Title of Invention	"6-(2,6-DIFLUORO-PHENYL)-TRIAZOLOPYRIMIDINES" AND A PROCESS FOR THEIR PREPARATION
Abstract	6-(2,6-Difluoro-phenyl)-triazolopyrimidines of formula I in which R<sup>1</sup> and R<sup>2</sup> independently denote hydrogen or alkyl, alkenyl, alkynyl, or alkadienyl, cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, where R<sup>1</sup> and R<sup>2</sup> radicals may be unsubstituted or substituted as defined in the description, or R<sup>1</sup> and R<sup>2</sup> together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted; X is halogen, cyano, alkoxy, haloalkoxy or alkenyloxy; processes for their preparation, compositions containing them and to their use for combating phytopathogenic fungi.

Title of Invention

"6-(2,6-DIFLUORO-PHENYL)-TRIAZOLOPYRIMIDINES" AND A PROCESS FOR THEIR PREPARATION

Abstract

6-(2,6-Difluoro-phenyl)-triazolopyrimidines of formula I in which R1 and R2 independently denote hydrogen or alkyl, alkenyl, alkynyl, or alkadienyl, cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, where R1 and R2 radicals may be unsubstituted or substituted as defined in the description, or R1 and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted; X is halogen, cyano, alkoxy, haloalkoxy or alkenyloxy; processes for their preparation, compositions containing them and to their use for combating phytopathogenic fungi.

