EP1725563A2 - 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds - Google Patents

Abstract

The invention relates to 5,6-dialkyl-7-amino-triazolopyrimidines of formula (I), in which the substituents are defined as follows: R1 represents alkyl, alkoxyalkyl, alkenyl or alkynyl; R2 represents alkyl, alkoxyalkyl, alkenyl or alkynyl, R1 and/or R2 being substituted according to the description. The invention also relates to a method for producing said compounds, to agents containing the latter and to their use for controlling plant-pathogenic fungi.

Description

5,6-dialkyl-7-amino-triazolopyrimidines, process for their preparation and their use for controlling harmful fungi and agents containing them

description

The present invention relates to 5,6-dialkyl-7-amino-triazolopyrimidines of the formula I.

in which the substituents have the following meaning: R ^{1 is} C ₂ -C ₁₂ alkenyl or C ₂ -C ₁₂ alkynyl, wherein the carbon chains are unsubstituted or carry one to three identical or different groups R ^a and / or R ^b ; or

C _r C ₄ alkyl, CrC ^ alkoxy-dC ^ alkyl, CC ₆ -alkoxy-C ₂ -C ₁₂ -alkenyl or C-ι-C ₆ - alkoxy-C ₂ -C ₂ alkynyl, wherein the carbon chains carry one to three identical or different groups R ^a ; R ^{a is} halogen, cyano, nitro, hydroxy, C ₁ -C ₆ -alkylthio, C ₃ -C ₁₂ -alkenyloxy, C ₃ -C ₁₂ -alkynyloxy, NR ¹¹ R ¹² , or

C ₃ -C ₆ -cycloalkyl, which may carry one to four identical or different groups R ^b ;

R ^b CC ₄ alkyl, cyano, nitro, hydroxy, Cι-C -alkoxy ₆ -A, C-rC ₆ alkylthio, C ₃ - Ce-alkenyloxy, C ₃ -C ₆ -alkynyloxy and NR ¹ R ¹²

R ¹¹ , R ^{12 are} hydrogen or CC ₆ alkyl; wherein the carbon chains of the groups R ^{a may in} turn be halogenated;

R ² C -C ₂ alkyl, C ₂ -C ₁₂ alkenyl or C ₂ -C ₂ alkynyl, wherein the carbon chains may be substituted by one to three groups R ^c :

R ° cyano, nitro, hydroxy, NR ¹¹ R ¹² ; or C ₃ -C ₆ -cycloalkyl which contains one to four identical or different groups C ₄ -alkyl, halogen, cyano, NR ¹¹ R ¹² can bear alkynyloxy, - nitro, hydroxy, CrC ₆ alkoxy, C _r C ₆ alkylthio, C ₃ -C ₆ alkenyloxy, C ₃ -C. ₆

In addition, the invention relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.

In GB 1 148629 5,6-dialkyl-7-amino-triazolopyrimidines are generally proposed. EP-A 141 317 discloses individual fungicidally active 5,6-dialkyl-7-amino-triazolopyrimidines. However, their effect is in many cases unsatisfactory.

On this basis, the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.

Accordingly, the compounds defined above were found. Furthermore, processes and intermediates for their preparation, agents containing them and methods for controlling harmful fungi using the compounds I have been found.

The compounds of the formula I differ from those mentioned above by the specific embodiment of the substituent in the 6-position of the triazolopyrimidine skeleton, which represents a haloalkyl group or an unsaturated aliphatic group.

The compounds of the formula I have an over the known compounds increased activity against harmful fungi.

The compounds of the invention can be obtained in various ways. Advantageously, the compounds according to the invention are obtained by reacting substituted β-keto esters of the formula II with 3-amino-1,2,4-triazole of the formula III to give 7-hydroxytriazolopyrimidines of the formula IV. The groups R ¹ and R ² in formulas II and IV have the meanings as for formula I and the group R in formula II is C 1 -C ₄ -alkyl, for practical reasons, methyl, ethyl or propyl is preferred therein.

"I" IV

The reaction of the substituted .beta.-keto esters of the formula II with the aminoazoles of the formula III can be carried out in the presence or absence of solvents. It is advantageous to use such solvents, over which the Feedstocks are largely inert and in which they are completely or partially soluble. The solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, especially alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alkoxides and Dimethoxymagnesium, also organic bases, for example tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and d 4-DimethyI- aminopyridine and bicyclic amines and mixtures of these solvents with water in question. Suitable catalysts are bases, as mentioned above, or acids, such as sulfonic acids or mineral acids. The reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. Particularly preferred bases are tertiary amines such as triisopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine. The temperatures are between 50 and 300 ° C, preferably at 50 to 18O ° C, when working in solution [see. EP-A 770 615; Adv. Het. Chem. Vol. 57, p. 81 ff. (1993)].

