbranched chains from 3 to 5 CH 2 groups, e.g. CH 2 , CH 2 CH, CH2CH2CH2. CH2CH2CH2CH2 and CH CH2CH2CH2CH2;
  • Oxyalkylene divalent unbranched chains of 2 to 4 CH 2 groups, with one valence bonded to the skeleton via an oxygen atom, for example OCH 2 CH 2 , OCH2CH2CH2 and OCH2CH 2 CH 2 CH 2 ;
  • Oxyalkyleneoxy divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bound to the skeleton via an oxygen atom, for example OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
  • the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal activity of the compounds I are suitable.
  • the cations used are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium, with one to four hydrogen atoms here if desired by C ⁇ - C-alkyl, hydroxy-C 4 -alkyl, C 1 -C 4 -alkoxy-dC-alkyl, hydroxy-dd-alkoxy-dd-alkyl, phenyl or benzyl can be replaced, preferably ammonium, dimethylammonium, diisopropylammonium, Tetramethylammonium, tetrabutylammonium, 2- (2-hydroxy-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, trimethylbenzylammonium, furthermore, phosphonium ions, sufonium ions, preferably tri (CC
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexaflourosilicate, hexafluorophosphate, benzoate and the anions of dC 4 -alkanoic acids, preferably formate and acetate, acetate ,
  • R 1 is dC 4 alkyl, C 2 -C 6 alkenyl or dCs haloalkyl.
  • R 1 is a 5- or 6-membered saturated or aromatic heterocycle containing one or two hetero atoms from the group N, O and S, which is substituted by one or two alkyl or halo - Genalkyl groups can be substituted.
  • R 1 represents a group B.
  • Y 1 is hydrogen, fluorine or dC 6 fluoroalkyl
  • Y 2 is hydrogen or fluorine, or Y 1 and Y 2 together form a double bond
  • n is 0 or 1
  • R 4 is hydrogen or methyl.
  • R1 is C 3 -C 6 cycloalkyl, which can be substituted by CC 4 alkyl.
  • R 1 and / or R 2 contain haloalkyl or haloalkenyl groups with a chiral center, the (S) isomers are preferred for these groups.
  • the (R) -configured isomers are preferred.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a saturated or unsaturated five- or six-membered ring which is interrupted by an atom from the group O, N and S and / or can carry one or more substituents from the group halogen, dC 6 -alkyl, dC 6 -haloalkyl and oxy-dC 3 -alkyleneoxy or in which two adjacent ring members can be connected by a CC -alkylene chain.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidinyl, morpholinyl or thiomorpholinyl ring, in particular a piperidinyl ring which may be replaced by a to three groups halogen, CC 4 alkyl or -CC haloalkyl, in particular substituted by 4-methyl.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a pyrrolidine ring which may be halogen, CC 4 -alkyl or dC 4 -haloalkyl, in particular by one or two groups is substituted by 2-methyl.
  • # is the point of attachment to the triazolopyrimidine backbone
  • L 2 , L 4 independently of one another are hydrogen or fluorine
  • L 3 is hydrogen, fluorine, chlorine, cyano, CH 3 or COOCH 3 ;
  • L 5 is hydrogen, fluorine or CH 3 .
  • X is halogen or C 1 -C 6 -alkyl, such as chlorine or methyl, in particular chlorine.
  • Table 1 Compounds of the formula I in which X is chlorine, L m is 2-fluoro-6-chlorine 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 characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts,
  • the compounds I are also suitable for combating harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Pacilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, 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 active amount of the active compounds.
  • the application can take place 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% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 10 g, preferably 0.01 to 2 g, per kg of seed are generally required.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.
  • solvents / auxiliaries Water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g.
  • Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • natural stone powder e.g. kaolins, clays, talc, chalk
  • synthetic stone powder e.g. highly disperse silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of sulfonic acid of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributyl
  • emulsions, pastes or oil dispersions mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives,
  • strongly polar solvents e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, Lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products, such as grain 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 s
  • 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 the NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a Water-soluble concentrates (SL) 10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.
  • Dispersible concentrates 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.
  • a dispersant e.g. Dissolved polyvinyl pyrrolidone
  • Emulsifiable concentrates 15 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% by weight). Dilution in water results in an emulsion.
  • D Emulsions (EW, EO) 40 parts by weight of a compound according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • a compound according to the invention 20 parts by weight of a compound according to the invention are comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient.
  • Dispersing and wetting agents are finely ground and manufactured using technical equipment (e.g. 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.
  • technical equipment e.g. extrusion, spray tower, fluidized bed
  • 75 parts by weight of a compound according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • 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 dusting agent.
  • I Granules 0.5 part by weight of a compound according to the invention are finely ground and combined with 95.5% carriers. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.
  • the active ingredients as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring can be applied.
  • the application forms depend entirely on the Uses; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water.
  • emulsions, pastes or old dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates composed of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. 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 process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • compositions according to the invention can also be present together with other active compounds which, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • 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, Dinitrocona- zol, epoxiconazole, fenbuconazole, Fluquiconazol, flusilazole, hexaconazole, Imaza- lil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, Prothioco- Nazole, tebuconazole, triadimefon, triadimenol, triflumizole , Triticonazole,
  • Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,
  • Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Poiycarbamat, Thiram, Ziram, Zineb,
  • Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, Dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronquin, prozolifene, proba Pyroquilon, Quinoxyfen, Silthiofam, Thiabendazol, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazol, Triforine,
  • Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,
  • Nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl
  • fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, Dazomet, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, fosetylamino, fefosetone, ferimosone, ferimzone Iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl,
  • Strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
  • Sulfenic acid derivatives such as Captafol, Captan, dichlofluanid, Folpet, Tolylfluanid • Cinnamic acid amides and analogues such as Dimethomorph, Flumetover or Flumorph.
  • the active ingredients were administered as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight.
  • Nekanil® LN Litensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • Wettol® EM non-ionic emulsifier based on ethoxylated castor oil
  • Pepper seedlings of the "Neusiedler Ideal Elite" variety after 4 to 5 leaves had developed well, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The next day the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber at 22 to 24 ° C and higher
  • the evaluation is carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies.
  • W (1 - ⁇ / ff) - 100 a corresponds to the fungal attack on the treated plants in% and ß corresponds to the fungal attack on the untreated (control) plants in%
  • the infestation of the treated plants corresponds to that of the untreated control plants; with an efficiency of 100, the treated plants show no infection.