Full Text	6-(2,6-Difluoro-phenyl)-triazolopyrimidines Descript10n The invent10n relates to 6-(2,6-difluoro-phenyl)-triazolopyrimidines of formula I I in which R1 and R2 independently denote hydrogen or C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or C4-C10-alka- dienyl, C3-C10-cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or where R1 and R2 radicals may be unsubstituted or may carry one to three groups Ra, Ra is cyano, nitro, hydroxyl, C1-Cg-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylth10, C1-C6-alkylamino, di-C1-C6-alkylamino, C2-C6~alkenyl, C2-Ce-alkenyloxy, C2~C6-alkynyl, C3-C6-alkynyloxy and C1-C4-alkylened10xy; or ll and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one to three Ra radicals; I is halogen, cyano, C1-C6~alkoxy, C1-C6-haloalkoxy or C3-Cs-al-kenyloxy. loreover, the invent10n relates to processes for their prepara-:10n, composit10ns containing them and to their use for combating )hytopathogenic fungi. 5-Phenyl-7-amino-triazolopyrimidines are generally known from JS 4,567,262 and US 5,593,996. Triazolopyrimidines with a trifluorophenyl group in 6-posit10n ire disclosed in WO-A 98/46607 and EP-A 945 453. ?rom WO-A 98/46608 some 6-(2,6-difluoro-phenyl)-triazolopyrimidi-ies are known, which are substituted in the 7-posit10n by fluori-lated alkylamines. ?he compounds disclosed in the documents discussed above are said :o be active against var10us phytopathogenic fungi. :t is an object of the present invent10n to provide compounds having improved fungiC1dal activity. le have found that this object is achieved by the compounds defi-Led at the outset. Furthermore, we have found processes for their reparat10n, composit10ns comprising them and methods for :ontrolling phytopathogenic fungi using the compounds I. 'he compounds of the formula I differ from the compounds known rom WO-A 98/46608 in the combinat10n of the 2,6-difluoro-phenyl roup with an halogen free amino group in the 7-posit10n of the riazolopyrimidine system. he present invent10n further provides a process for the prepara-10n of compounds of formula I as defined above which comprises reating a 5,7-dihalo compound of formula II in which X is halo-en with an amine of formula III. he react10n between the 5,7-dihalo compound II and the amine of ormula III can be carried out under condit10ns known from WO-A 8/46608. Dmpounds of formula II are known from EP-A 550 113; they can be repared by known methods [cf. EP-A 550 113 or EP-A 770 615]. le react10n is preferably carried out in the presence of a Solent . Suitable solvents include ethers, such as d10xane, diethyl :her and, espeC1ally, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons, for example toluene. The react10n is suitably carried out at a temperature in the range from 0°C to 70°C/ the preferred react10n temperature being from 10°C to 3 5°C. It is also preferred that the react10n is carried out in the presence of a base. Suitable bases include tertiary amines, such as triethylamine, and inorganic bases, such as potassium carbonate or sodium carbonate. Alternatively, an excess of the compound of formula III may serve as a base. The react10n mixtures are worked up in a customary manner, for example by mixing with water, phase separat10n and, if required, chromatographic purificat10n of the crude products. Some of the end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperatures. If the end products are obtained as solids, purificat10n can also be carried out by recrystallizat10n or digest10n. Compounds of formula II are known in the art and can be obtained by synthesis routes disclosed in EP-A 550 113, EP-A 770 615 and WO-A 98/46608. Compounds of formula I in which X denotes cyano, C1-C6~alkoxy, C1-C6-haloalkoxy or C3-Cs-alkenyloxy can be prepared by reacting compounds I in which X is halogen, preferably chloro, with compounds of formula IV, which are, dependent from the value of X' to be introduced to yield formula I compounds, an anorganic cyano salt, an alkoxylate, haloalkoxylate or an alkenyloxylate, respectively, preferably in the presence of a a solvent. The cat10n M in formula IV has minor influence; for practical and economical reasons usually ammonium-, tetraalkylammonium- or alkalimetal-and earth metal salts are preferred. The react10n is suitably carried out at a temperature in the range from 0 to 120°C, the preferred react10n temperature being from 10 to 40°C [cf. J. Heterocycl. Chem. , Vol. 12, p. 861-863 (1975) ] . suitable solvents include ethers, such as d10xane, diethyl ether and, espeC1ally, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons, for example toluene. If individual compounds I are not obtainable by the routes described above, they can be prepared by derivatizat10n of other compounds I. In the symbol definit10ns given in the formulae above, collective terms were used which generally represent the following sub-stituents: - halogen: fluorine, chlorine, bromine and 10dine; - C1-C10-alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 10, espeC1ally 1 to 6 carbon atoms, for example C1~C4-alkyl as ment10ned above or pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethyl-butyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methyl-propyl and l-ethyl-2-methylpropyl; - C2~C10-alkenyl: unsaturated, straight-chain or branched hydro carbon radicals having 2 to 10, espeC1ally 2 to 6 carbon atoms and a double bond in any posit10n, for example ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-l-propenyl, l-methyl-2-propenyl and 2-methyl-2-propenyl; C2-C10~alkynyl: straight-chain or branched hydrocarbon radicals having 2 to 10, espeC1ally 2 to 4 carbon atoms and a triple bond in any posit10n, for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl; haloalkyl moieties of C1-C6-haloalkoxy: straight-chain or branched alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms (as ment10ned above), where the hydrogen atoms in these groups may be partially or fully replaced by halogen atoms as ment10ned above, for example C1-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluorome-thoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-tri- fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy; C3-C10~cycloalkyl: mono- or bicyclic cycloalkyl groups having 3 to 10 carbon atoms; monocyclic groups preferably have 3 to 8, espeC1ally 3 to 6 ring members, bicyclic groups preferably have 8 to 10 ring members. A 5- or 6-membered heterocyclyl group, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, preferably one oxygen atom. 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, in addit10n to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-iso-thiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl; 6-membered heteroaryl, containing one to four nitrogen atoms: 6-membered heteroaryl groups which, in addit10n to carbon atoms, nay contain one to three or one to four nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-py-ridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimi-iinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl. Vith respect to their intended use, preference is given to tria-solopyrimidines of the formula I having the following sub-stituents, where the preference is valid in each case on its own :>r in combinat10n: i. preferred cycloalkyl moiety is cyclopentyl being opt10nally substituted by one or more nitro, cyano, C1-C6-alkyl, C1-C6-alkoxy groups . L preferred heteroaryl moiety is pyridyl, pyrimidyl, pyrazolyl or ;hienyl. Preference is given to compounds of formula I in which any alkyl part of the groups R1 or R2, which may be straight chained or branched, contains 1 to 9 carbon atoms, more preferably 2 to 6 carbon atoms, any alkenyl or alkynyl part of the substituents R1 or R2 contains 2 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, any cycloalkyl part of the substituents R1 or R2 contains from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms, and any bicycloalkyl part of the substituents R1 or R2 contains from 7 to 9 carbon atoms. Any alkyl, alkenyl or alkynyl group may be linear or branched. Compounds of formula I are preferred in which R1 is not hydrogen. Moreover, compounds of formula I are preferred in which R1 represents a straight-chained or branched Ci-C10~alkyl, in particular a branched C3-C10~aikyl group, a C3-Cs-cycloalkyl, a Cs-Cg-bicycloal-kyl, a C3-C8-cycloalkyl-Ci-C6-alkyl, Ci-Ci0-alkoxy-Ci-C6-alkyl, or a phenyl group being opt10nally substituted by one to three C1-C10-alkyl or Ci-C10-alkoxy groups. Particular preference is given to compounds I in which R2 represents a hydrogen atom or a C1-C10-alkyl group, in particular a hydrogen atom. Moreover, particular preference is given to compounds I in which R2 is methyl or ethyl. If R1 denotes an opt10nally substituted C3-C8~cycloalkyl group, preferably a cyclopentyl or cyclohexyl group, R2 preferably represents a hydrogen atom or Ci-Ce-alkyl group. Moreover, particular preference is given to compounds I in which R1 and R2 together with the interjacent nitrogen atom form an opt10nally substituted heterocyclic ring, preferably an opt10nally substituted C3-C7~heterocyclic ring, in particular a pyrrolidine, piperidine, tetrahydropyridine, in particular 1,2,3,6-tetrahydro-pyridine or azepane ring which is opt10nally substituted by one or more C1-C10-alkyl groups. Besides, particular preference is given to compounds I in which X is chloro or bromo, especially chloro. Moreover, preference is given to compounds I in which X is cyano or methoxy. Furthermore, particular preference is given to compounds I in which X is ethoxy, n-propoxy, iso-propoxy, allyloxy, or 3-methy-lallyloxy. Included in the scope of the present invent10n are (R) and (S) isomers of compounds of general formula I having a chiral center and the racemates thereof, and salts, N-oxides and aC1d addit10n compounds. With respect to their use, particular preference is given to the compounds I compiled in the tables below. The groups ment10ned in the tables for a substituent are furthermore for their part, independently of the combinat10n in which they are ment10ned, a particularly preferred embodiment of the respective substituents. Table 1 Compounds of the formula I, in which X is chloro and R1 and R2 correspond to one row in Table A Table 2 Compounds of the formula I, in which X is bromo and R1 and R2 correspond to one row in Table A Table 3 Compounds of the formula I, in which X is cyano and R1 and R2 correspond to one row in Table A Table 4 Compounds of the formula I, in which X is methoxy and R1 and R2 correspond to one row in Table A Table 5 Compounds of the formula I, in which X is ethoxy and R1 and R2 correspond to one row in Table A Table 6 Compounds of the formula I, in which X is n-propoxy and R1 and R2 correspond to one row in Table A Table 7 Compounds of the formula I, in which X is iso-propoxy and R1 and R.2 correspond to one row in Table A Table 8 Compounds of the formula I, in which X is allyloxy and R1 and R2 :orrespond to one row in Table A ■raC1e y Compounds of the formula I, in which X is 3-methylallyloxy and R1 and R2 correspond to one row in Table A The compounds I are suitable as fungiC1des. They have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and 23asid10;nycetes. Some of them act systemically, and they can be employed in crop protect10n as foliar- and soil-acting fungiC1des. They are espeC1ally important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit speC1es, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants. SpeC1fically, they are suitable for controlling the following plant diseases: • Alternaria speC1es, Podosphaera speC1es, Sclerotinia speC1es, Physalospora canker on vegetables and fruit, • Botrytis C1nerea (gray mold) an strawberries, vegetables , or- ■ namentals and grapevines, • Corynespora cassiicola on cucumbers, • Colletotrichum speC1es on fruit and vegetables, • Diplocarpon rosae on roses, • Elsinoe fawcetti and Diaporthe C1tri on C1trus fruit, • Sphaerotheca speC1es on cucurbits, strawberries and roses, • Cercospora speC1es on peanuts, sugar beets and aubergines, • Erysiphe C1choracearum on cucurbits, • Leveillula taurica on paprika, tomatoes and aubergines, • Mycosphaerella speC1es on apples and Japanese apricot, • Phyllactinia kakicola, Gloesporium kaki on Japanese apricot, • Gyiunosporangium yamadae, Leptothyrium pomi, Podosphaera leuco-tricha and Gloedes pomigena on apples, • Cladosporium carpophilum on pears and Japanese apricot, • Phomopsis speC1es on pears, • Phytophthora speC1es on C1trus fruit, potatoes, on10ns, espeC1ally Phytophthora infestans on potatoes and tomatoes, • Blumeria graminis (powdery mildew) on cereals, • Fusarium- and VertiC1llium speC1es on var10us plants, • Glomerella C1ngulata on tee, • Drechslera- and Bipolaris speC1es on cereals and rice, • Mycosphaerella speC1es on bananas and peanuts, • Plasmopara viticola on grapevines, • Personospora speC1es on on10ns, spinach and chrysantemum, • Phaeoisar10psis vitis and Sphaceloma ampelina on grapefruits, • Pseudocercosporella herpotrichoides on wheat and barley, • Pseudoperonospora speC1es on hop and cucumbers, • PucC1nia speC1es and Typhula speC1es on cereals and turf, • Pyricularia oryzae on rice, • Rhizoctonia speC1es on cotton, rice and turf, • Stagonospora nodorum and Septoria tritiC1 on wheat, • UnC1nula necator on grapevines, • Ustilago speC1es on cereals and sugar cane, and • Venturis speC1es (scab) on apples and pears. Moreover, the compounds I are suitable for controlling harmful fungi such as PaeC1lomyces var10tii in the protect10n of materials (e.g. wood, paper, paint dispers10ns, fibers and tissues) and in the protect10n of stored products. The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infect10n, with a fungiC1dally active amount of the active ingredients. Applicat10n can be effected both before and after infect10n of the materials, plants or seeds by the fungi. In general, the fungiC1dal composit10ns comprise from 0.1 to 95, preferably 0.5 to 90, % by weight of active ingredient. When used in crop protect10n, the rates of applicat10n are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the effect desired. Ln the treatment of seed, amounts of active ingredient of from 3.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed. tfhen used in the protect10n of materials or stored products, the rate of applicat10n of active ingredient depends on the nature of the field of applicat10n and on the effect desired. Rates of applicat10n convent10nally used in the protect10n of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated. The compounds I can be converted into the customary formulat10ns, e.g. solut10ns, emuls10ns, suspens10ns, dusts, powders, pastes and granules. The use form depends on the particular purpose; in any case, it should guarantee a fine and uniform distribut10n of the compound according to the invent10n. The formulat10ns are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fract10ns), alcohols (e.g. methanol, butanol), ketones (e.g. cy-clohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly-disperse silica, silicates); emulsifiers such as non-10nic and an10nic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as li-gnin-sulfite waste liquors and methylcellulose. Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic aC1d, naphthalenesulfonic aC1d, phenolsulfonic aC1d, dibutylnaphthalenesulfonic aC1d, alkylaryl-sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty aC1ds and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthaiene-sulfonic aC1d with phenol or formaldehyde, polyoxyethylene octyl-phenyl ether, ethoxylated isooctylphenol, octylphenol, nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose. Substances which are suitable for the preparat10n of directly sprayable solut10ns, emuls10ns, pastes or oil dispers10ns are mineral oil fract10ns of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphtha-lene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethyIformamide, dimethyl sulfoxide, N-me-thylpyrrolidone and water. Powders, materials for scattering and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier. Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calC1um sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. In general, the formulat10ns comprise of from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient . The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum). The following are exemplary formulat10ns: I. 5 parts by weight of a compound according to the invent10n are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient. II. 30 parts by weight of a compound according to the invent10n are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a formulat10n of the active ingredient with good adhes10n properties (comprises 23% by weight of active ingredient) . 10 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic aC1d N-monoethanolamide, 2 parts by weight of calC1um dodecylbenzenesulfonate and 2 parts by weight of the adduct of 4 0 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient). 2 0 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 3 0 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient). 80 parts by weight of a compound according to the invent10n are mixed thoroughly with 3 parts by weight of sodium diiso-butylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic aC1d from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient). 90 parts by weight of a compound according to the invent10n are mixed with 10 parts by weight of N-methyl-CC-pyrrolidone, which gives a solut10n which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient) . 2 0 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 3 0 parts by weight of isobutanol, 2 0 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solut10n into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispers10n which comprises 0.02% by weight of the active ingredient. . 2 0 parts by weight of a compound according to the invent10n are mixed thoroughly with 3 parts by weight of sodium diiso- butylnaphthalene-Ct-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic aC1d from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient. The active ingredients can be used as such, in the form of their formulat10ns or the use forms prepared therefrom, e.g. in the form of directly sprayable solut10ns, powders, suspens10ns or dispers10ns, emuls10ns, oil dispers10ns, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring. The use forms depend entirely on the intended purposes; in any case, this is intended to guarantee the finest possible distribut10n of the active ingredients according to the invent10n. Aqueous use forms can be prepared from emuls10n concentrates, pastes or wettable powders (sprayable powders, oil dispers10ns) by adding water. To prepare emuls10ns, pastes or oil dispers10ns, the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilut10n with water. The active ingredient concentrat10ns in the ready-to-use products can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%. The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulat10ns comprising over 95% by weight of active ingredient, or even the active ingredient without additives. Var10us types of oils, herbiC1des, fungiC1des, other pestiC1des, or bacteriC1des may be added to the active ingredients, if appropriate also only immediately pr10r to use (tank mix). These agents can be admixed with the agents according to the invent10n in a weight rat10 of 1:10 to 10:1. In the use form as fungiC1des, the composit10ns according to the invent10n can also be present together with other active ingre-dients, e.g. with herbiC1des, insectiC1des, growth regulators, fungiC1des or else with fertilizers. Mixing the compounds I or tne composit10ns comprising them in the use form as fungiC1des with other fungiC1des frequently results in a broader fungiC1dal spectrum of act10n. The following list of fungiC1des, together with which the compounds according to the invent10n can be used, is intended to illustrate the possible combinat10ns, but not to impose any limitat10n: sulfur, dith10carbamates and their derivatives, such as iron(III) dimethyldith10carbamate, zinc dimethyldith10carba-mate, zinc ethylenebisdith10carbamate, manganese ethylenebis-dith10carbamate, manganese zinc ethylenediaminebisdith10car-bamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdith10carbamate) , ammonia complex of zinc (N,N'-propylenebisdith10carbamate), zinc (N,N'-propylenebis-dith10carbamate), N,N'-polypropylenebis(th10carbamoyl)disulfide; nitro derivatives, such as dinitro(1-methylheptyl)phenyl cro-tonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonoth10ate, 5-amino-l-[bis(dime-thylamino)phosphinyl]-3-phenyl-1,2,4- triazole, 2,3-dicya-no-1,4-dith10anthraquinone, 2-th10-l,3-dith10lo[4,5-b]quino-xaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, N-(1,1,2,2-tetrachloroe-thylth10)tetrahydrophthalimide, N-trichloromethylth10tetrahy-drophthalimide, N-trichloromethylth10phthalimide, 5-Chloro-2-cyano-4-p-tolyl-imidazole-l-sulfonic aC1d dimethylamide, N-dichlorofluoromethylth10-N',N'-dimethyl -N-phenylsulfo-diamide, 5-ethoxy-3~trichlorome-thyl-1,2,3-thiadiazole, 2-th10cyanatomethylth10benzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazo-no)-3-methyl-5~isoxazolone, pyridine-2-th10l 1-oxide, 8-hy-droxyquinoline or its copper salt, 2,3-dihydro-5-carboxanili-do-6-methyl-l,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-me-thyl-1,4-oxathiine 4,4-d10xide, 2-methyl-5,6-dihydro-4H-py-ran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dime-thylfuran-3-carboxanilide, 2-Chloro-N-(4'-chloro-biphe-nyl-2-yl)-nicotinamide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl- 2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanili-de, 2-10dobenzanilide, N-formyl-N-morpholine-2,2,2-trichlo- roethyl acetal, piperazine-1,4-diylbis-l-(2,2,2-trichloro-ethyl) formamide, 1- (3 , 4-dichloroanilino) -1-f ormylami-no-2,2,2-trichloroethane; 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-C1s-2,6-di-methyl- morpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl] -piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-d10xo-lan-2-yl-ethyl]-lH-l,2,4-triazole, 1-[2-(2 , 4-dichlorophenyl) -4-n-propyl-l,3-d10xolan-2-yl-ethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazo-lyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-tri-azol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1- (lH-l,2,4-triazol-l-yl)-2-butanol, (2RS,3RS)-1-[3-(2-chlo-rophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidineme-thanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycar-bonyl-2-th10ureido)benzene, 1,2-bis(3-methoxycarbonyl-2~th10-ureido)benzene, strobilurines such as azoxystrobin, kresoxim methyl, methyl-E-methoxyimino-[a-(2-phenoxyphenyl)]-acetamide, methyl E-methoxyimino-[a-(2,5-dimethylphenoxy)-o-tolyl]acetamide, picoxystrobin, pyraclostrobin, trifloxystrobin, anilinopyrimidines such as N-(4,6-dimethylpyrimidin~2-yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]-aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles such as 4-(2,2-difluoro-1,3-benzod10xol-4-yl)pyrrole-3-carbonitrile, C1nnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine, 3-(4-fluorophenyl)-3-(3,4-di-methoxy-phenyl)acryloylmorpholine, and a variety of fungiC1des such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutar-imide, hexachlorobenzene, methyl N-(2,6-dimethylphe-nyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphe-nyl)-N-(2'-methoxyacetyl)-alanine methyl ester, N-(2,6-dime-thylphenyl)-N-chloroacetyl-D, L~2-arnino- butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5~vinyl-3-(3,5-dichlorophenyl)-2,4-di-oxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl(5-methyl-5-me-thoxymethyl]-1,3-oxazolidine-2,4-d10ne, 3-(3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl) -1,2-dimethylcyclopropane-l,2-dicarboximide, 2-cya-no-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, 3,5-Dichloro-N-(3~chloro-l-ethyl-l-methyl-2-oxo-propyl)-4-methyl-benzamide, 1-(3-Bromo~6-methoxy-2-methyl-phenyl)-1-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 1-[2-(2,4-di- chl oro—phenyl)pentyl]—1H—1, 2,4—triazole, 2,4—difluoro— a- (1H-1,2 ,4-triazolyl-l-methyDbenzhydryl alcohol, N- (3-chlo-ro-2 , 6-dinitro-4-trifluoromethylphenyl) -5-trif luorome-thyl-3-chloro-2-aminopyridine, 1- ( (bis (4-f luorophenyl)methyl-silyl)methyl)-1H-1,2,4-triazole. Synthesis Examples With due modificat10n of the starting compounds, the protocol shown in the synthesis example below was used for obtaining further compounds I. The resulting compounds I, together with physical data, are listed in the Table I which follows. Example 1 Preparat10n of 5,7-dihydroxy-6-(2,6-difluorophenyl) -[1,2,4]-triazolo[1,5-a]-pyrimidine A mixture of 3-amino-l,2,4-triazole (14 g), diethyl (2,6-difluo-xophenyl)-malonate (0,17 mol, cf. EP-A 10 02 788) and tributyl-amine (50 ml) was heated at about 180°C for six hours. The react10n mixture was cooled to about 70°C. 200 ml of 10 % aqueous sodium hydroxide solut10n were added and the react10n mixture were stirred for 30 minutes. The phases were separated, the aqueous phase was extracted with diethyl ether. The aqueous phase is aC1dified. The preC1pitate was filtered off and dried to yield 40 g of the title compound. Example 2 Preparat10n of 5,7-dichloro-6-(2,6-difluorophenyl) -[l,2,4]-triazolo[l,5-a]-pyrimidine A mixture of 5,7-dihydroxy-6-(2 , 6-difluorophenyl)-[1,2,4]-triazolo- [1, 5-a]pyrimidine (30 g, obtained from Ex. 1) and phosphorous oxychloride (50 ml) was refluxed for about eight hours. Phosphorous oxychloride was partly distilled off. The residue was poured into a mixture of dichloromethane and water. The organic layer was separated, dried and filtered. The filtrate was concentrated in vacuo to yield 28 g of the title compound of mp. 121°C. Example 3 Preparat10n of 5-chloro-6-(2,6-difluorophenyl)-7-iso- propylamino-[1,2,4]-triazolo[1,5-a]pyrimidine [1-3] \ mixture of isopropylamine (1,5 mmol), triethylamine (1,5 mmol) md dichloromethane (10 ml) was added to a mixture of 5,7-di-:hloro-6-(2,6-difluorophenyl)-[l,2,4]-triazolo[l,5-a]-pyrimidine (1,5 mmol, obtained from Ex. 2) and dichloromethane (2 0 ml) under stirring. The react10n mixture was stirred for about 16 hours at ibout 2 0 to 2 5°C and subsequently washed with dilute hydrocloric aC1d (5%). The organic layer was separated, dried and filtered. The filtrate was evaporated under reduced pressure and the residue was chromatographed to yield 0,43 g of the title compound of mp. 169°C. Example 4 Preparat10n of 5-cyano-6-(2,6-difluorophe- nyl)-7-(4-methylpiperidin-l-yl)-[1,2,4]-triazolo [1, 5-a]pyrimidine [1-18] A mixture of 5-chloro-6-(2,6-difluorophenyl)-7-(4-methylpiperi-din-l-yl)-[1,2,4]-triazolo-[1,5-a]-pyrimidine (0,1 mol; 1-4) and tetraethylammonium cyanide (0,25 mol) in 750 ml Dimethylformamide (DMF) (750 ml) was stirred for 16 hours at about 20 to 25°C. To this mixture water was added and methyl tert.butyl ether (MTBE), the organic phase was separated, washed with water, dried and filtered. The filtrate was evaporated and the residue was chromatographed to yield 6,95 g of the title compound of mp. 212°C. Example 5 Preparat10n of 5-methoxy-6-(2,6-difluorophenyl) -7-(diethylamino)-[1,2,4]-triazolo[1,5-a]pyrimidine [1-19] To a solut10n of 5-chloro-6-(2,6-difluorophenyl)-7-(diethyl-amino) - [1 , 2 , 4] -triazolo- [1 , 5-a] -pyrimidine (65 mmol; 1-6) in 400 ml dry methanol was added a 3 0% solut10n of sodium methano-late (71,5 mmol) at about 20 to 25°C. This mixture was further stirred for 16 hours. Methanol was evaporated and the residue was dissolved with dichloromethane. The organic phase was washed with water, dried and filtered. The filtrate was evaporated and the residue was chromatographed to yield 16,3 g of the title compound of mp. 153°C. Examples of the act10n against harmful fungi The fungiC1dal act10n of the compounds of the formula I was demonstrated by the following experiments: The active compounds, separately or together, were formulated as a 10% emuls10n in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersant act10n based on ethoxylated alkyl-phenols) and 10% by weight of Wettol® EM (non10nic emulsifier based on ethoxylated castor oil) and diluted with water to the desired concentrat10n. 310logical activity trial - FungiC1dal control of early blight on tomatoes (Alternaria solani) ifoung seedlings of tomato plants of the variety "Grofie Fleischto-nate St. Pierre" were grown in pots to the 2 to 4 leaf stage. These plants were sprayed to run-off with an aqueous suspens10n, :ontaining the concentrat10n of active ingredient ment10ned in :he table below, prepared from a stock solut10n containing 10 % Df the active ingredient, 85 % cyclohexanone and 5 % emulsifier. The next day, the treated plants were inoculated with an aqueous suspens10n of Alternaria solani containing 0,2 x 106 spores per nl. Then the trial plants were immediately transferred to a hu-nid chamber. After 6 days at 2 0 to 23°C and a relative humidity close to 100 %, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 250 ppm of > compounds 1-2 to 1-9, 1-11, 1-12, 1-14, 1-15 and 1-17 showed an infect10n of not more than 1%, whereas the untreated plants were infected to 90%. Active compounds A and B known from WO-A 98/46608 were used as i comparison compounds: Comparison trial - Control of gray mould {Botrytis C1nerea) on fruit slices of green pepper Fruit slices of green pepper were sprayed to run-off with an aqueous suspens10n, containing the concentrat10n of active ingredient or their mixture ment10ned in the table below, prepared from a stock solut10n containing 10 % of the active ingredient, 85 % cyclohexanone and 5 % emulsifier. After 2 hours the sprayed-on layer had dried, the disks were inoculated with a spore suspens10n of Botrytis C1nerea containing 1,7 x 106 spores per ml in 2 wt. % aqueous b10malt solut10n. The infected fruit slices were then incubated in chambers with high humidity for four days at 18-20°C. The fruit slice area under fungal attack was then assessed visually in percent. In this test, the plants which had been treated with 500 ppm of compounds 1-2, 1-8 and 1-14, resp., showed an infect10n of not more than 3%, whereas the the plants treated with 5 00 ppm of comparison compounds A and B, resp., were infected to 100 and 20%, and the unteated plants were infected to 100%. Claims : 1. 6-(2,6-Difluoro-phenyl)-triazolopyrimidines of formula I I in which R1 and R2 independently denote hydrogen or C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or C4-C10-al-kadienyl, C3-C10-cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or where R1 and R2 radicals may be unsubstituted or may carry one to three groups Ra, Ra is cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C6-haloal-kyl, C3-C6-cycloalkyl, C1-C6e-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylth10, C1-C6-alkylamino, di-C1-C6-alkyl-amino, C2-Cg-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy and C1-C4-alkylened10xy; or R1 and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one to three Ra radicals; X is halogen, cyano, C1-C6-alkoxy, C1-C6-haloalkoxy or C3-Ce-alkenyloxy. Compounds of formula I according to claim 1, in which R1 is straight chained or branched C1-C6-alkyl, C2-C6-alkenyl / or C3-C6-cycloalkyl, and R2 is hydrogen or C1-C6-alkyl, or R1 and R2 together with the interjacent nitrogen atom represent a heterocyclic ring with 5 or 6 carbon atoms being opt10nally substituted with one or two Ci-Cg-alkyl groups. Compounds according to claims 1 or 2 in which R2 is hydrogen. Compounds according to claims 1 to 3 in which X is halogen. A process for the preparat10n of compounds of formula I as defined in claim 4 which comprises reacting 5,7-dihalogen-6-(2,6-difluoro-phenyl)-triazolopyrimidines of formula II II in which Y is halogen with an amine of formula III III in which R1 and R2 are defined as for formula I to produce compounds of formula I. A composit10n suitable for controlling phytopathogenic fungi, comprising a solid or liquid carrier and a compound of the formula I as claimed in claim 1. A method for controlling phytopathogenic fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack with an effective amount of a compound of the formula I as claimed in claim 1. 8. 6-(256-difluoro-phenyl)-triazolopyrmidines substantially as herein above described and exemplified. 9. A method for controlling phytopathogenic fungi substantially as herein above described and exemplified. V