The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The condensation products of the formula IV thus obtained are usually precipitated from the reaction solutions in pure form and are, after washing with the same solvent or with water and subsequent drying with halogenating agents, in particular chlorinating or brominating agents, the compounds of the formula V in the US Pat Hal is chlorine or bromine, in particular chlorine, reacted. The reaction is preferably carried out with chlorinating agents, such as phosphorus oxychloride, thionyl chloride or sulfuryl chloride at 50 ° C. to 150 ° C., preferably in excess phosphorus oxytrichloride at reflux temperature. After evaporation of the excess phosphorus oxytrichloride, the residue is treated with ice-water, if appropriate with the addition of a water-immiscible solvent. The chlorination product isolated from the dried organic phase optionally after evaporation of the inert solvent is usually very pure and is then treated with ammonia in inert solvents at 100 ° C. to 200 ° C. to give the 7-amino-triazolino [1, 5]. a] -pyrimidines reacted. The reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.

The new 7-amino-azolo [1,5-a] -pyrimidines are optionally isolated after evaporation of the solvent by trituration in water as crystalline compounds.

The β-keto esters of the formula II can be prepared as described in Organic Synthesis Coll. Vol. 1, p. 248, or are commercially available.

Alternatively, the novel compounds of the formula I can be obtained by reacting substituted acyl cyanides of the formula VI, in which R ¹ and R ^{2 have} the meanings indicated above, with 3-amino-1, 2,4-triazole of the formula III.

The reaction can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble. The solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, acetic acid , Propionsäure or bases, as mentioned above, and mixtures of these solvents with water in question. The reaction temperatures are between 50 and 300 ^° C, preferably at 50 to 150 ^° C, when working in solution.

The substituted alkyl cyanides of the formula VI required for the preparation of the 7-amino-azolo [1,5-a] -pyrimidines are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic acid esters with strong bases, e.g. Alkali hydrides, alkali metal alcoholates, alkali metal amides or metal alkyls, are prepared (see: J. Amer., Chem. Soc., Vol. 73, (1951) p. 3766).

Compounds of formula I in which R ¹ is C _r C ₁ haloalkyl, Cι-C -haloalkoxy-C ₁₂ Ci ₂ -alkyl, Ci2-alkoxy-C C ₁₂ haloalkyl, C ₂ -C ₁₂ or C -HaIogenalkenyl C ₂ -C ₁₂ -haloalkynyl, are advantageously obtainable by halogenation of corresponding triazolopyrimidines of the formula VII:

In formula VII R is CC ₁₄ -alkyl, C ₁₂ rAlkoxy-Cι-C ₂ -alkyl, C ₂ -C ₁₂ alkenyl, C ₂ - C ₂ alkynyl, wherein the carbon chains carry one to three groups R ^a can.

The halogenation is usually carried out at temperatures of 0 ° C to 200 ° C, preferably 20 ° C to 110 ° C, in an inert organic solvent in the presence of a radical initiator (eg dibenzoyl peroxide or azobisisobutyronitrile or under UV irradiation, eg with a Hg Vapor lamp) or an acid [cf. Synthetic Reagents, Vol. 2, pp. 1-63, Wiley, New York (1974)].

The reactants are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the halogenating agent in an excess based on VII.

As halogenating agents are, for example, elemental halogens (eg Cl ₂ , Br ₂ , J ₂ ), N-bromo-succinimide, N-chloro-succinimide or Dibromdimethylhydrantoin. The halogenating agents are generally used equimolar, in excess or optionally as solvent.

Compounds of formula I in which R ¹ is C _r C ₁₄ haloalkyl, C ₂ -C ₁₂ haloalkenyl or C ₂ -Cι means ₂ haloalkynyl, alternatively by ether cleavage of corresponding triazolopyrimidines of the formula VIIa accessible:

In formula VIIa, R ^A is alkyl of Cι-Cι _4, C ₂ -C ₁₂ alkenyl or C ₂ -Cι ₂ alkynyl, where the groups R ^A are substituted by hydroxy or alkoxy groups. By heating the compounds VIIa in the presence of mineral acids [HX], such as hydrochloric acid or hydrobromic acid, or nitric acid, the compounds I are obtained [see. Organikum, 15th edition, p. 237 ff, VEB Deutscher Verlag der Wissenschaften, Berlin 1981].

The triazolopyrimidines of the formulas VII and VIIa required for the preparation of the above-described compounds I are in some cases known or can be prepared by known methods [cf. EP-A 141 317].

If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.

However, if mixtures of isomers are obtained in the synthesis, separation is generally not necessary, since the individual isomers partly decompose during preparation for use or during use (for example under light, acid or or base action) can be converted into each other. 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.