Abstract

L'invention se rapporte à des triazolopyrimidines substituées par un groupe mercapto en position 2, définies par la formule (I) dans laquelle les substituants ont la signification suivante : L représente halogène, cyano, nitro, alkyle, alcényle, alcynyle, halogénure d'alkyle, halogénure d'alcényle, alcoxy, alcényloxy, alcynyloxy, halogénure d'alcoxy ou -C(=O)-A ; A représente hydrogène, hydroxy, alkyle, alcényle, alcoxy, halogénure d'alcoxy, alkylamino ou dialkylamino ; m représente 0 ou 1, 2, 3, 4 ou 5 ; X représente halogène, cyano, alkyle, halogénure d'alkyle, alcoxy ou halogénure d'alcoxy ; R1, R2 représentent hydrogène, alkyle, halogénure d'alkyle, cycloalkyle, halogénure de cycloalkyle, alcényle, alcadiényle, halogénure d'alcényle, cycloalcényle, alcynyle, halogénure d'alcynyle ou cycloalcynyle, phényle, naphthyle ou un hétérocycle saturé, partiellement insaturé ou aromatique comprenant cinq à dix chaînons et un à quatre hétéroatomes sélectionnés dans le groupe rassemblant les éléments O, N ou S, R1 et R2 pouvant en outre former avec l'atome d'azote auquel ils sont reliés un cycle à cinq ou six chaînons qui peut être interrompu par un atome issu du groupe rassemblant les éléments O, N et S, et R1 et/ou R2 pouvant être substitué(s) tel qu'explicité dans la description. La présente invention concerne en outre des procédés de production de ces composés, des agents les contenant ainsi que leur utilisation pour lutter contre des champignons phytopathogènes.
EP03782202A 2002-11-15 2003-11-14 Triazolopyrimidines substituees par un groupe mercapto en position 2, leurs procedes de production, leur utilisation pour lutter contre des champignons nuisibles et agents les contenant Withdrawn EP1575957A1 (fr)

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DE10253593 2002-11-15
DE10253593 2002-11-15
DE10304076 2003-01-31
DE10304076 2003-01-31
PCT/EP2003/012773 WO2004046149A1 (fr) 2002-11-15 2003-11-14 Triazolopyrimidines substituees par un groupe mercapto en position 2, leurs procedes de production, leur utilisation pour lutter contre des champignons nuisibles et agents les contenant

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US (1) US20050272748A1 (fr)
EP (1) EP1575957A1 (fr)
JP (1) JP2006514676A (fr)
AR (1) AR042060A1 (fr)
AU (1) AU2003289871A1 (fr)
BR (1) BR0316033A (fr)
PL (1) PL376886A1 (fr)
TW (1) TW200505341A (fr)
WO (1) WO2004046149A1 (fr)

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TW200643022A (en) * 2005-03-02 2006-12-16 Basf Ag 2-substituted 7-aminoazolopyrimidines, processes for their preparation and their use for controlling harmful fungi, and compositions comprising these compounds
US20080146839A1 (en) * 2005-03-18 2008-06-19 Basf Aktiengesellschaft Method for Producing 5-Halo-2,4,6-Trifluoroisophthalic Acid
US7490305B2 (en) * 2006-07-17 2009-02-10 International Business Machines Corporation Method for driving values to DC adjusted/untimed nets to identify timing problems
CL2007003256A1 (es) * 2006-11-15 2008-07-25 Du Pont Mezcla fungicida que comprende al menos tres compuestos diferentes; composicion fungicida que comprende dicha mezcla; y metodo para controlar una enfermedad en plantas causada por el patogeno fungico vegetal que comprende aplicar una cantidad de la m
US20100087640A1 (en) * 2007-01-11 2010-04-08 Basf Se Method for production of aryl-substituted annelated pyrimidines

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DE3130633A1 (de) * 1981-08-01 1983-02-17 Basf Ag, 6700 Ludwigshafen 7-amino-azolo(1,5-a)pyrimidine und diese enthaltende fungizide
TW224044B (fr) * 1991-12-30 1994-05-21 Shell Internat Res Schappej B V
DE10121102A1 (de) * 2001-04-27 2002-11-07 Bayer Ag Triazolopyrimidine

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WO2004046149A1 (fr) 2004-06-03
PL376886A1 (pl) 2006-01-09
TW200505341A (en) 2005-02-16
AR042060A1 (es) 2005-06-08
AU2003289871A1 (en) 2004-06-15

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