Full Text

6-(2,6-Difluoro-phenyl)-triazolopyrimidines
Descript10n
The invent10n relates to 6-(2,6-difluoro-phenyl)-triazolopyrimidines of formula I
I
in which
R1 and R2 independently denote hydrogen or
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or C4-C10-alka-
dienyl, C3-C10-cycloalkyl, phenyl, naphthyl, or
5- or 6-membered heterocyclyl, containing one to four
nitrogen atoms or one to three nitrogen atoms and one sulfur
or oxygen atom, or
5- or 6-membered heteroaryl, containing one to four nitrogen
atoms or one to three nitrogen atoms and one sulfur or oxygen
atom, or
where R1 and R2 radicals may be unsubstituted or may carry one to three groups Ra,
Ra is cyano, nitro, hydroxyl, C1-Cg-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylth10, C1-C6-alkylamino, di-C1-C6-alkylamino, C2-C6~alkenyl, C2-Ce-alkenyloxy, C2~C6-alkynyl, C3-C6-alkynyloxy and C1-C4-alkylened10xy; or
ll and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one to three Ra
radicals;
I is halogen, cyano, C1-C6~alkoxy, C1-C6-haloalkoxy or C3-Cs-al-kenyloxy.
loreover, the invent10n relates to processes for their prepara-:10n, composit10ns containing them and to their use for combating )hytopathogenic fungi.

5-Phenyl-7-amino-triazolopyrimidines are generally known from JS 4,567,262 and US 5,593,996.
Triazolopyrimidines with a trifluorophenyl group in 6-posit10n ire disclosed in WO-A 98/46607 and EP-A 945 453.
?rom WO-A 98/46608 some 6-(2,6-difluoro-phenyl)-triazolopyrimidi-ies are known, which are substituted in the 7-posit10n by fluori-lated alkylamines.
?he compounds disclosed in the documents discussed above are said :o be active against var10us phytopathogenic fungi.
:t is an object of the present invent10n to provide compounds having improved fungiC1dal activity.
le have found that this object is achieved by the compounds defi-Led at the outset. Furthermore, we have found processes for their reparat10n, composit10ns comprising them and methods for :ontrolling phytopathogenic fungi using the compounds I.
'he compounds of the formula I differ from the compounds known rom WO-A 98/46608 in the combinat10n of the 2,6-difluoro-phenyl roup with an halogen free amino group in the 7-posit10n of the riazolopyrimidine system.
he present invent10n further provides a process for the prepara-10n of compounds of formula I as defined above which comprises reating a 5,7-dihalo compound of formula II in which X is halo-en with an amine of formula III.

he react10n between the 5,7-dihalo compound II and the amine of ormula III can be carried out under condit10ns known from WO-A 8/46608.
Dmpounds of formula II are known from EP-A 550 113; they can be repared by known methods [cf. EP-A 550 113 or EP-A 770 615].
le react10n is preferably carried out in the presence of a Solent . Suitable solvents include ethers, such as d10xane, diethyl :her and, espeC1ally, tetrahydrofuran, halogenated hydrocarbons

such as dichloromethane and aromatic hydrocarbons, for example toluene.
The react10n is suitably carried out at a temperature in the range from 0°C to 70°C/ the preferred react10n temperature being from 10°C to 3 5°C.
It is also preferred that the react10n is carried out in the presence of a base. Suitable bases include tertiary amines, such as triethylamine, and inorganic bases, such as potassium carbonate or sodium carbonate. Alternatively, an excess of the compound of formula III may serve as a base.
The react10n mixtures are worked up in a customary manner, for example by mixing with water, phase separat10n and, if required, chromatographic purificat10n of the crude products. Some of the end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperatures. If the end products are obtained as solids, purificat10n can also be carried out by recrystallizat10n or digest10n.
Compounds of formula II are known in the art and can be obtained by synthesis routes disclosed in EP-A 550 113, EP-A 770 615 and WO-A 98/46608.
Compounds of formula I in which X denotes cyano, C1-C6~alkoxy, C1-C6-haloalkoxy or C3-Cs-alkenyloxy can be prepared by reacting compounds I in which X is halogen, preferably chloro, with compounds of formula IV, which are, dependent from the value of X' to be introduced to yield formula I compounds, an anorganic cyano salt, an alkoxylate, haloalkoxylate or an alkenyloxylate, respectively, preferably in the presence of a a solvent. The cat10n M in formula IV has minor influence; for practical and economical reasons usually ammonium-, tetraalkylammonium- or alkalimetal-and earth metal salts are preferred.

The react10n is suitably carried out at a temperature in the range from 0 to 120°C, the preferred react10n temperature being from 10 to 40°C [cf. J. Heterocycl. Chem. , Vol. 12, p. 861-863 (1975) ] .

suitable solvents include ethers, such as d10xane, diethyl ether and, espeC1ally, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons, for example toluene.
If individual compounds I are not obtainable by the routes described above, they can be prepared by derivatizat10n of other compounds I.
In the symbol definit10ns given in the formulae above, collective terms were used which generally represent the following sub-stituents:
- halogen: fluorine, chlorine, bromine and 10dine;
- C1-C10-alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 10, espeC1ally 1 to 6 carbon atoms, for example C1~C4-alkyl as ment10ned above or pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethyl-butyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methyl-propyl and l-ethyl-2-methylpropyl;
- C2~C10-alkenyl: unsaturated, straight-chain or branched hydro
carbon radicals having 2 to 10, espeC1ally 2 to 6 carbon atoms
and a double bond in any posit10n, for example ethenyl,
1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,
3-butenyl, 1-methyl-l-propenyl, 2-methyl-l-propenyl,
l-methyl-2-propenyl and 2-methyl-2-propenyl;
C2-C10~alkynyl: straight-chain or branched hydrocarbon radicals having 2 to 10, espeC1ally 2 to 4 carbon atoms and a triple bond in any posit10n, for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl;
haloalkyl moieties of C1-C6-haloalkoxy: straight-chain or branched alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms (as ment10ned above), where the hydrogen atoms in these groups may be partially or fully replaced by halogen atoms as ment10ned above, for example C1-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluorome-thoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-tri-

fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy;
C3-C10~cycloalkyl: mono- or bicyclic cycloalkyl groups having 3 to 10 carbon atoms; monocyclic groups preferably have 3 to 8, espeC1ally 3 to 6 ring members, bicyclic groups preferably have 8 to 10 ring members.
A 5- or 6-membered heterocyclyl group, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, preferably one oxygen atom.
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, in addit10n to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-iso-thiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,
1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;
6-membered heteroaryl, containing one to four nitrogen atoms: 6-membered heteroaryl groups which, in addit10n to carbon atoms, nay contain one to three or one to four nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-py-ridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimi-iinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
Vith respect to their intended use, preference is given to tria-solopyrimidines of the formula I having the following sub-stituents, where the preference is valid in each case on its own :>r in combinat10n:
i. preferred cycloalkyl moiety is cyclopentyl being opt10nally substituted by one or more nitro, cyano, C1-C6-alkyl, C1-C6-alkoxy groups .
L preferred heteroaryl moiety is pyridyl, pyrimidyl, pyrazolyl or ;hienyl.

Preference is given to compounds of formula I in which any alkyl part of the groups R1 or R2, which may be straight chained or branched, contains 1 to 9 carbon atoms, more preferably 2 to 6 carbon atoms, any alkenyl or alkynyl part of the substituents R1 or R2 contains 2 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, any cycloalkyl part of the substituents R1 or R2 contains from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms, and any bicycloalkyl part of the substituents R1 or R2 contains from 7 to 9 carbon atoms. Any alkyl, alkenyl or alkynyl group may be linear or branched.
Compounds of formula I are preferred in which R1 is not hydrogen.
Moreover, compounds of formula I are preferred in which R1 represents a straight-chained or branched Ci-C10~alkyl, in particular a branched C3-C10~aikyl group, a C3-Cs-cycloalkyl, a Cs-Cg-bicycloal-kyl, a C3-C8-cycloalkyl-Ci-C6-alkyl, Ci-Ci0-alkoxy-Ci-C6-alkyl, or a phenyl group being opt10nally substituted by one to three C1-C10-alkyl or Ci-C10-alkoxy groups.
Particular preference is given to compounds I in which R2 represents a hydrogen atom or a C1-C10-alkyl group, in particular a hydrogen atom.
Moreover, particular preference is given to compounds I in which R2 is methyl or ethyl.
If R1 denotes an opt10nally substituted C3-C8~cycloalkyl group, preferably a cyclopentyl or cyclohexyl group, R2 preferably represents a hydrogen atom or Ci-Ce-alkyl group.
Moreover, particular preference is given to compounds I in which R1 and R2 together with the interjacent nitrogen atom form an opt10nally substituted heterocyclic ring, preferably an opt10nally substituted C3-C7~heterocyclic ring, in particular a pyrrolidine, piperidine, tetrahydropyridine, in particular 1,2,3,6-tetrahydro-pyridine or azepane ring which is opt10nally substituted by one or more C1-C10-alkyl groups.
Besides, particular preference is given to compounds I in which X is chloro or bromo, especially chloro.
Moreover, preference is given to compounds I in which X is cyano or methoxy.

Furthermore, particular preference is given to compounds I in which X is ethoxy, n-propoxy, iso-propoxy, allyloxy, or 3-methy-lallyloxy.
Included in the scope of the present invent10n are (R) and (S)
isomers of compounds of general formula I having a chiral center
and the racemates thereof, and salts, N-oxides and aC1d addit10n
compounds.
With respect to their use, particular preference is given to the compounds I compiled in the tables below. The groups ment10ned in the tables for a substituent are furthermore for their part, independently of the combinat10n in which they are ment10ned, a particularly preferred embodiment of the respective substituents.
Table 1
Compounds of the formula I, in which X is chloro and R1 and R2
correspond to one row in Table A
Table 2
Compounds of the formula I, in which X is bromo and R1 and R2
correspond to one row in Table A
Table 3
Compounds of the formula I, in which X is cyano and R1 and R2
correspond to one row in Table A
Table 4
Compounds of the formula I, in which X is methoxy and R1 and R2
correspond to one row in Table A
Table 5
Compounds of the formula I, in which X is ethoxy and R1 and R2
correspond to one row in Table A
Table 6
Compounds of the formula I, in which X is n-propoxy and R1 and R2
correspond to one row in Table A
Table 7
Compounds of the formula I, in which X is iso-propoxy and R1 and
R.2 correspond to one row in Table A
Table 8
Compounds of the formula I, in which X is allyloxy and R1 and R2
:orrespond to one row in Table A

■raC1e y
Compounds of the formula I, in which X is 3-methylallyloxy and R1
and R2 correspond to one row in Table A

The compounds I are suitable as fungiC1des. They have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and 23asid10;nycetes. Some of them act systemically, and they can be employed in crop protect10n as foliar- and soil-acting fungiC1des.
They are espeC1ally important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit speC1es, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
SpeC1fically, they are suitable for controlling the following plant diseases:
• Alternaria speC1es, Podosphaera speC1es, Sclerotinia speC1es,
Physalospora canker on vegetables and fruit,
• Botrytis C1nerea (gray mold) an strawberries, vegetables , or-
■ namentals and grapevines,
• Corynespora cassiicola on cucumbers,
• Colletotrichum speC1es on fruit and vegetables,
• Diplocarpon rosae on roses,

• Elsinoe fawcetti and Diaporthe C1tri on C1trus fruit,
• Sphaerotheca speC1es on cucurbits, strawberries and roses,
• Cercospora speC1es on peanuts, sugar beets and aubergines,

• Erysiphe C1choracearum on cucurbits,
• Leveillula taurica on paprika, tomatoes and aubergines,
• Mycosphaerella speC1es on apples and Japanese apricot,
• Phyllactinia kakicola, Gloesporium kaki on Japanese apricot,
• Gyiunosporangium yamadae, Leptothyrium pomi, Podosphaera leuco-tricha and Gloedes pomigena on apples,
• Cladosporium carpophilum on pears and Japanese apricot,
• Phomopsis speC1es on pears,
• Phytophthora speC1es on C1trus fruit, potatoes, on10ns, espeC1ally Phytophthora infestans on potatoes and tomatoes,
• Blumeria graminis (powdery mildew) on cereals,
• Fusarium- and VertiC1llium speC1es on var10us plants,
• Glomerella C1ngulata on tee,
• Drechslera- and Bipolaris speC1es on cereals and rice,
• Mycosphaerella speC1es on bananas and peanuts,
• Plasmopara viticola on grapevines,
• Personospora speC1es on on10ns, spinach and chrysantemum,
• Phaeoisar10psis vitis and Sphaceloma ampelina on grapefruits,
• Pseudocercosporella herpotrichoides on wheat and barley,
• Pseudoperonospora speC1es on hop and cucumbers,
• PucC1nia speC1es and Typhula speC1es on cereals and turf,
• Pyricularia oryzae on rice,
• Rhizoctonia speC1es on cotton, rice and turf,
• Stagonospora nodorum and Septoria tritiC1 on wheat,
• UnC1nula necator on grapevines,
• Ustilago speC1es on cereals and sugar cane, and
• Venturis speC1es (scab) on apples and pears.
Moreover, the compounds I are suitable for controlling harmful fungi such as PaeC1lomyces var10tii in the protect10n of materials (e.g. wood, paper, paint dispers10ns, fibers and tissues) and in the protect10n of stored products.
The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infect10n, with a fungiC1dally active amount of the active ingredients. Applicat10n can be effected both before and after infect10n of the materials, plants or seeds by the fungi.
In general, the fungiC1dal composit10ns comprise from 0.1 to 95, preferably 0.5 to 90, % by weight of active ingredient.
When used in crop protect10n, the rates of applicat10n are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the effect desired.

Ln the treatment of seed, amounts of active ingredient of from 3.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.
tfhen used in the protect10n of materials or stored products, the rate of applicat10n of active ingredient depends on the nature of the field of applicat10n and on the effect desired. Rates of applicat10n convent10nally used in the protect10n of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.
The compounds I can be converted into the customary formulat10ns, e.g. solut10ns, emuls10ns, suspens10ns, dusts, powders, pastes and granules. The use form depends on the particular purpose; in any case, it should guarantee a fine and uniform distribut10n of the compound according to the invent10n.
The formulat10ns are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fract10ns), alcohols (e.g. methanol, butanol), ketones (e.g. cy-clohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly-disperse silica, silicates); emulsifiers such as non-10nic and an10nic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as li-gnin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic aC1d, naphthalenesulfonic aC1d, phenolsulfonic aC1d, dibutylnaphthalenesulfonic aC1d, alkylaryl-sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty aC1ds and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthaiene-sulfonic aC1d with phenol or formaldehyde, polyoxyethylene octyl-phenyl ether, ethoxylated isooctylphenol, octylphenol, nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl

alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparat10n of directly sprayable solut10ns, emuls10ns, pastes or oil dispers10ns are mineral oil fract10ns of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphtha-lene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethyIformamide, dimethyl sulfoxide, N-me-thylpyrrolidone and water.
Powders, materials for scattering and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calC1um sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulat10ns comprise of from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient . The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are exemplary formulat10ns:
I. 5 parts by weight of a compound according to the invent10n are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.
II. 30 parts by weight of a compound according to the invent10n are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel.

This gives a formulat10n of the active ingredient with good adhes10n properties (comprises 23% by weight of active ingredient) .
10 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic aC1d N-monoethanolamide, 2 parts by weight of calC1um dodecylbenzenesulfonate and 2 parts by weight of the adduct of 4 0 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).
2 0 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 3 0 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient).
80 parts by weight of a compound according to the invent10n are mixed thoroughly with 3 parts by weight of sodium diiso-butylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic aC1d from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).
90 parts by weight of a compound according to the invent10n are mixed with 10 parts by weight of N-methyl-CC-pyrrolidone, which gives a solut10n which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient) .
2 0 parts by weight of a compound according to the invent10n are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 3 0 parts by weight of isobutanol, 2 0 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solut10n into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispers10n which comprises 0.02% by weight of the active ingredient.
. 2 0 parts by weight of a compound according to the invent10n are mixed thoroughly with 3 parts by weight of sodium diiso-

butylnaphthalene-Ct-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic aC1d from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.
The active ingredients can be used as such, in the form of their formulat10ns or the use forms prepared therefrom, e.g. in the form of directly sprayable solut10ns, powders, suspens10ns or dispers10ns, emuls10ns, oil dispers10ns, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring. The use forms depend entirely on the intended purposes; in any case, this is intended to guarantee the finest possible distribut10n of the active ingredients according to the invent10n.
Aqueous use forms can be prepared from emuls10n concentrates, pastes or wettable powders (sprayable powders, oil dispers10ns) by adding water. To prepare emuls10ns, pastes or oil dispers10ns, the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilut10n with water.
The active ingredient concentrat10ns in the ready-to-use products can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulat10ns comprising over 95% by weight of active ingredient, or even the active ingredient without additives.
Var10us types of oils, herbiC1des, fungiC1des, other pestiC1des, or bacteriC1des may be added to the active ingredients, if appropriate also only immediately pr10r to use (tank mix). These agents can be admixed with the agents according to the invent10n in a weight rat10 of 1:10 to 10:1.
In the use form as fungiC1des, the composit10ns according to the invent10n can also be present together with other active ingre-dients, e.g. with herbiC1des, insectiC1des, growth regulators, fungiC1des or else with fertilizers. Mixing the compounds I or

tne composit10ns comprising them in the use form as fungiC1des with other fungiC1des frequently results in a broader fungiC1dal spectrum of act10n.
The following list of fungiC1des, together with which the compounds according to the invent10n can be used, is intended to illustrate the possible combinat10ns, but not to impose any limitat10n:
sulfur, dith10carbamates and their derivatives, such as iron(III) dimethyldith10carbamate, zinc dimethyldith10carba-mate, zinc ethylenebisdith10carbamate, manganese ethylenebis-dith10carbamate, manganese zinc ethylenediaminebisdith10car-bamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdith10carbamate) , ammonia complex of zinc (N,N'-propylenebisdith10carbamate), zinc (N,N'-propylenebis-dith10carbamate), N,N'-polypropylenebis(th10carbamoyl)disulfide;
nitro derivatives, such as dinitro(1-methylheptyl)phenyl cro-tonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate;
heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonoth10ate, 5-amino-l-[bis(dime-thylamino)phosphinyl]-3-phenyl-1,2,4- triazole, 2,3-dicya-no-1,4-dith10anthraquinone, 2-th10-l,3-dith10lo[4,5-b]quino-xaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, N-(1,1,2,2-tetrachloroe-thylth10)tetrahydrophthalimide, N-trichloromethylth10tetrahy-drophthalimide, N-trichloromethylth10phthalimide, 5-Chloro-2-cyano-4-p-tolyl-imidazole-l-sulfonic aC1d dimethylamide, N-dichlorofluoromethylth10-N',N'-dimethyl -N-phenylsulfo-diamide, 5-ethoxy-3~trichlorome-thyl-1,2,3-thiadiazole, 2-th10cyanatomethylth10benzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazo-no)-3-methyl-5~isoxazolone, pyridine-2-th10l 1-oxide, 8-hy-droxyquinoline or its copper salt, 2,3-dihydro-5-carboxanili-do-6-methyl-l,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-me-thyl-1,4-oxathiine 4,4-d10xide, 2-methyl-5,6-dihydro-4H-py-ran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dime-thylfuran-3-carboxanilide, 2-Chloro-N-(4'-chloro-biphe-nyl-2-yl)-nicotinamide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl- 2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanili-de, 2-10dobenzanilide, N-formyl-N-morpholine-2,2,2-trichlo-

roethyl acetal, piperazine-1,4-diylbis-l-(2,2,2-trichloro-ethyl) formamide, 1- (3 , 4-dichloroanilino) -1-f ormylami-no-2,2,2-trichloroethane; 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-C1s-2,6-di-methyl- morpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl] -piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-d10xo-lan-2-yl-ethyl]-lH-l,2,4-triazole, 1-[2-(2 , 4-dichlorophenyl) -4-n-propyl-l,3-d10xolan-2-yl-ethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazo-lyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-tri-azol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1- (lH-l,2,4-triazol-l-yl)-2-butanol, (2RS,3RS)-1-[3-(2-chlo-rophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidineme-thanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycar-bonyl-2-th10ureido)benzene, 1,2-bis(3-methoxycarbonyl-2~th10-ureido)benzene,
strobilurines such as azoxystrobin, kresoxim methyl, methyl-E-methoxyimino-[a-(2-phenoxyphenyl)]-acetamide, methyl E-methoxyimino-[a-(2,5-dimethylphenoxy)-o-tolyl]acetamide, picoxystrobin, pyraclostrobin, trifloxystrobin, anilinopyrimidines such as N-(4,6-dimethylpyrimidin~2-yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]-aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles such as 4-(2,2-difluoro-1,3-benzod10xol-4-yl)pyrrole-3-carbonitrile,
C1nnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine, 3-(4-fluorophenyl)-3-(3,4-di-methoxy-phenyl)acryloylmorpholine,
and a variety of fungiC1des such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutar-imide, hexachlorobenzene, methyl N-(2,6-dimethylphe-nyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphe-nyl)-N-(2'-methoxyacetyl)-alanine methyl ester, N-(2,6-dime-thylphenyl)-N-chloroacetyl-D, L~2-arnino- butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5~vinyl-3-(3,5-dichlorophenyl)-2,4-di-oxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl(5-methyl-5-me-thoxymethyl]-1,3-oxazolidine-2,4-d10ne, 3-(3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl) -1,2-dimethylcyclopropane-l,2-dicarboximide, 2-cya-no-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, 3,5-Dichloro-N-(3~chloro-l-ethyl-l-methyl-2-oxo-propyl)-4-methyl-benzamide, 1-(3-Bromo~6-methoxy-2-methyl-phenyl)-1-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 1-[2-(2,4-di-

chl oro—phenyl)pentyl]—1H—1, 2,4—triazole, 2,4—difluoro— a- (1H-1,2 ,4-triazolyl-l-methyDbenzhydryl alcohol, N- (3-chlo-ro-2 , 6-dinitro-4-trifluoromethylphenyl) -5-trif luorome-thyl-3-chloro-2-aminopyridine, 1- ( (bis (4-f luorophenyl)methyl-silyl)methyl)-1H-1,2,4-triazole.
Synthesis Examples
With due modificat10n of the starting compounds, the protocol shown in the synthesis example below was used for obtaining further compounds I. The resulting compounds I, together with physical data, are listed in the Table I which follows.
Example 1 Preparat10n of 5,7-dihydroxy-6-(2,6-difluorophenyl) -[1,2,4]-triazolo[1,5-a]-pyrimidine
A mixture of 3-amino-l,2,4-triazole (14 g), diethyl (2,6-difluo-xophenyl)-malonate (0,17 mol, cf. EP-A 10 02 788) and tributyl-amine (50 ml) was heated at about 180°C for six hours. The react10n mixture was cooled to about 70°C. 200 ml of 10 % aqueous sodium hydroxide solut10n were added and the react10n mixture were stirred for 30 minutes. The phases were separated, the aqueous phase was extracted with diethyl ether. The aqueous phase is aC1dified. The preC1pitate was filtered off and dried to yield 40 g of the title compound.
Example 2 Preparat10n of 5,7-dichloro-6-(2,6-difluorophenyl) -[l,2,4]-triazolo[l,5-a]-pyrimidine
A mixture of 5,7-dihydroxy-6-(2 , 6-difluorophenyl)-[1,2,4]-triazolo- [1, 5-a]pyrimidine (30 g, obtained from Ex. 1) and phosphorous oxychloride (50 ml) was refluxed for about eight hours. Phosphorous oxychloride was partly distilled off. The residue was poured into a mixture of dichloromethane and water. The organic layer was separated, dried and filtered. The filtrate was concentrated in vacuo to yield 28 g of the title compound of mp. 121°C.
Example 3 Preparat10n of 5-chloro-6-(2,6-difluorophenyl)-7-iso-
propylamino-[1,2,4]-triazolo[1,5-a]pyrimidine [1-3]
\ mixture of isopropylamine (1,5 mmol), triethylamine (1,5 mmol) md dichloromethane (10 ml) was added to a mixture of 5,7-di-:hloro-6-(2,6-difluorophenyl)-[l,2,4]-triazolo[l,5-a]-pyrimidine (1,5 mmol, obtained from Ex. 2) and dichloromethane (2 0 ml) under stirring. The react10n mixture was stirred for about 16 hours at ibout 2 0 to 2 5°C and subsequently washed with dilute hydrocloric

aC1d (5%). The organic layer was separated, dried and filtered. The filtrate was evaporated under reduced pressure and the residue was chromatographed to yield 0,43 g of the title compound of mp. 169°C.
Example 4 Preparat10n of 5-cyano-6-(2,6-difluorophe-
nyl)-7-(4-methylpiperidin-l-yl)-[1,2,4]-triazolo [1, 5-a]pyrimidine [1-18]
A mixture of 5-chloro-6-(2,6-difluorophenyl)-7-(4-methylpiperi-din-l-yl)-[1,2,4]-triazolo-[1,5-a]-pyrimidine (0,1 mol; 1-4) and tetraethylammonium cyanide (0,25 mol) in 750 ml Dimethylformamide (DMF) (750 ml) was stirred for 16 hours at about 20 to 25°C. To this mixture water was added and methyl tert.butyl ether (MTBE), the organic phase was separated, washed with water, dried and filtered. The filtrate was evaporated and the residue was chromatographed to yield 6,95 g of the title compound of mp. 212°C.
Example 5 Preparat10n of 5-methoxy-6-(2,6-difluorophenyl) -7-(diethylamino)-[1,2,4]-triazolo[1,5-a]pyrimidine [1-19]
To a solut10n of 5-chloro-6-(2,6-difluorophenyl)-7-(diethyl-amino) - [1 , 2 , 4] -triazolo- [1 , 5-a] -pyrimidine (65 mmol; 1-6) in 400 ml dry methanol was added a 3 0% solut10n of sodium methano-late (71,5 mmol) at about 20 to 25°C. This mixture was further stirred for 16 hours. Methanol was evaporated and the residue was dissolved with dichloromethane. The organic phase was washed with water, dried and filtered. The filtrate was evaporated and the residue was chromatographed to yield 16,3 g of the title compound of mp. 153°C.

Examples of the act10n against harmful fungi
The fungiC1dal act10n of the compounds of the formula I was demonstrated by the following experiments:
The active compounds, separately or together, were formulated as a 10% emuls10n in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersant act10n based on ethoxylated alkyl-phenols) and 10% by weight of Wettol® EM (non10nic emulsifier based on ethoxylated castor oil) and diluted with water to the desired concentrat10n.
310logical activity trial - FungiC1dal control of early blight on tomatoes (Alternaria solani)
ifoung seedlings of tomato plants of the variety "Grofie Fleischto-nate St. Pierre" were grown in pots to the 2 to 4 leaf stage. These plants were sprayed to run-off with an aqueous suspens10n, :ontaining the concentrat10n of active ingredient ment10ned in :he table below, prepared from a stock solut10n containing 10 % Df the active ingredient, 85 % cyclohexanone and 5 % emulsifier. The next day, the treated plants were inoculated with an aqueous suspens10n of Alternaria solani containing 0,2 x 106 spores per nl. Then the trial plants were immediately transferred to a hu-nid chamber. After 6 days at 2 0 to 23°C and a relative humidity

close to 100 %, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the plants which had been treated with 250 ppm of > compounds 1-2 to 1-9, 1-11, 1-12, 1-14, 1-15 and 1-17 showed an infect10n of not more than 1%, whereas the untreated plants were infected to 90%.
Active compounds A and B known from WO-A 98/46608 were used as i comparison compounds:

Comparison trial - Control of gray mould {Botrytis C1nerea) on fruit slices of green pepper
Fruit slices of green pepper were sprayed to run-off with an aqueous suspens10n, containing the concentrat10n of active ingredient or their mixture ment10ned in the table below, prepared from a stock solut10n containing 10 % of the active ingredient, 85 % cyclohexanone and 5 % emulsifier. After 2 hours the sprayed-on layer had dried, the disks were inoculated with a spore suspens10n of Botrytis C1nerea containing 1,7 x 106 spores per ml in 2 wt. % aqueous b10malt solut10n. The infected fruit slices were then incubated in chambers with high humidity for four days at 18-20°C. The fruit slice area under fungal attack was then assessed visually in percent.
In this test, the plants which had been treated with 500 ppm of compounds 1-2, 1-8 and 1-14, resp., showed an infect10n of not more than 3%, whereas the the plants treated with 5 00 ppm of comparison compounds A and B, resp., were infected to 100 and 20%, and the unteated plants were infected to 100%.

Claims :
1. 6-(2,6-Difluoro-phenyl)-triazolopyrimidines of formula I
I
in which
R1 and R2 independently denote hydrogen or
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or C4-C10-al-kadienyl,
C3-C10-cycloalkyl, phenyl, naphthyl, or
5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or
5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or
where R1 and R2 radicals may be unsubstituted or may carry one to three groups Ra,
Ra is cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C6-haloal-kyl, C3-C6-cycloalkyl, C1-C6e-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylth10, C1-C6-alkylamino, di-C1-C6-alkyl-amino, C2-Cg-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy and C1-C4-alkylened10xy; or
R1 and R2 together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one to three Ra radicals;
X is halogen, cyano, C1-C6-alkoxy, C1-C6-haloalkoxy or C3-Ce-alkenyloxy.

Compounds of formula I according to claim 1, in which
R1 is straight chained or branched C1-C6-alkyl, C2-C6-alkenyl / or C3-C6-cycloalkyl, and
R2 is hydrogen or C1-C6-alkyl, or
R1 and R2 together with the interjacent nitrogen atom represent a heterocyclic ring with 5 or 6 carbon atoms being opt10nally substituted with one or two Ci-Cg-alkyl groups.
Compounds according to claims 1 or 2 in which R2 is hydrogen.
Compounds according to claims 1 to 3 in which X is halogen.
A process for the preparat10n of compounds of formula I as defined in claim 4 which comprises reacting 5,7-dihalogen-6-(2,6-difluoro-phenyl)-triazolopyrimidines of formula II
II
in which Y is halogen with an amine of formula III
III
in which R1 and R2 are defined as for formula I to produce compounds of formula I.
A composit10n suitable for controlling phytopathogenic fungi, comprising a solid or liquid carrier and a compound of the formula I as claimed in claim 1.
A method for controlling phytopathogenic fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack with an effective amount of a compound of the formula I as claimed in claim 1.

8. 6-(256-difluoro-phenyl)-triazolopyrmidines substantially as herein
above described and exemplified.
9. A method for controlling phytopathogenic fungi substantially as
herein above described and exemplified.

V

Documents:

0313-chenp-2004 abstract-duplicate.pdf

0313-chenp-2004 abstract.pdf

0313-chenp-2004 claims-duplicate.pdf

0313-chenp-2004 claims.pdf

0313-chenp-2004 correspondence-others.pdf

0313-chenp-2004 correspondence-po.pdf

0313-chenp-2004 description (complete)-duplicate.pdf

0313-chenp-2004 description (complete).pdf

0313-chenp-2004 form-1.pdf

0313-chenp-2004 form-18.pdf

0313-chenp-2004 form-26.pdf

0313-chenp-2004 form-3.pdf

0313-chenp-2004 form-5.pdf

0313-chenp-2004 others document.pdf

0313-chenp-2004 pct.pdf

313-chenp-2004-abstract.pdf

313-chenp-2004-claims.pdf

313-chenp-2004-correspondnece-others.pdf

313-chenp-2004-correspondnece-po.pdf

313-chenp-2004-description(complete).pdf

313-chenp-2004-form 1.pdf

313-chenp-2004-form 3.pdf

313-chenp-2004-form 5.pdf

313-chenp-2004-pct.pdf

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Patent Number

214347

Indian Patent Application Number

313/CHENP/2004

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

11-Feb-2008

Date of Filing

16-Feb-2004

Name of Patentee

BASF AKTIENGESELLSCHAFT

Applicant Address

D-67056 LUDWIGSHAFEN,

Inventors:

#	Inventor's Name	Inventor's Address
1	TORMO I BLASCO, JORDI	MUHLWEG 47, 67117 LIMBURGERHOF,
2	SAUTER, HUBERT	NECKARPOMENADE 20, 68167 MANNHEIM,
3	MULLER, BERND	JEAN-GANSS-STR. 21, FRANKENTHAL,
4	GEWEHR, MARKUS	GOETHESTRASSE 21, 56288 KASTELLAUM,
5	GRAMMENOS, WASSILLIOS	SAMUEL-HAHNEMANN-WEG 9, 67071 LUDWIGSHAFEN,
6	GROTE, THOMAS	IM HOEHNHAUSEN 18, 67157 WACHENHEIM,
7	GYPSER, ANDREAS	B 4, 4, 68159 MANNHEIM, GERMANY
8	RHEINHEIMER, JOACHIM	MERZIGER STRASSE 24, 67063 LUDWIGSHAFEN,
9	SCHAFER, PETER	ROMERSTRASSE 1, 67308 OTTERSHEIM,
10	SCHIEWECK, FRANK	LINDENWEG 4, 67258 HESSHEIM,
11	RACK, MICHAEL	SANDWINGERT 67, 69123 HEIDELBERG,
12	AMMERMANN, EBERHARD	VON-GAGERN-STRASSE 2, 64646 HEPPENHEIM,
13	STRATHMANN, SIGFRIED	DONNERSBERGSTRASSE 9, 67117 LIMBURGERHOF,
14	LORENZ, GISELA	ERLENWEG 13, 67434 HAMBACH,
15	STIERL, REINHARD	GINSTERSTR. 17, 67112 MUTTERSTADT,

PCT International Classification Number

C07D 487/04

PCT International Application Number

PCT/EP02/07575

PCT International Filing date

2002-07-08

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	01117404.2	2001-07-18	EUROPEAN UNION