In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine, in particular fluorine or chlorine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, e.g. d-Ce-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-ethylbutyl, 1,1,2-trimethylpropyl, 1,2 , 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular -C-C ₂ -haloalkyl such as chloromethyl, bromomethyl , Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl , 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl ;

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 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-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-centenyl, 1,1-dimethyl-2-propenyl, 1,2 Dimethyl 1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- Hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl 2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2- Dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2- 1-ethyl-2-methyl-1-propenyl 2-methyl-2-propenyl;

Alkoxyalkyl: saturated, straight-chain or mono-, di- or tri-branched hydrocarbon chain which is interrupted by an oxygen atom, for. B. C ₅ -C ₂ -alkoxyalkyl: hydrocarbon chain as described above having 5 to 12 carbon atoms, which may be interrupted by an oxygen atom at any position, such as propoxy-ethyl, butoxy-ethyl, pentoxy-ethyl, hexyloxy-ethyl, Heptyloxyethyl, octyloxyethyl, nonyloxyethyl, 3- (3-ethyl-hexyloxy) -ethyl, 3- (2,4,4-trimethyl-pentyloxy) -ethyl, 3- (1-ethyl-3-methyl -butoxy) -ethyl, ethoxy-propyl, propoxy-propyl, butoxy-propyl, pentoxy-propyl, hexyloxy-propyl, heptyloxy-propyl, octyloxy-propyl, nonyloxy-propyl, 3- (3-ethyl-hexyloxy) - propyl, 3- (2,4,4-trimethyl-pentyloxy) -propyl, 3- (1-ethyl-3-methyl-butoxy) -propyl, ethoxy-butyl, propoxy-butyl, butoxy-butyl, pentoxy-butyl, Hexyloxy-butyl, heptyloxy-butyl, octyloxy-butyl, nonyloxy-butyl, 3- (3-ethyl-hexyloxy) -butyl, 3- (2,4,4-trimethyl-pentyloxy) -butyl, 3- (1-ethyl 3-methyl-butoxy) -butyl, methoxy-pentyl, ethoxy-pentyl, propoxy-pentyl, butoxy-pentyl, pentoxy-pentyl, hexyloxy-pentyl, heptyl-oxy-pentyl, 3- (3-methyl-hexyloxy ) -pentyl, 3- (2,4-dimethyl-pentyloxy) -pentyl, 3- (1-ethyl-3-methyl-butoxy) -pentyl;

Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one or two double bonds in any position (as mentioned above), in which groups the hydrogen atoms are partially or completely substituted by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, can be replaced;

Alkynyl: straight-chain or branched hydrocarbon groups having 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 Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-ethyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3 Methyl 4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3 -butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl -1-methyl-2-propynyl; Cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

Included within the scope of the present invention are the (R) and (S) isomers and the racemates of compounds of formula I having chiral centers.

With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

Compounds I are preferred in which the group R ^{1 has} a maximum of 9 carbon atoms.

Likewise preferred are compounds of the formula I in which R ^{1 represents} an unbranched or mono-, di-, tri- or poly-branched haloalkyl group.

If R ^{1 is} haloalkyl, the halogenation is preferably present at the terminal carbon atom. Monohaloalkyl groups are preferred.

In one embodiment of the compounds I of the invention R ¹ is CτC ₁₄ - haloalkyl, CrC ^ haloalkoxy-d-dralkyl, C ₁ -C ₁₂ alkoxy-C ₁ -C ₁₂ -halogenaIkyI, C ₂ -C ₁₂ haloalkenyl or C C ₂ -C ₁₂ -haloalkynyl, which groups have one or two halogen atoms. Here, CrCg-haloalkoxy-propyl and CrCg-alkoxy-halo-propyl groups are preferred.

Haloalkyl, CrCl ₂ -HalogenaIkoxy C-C ₁₂ alkyl, dC ^ alkoxy-CrC ^ -haloalkyl, C ₂ -C ₁₂ haloalkenyl, or - in another embodiment of the compounds I, R ¹ represents a group C-ι-C ₁₄ C ₂ -C ₁₂ -haloalkynyl, which groups contain a halogen atom on the α-carbon atom.

In addition, compounds of formula I are preferred in which R ¹ is a group (CH _{2) n} CH ₂ CI, (CH _{2) n} CH ₂ Br, CH (CH ₃₎ (CH ₂₎ m CH ₂ CI, CH (CH ₃ ) (CH ₂ ) m CH ₂ BR, (CH ₂ ) _n CF ₃ or CH (CH ₃ ) (CH ₂ ) _m CF _{3 l} wherein n is a number from 0 to 1 3 and m is a number from 0 to 11.

Particular preference is given to compounds I in which R ^{1 is} chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2.2 -Difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-di-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl , 1, 1, 1-trifluoroprop-2-yl, 1-chloropropyl, 1-fluoropropyl, 3-chloropropyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 1-chlorobutyl, 1-fluorobutyl, 4 Chlorobutyl, 4-fluorobutyl, 4,4,4-trifluorobutyl, 1-chloropentyl, 1-fluoropentyl, 5,5,5-trifluoropentyl, 5-chloropentyl, 5-fluoropentyl, 1-chloro-hexyl, 1-fluorohexyl, 6-chlorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl, 1-chloroheptyl, 1-fluoroheptyl, 7-chloroheptyl, 7-fluoroheptyl, 7,7,7-trifluoroheptyl, 1-chlorooctyl, 1-fluoro-octyl, 8-fluorooctyl, 8,8,8-trifluorooctyl, 1-chlorononyl, 1-fluorononyl, 9-fluorononyl, 9,9,9-trifluorononyl, 9-chloromonyl, 1-fluorodecyl, 1-chlorodecyl, 10-fluorodecyl,

.10,10,10-trifluorodecyl, 10-chlorodecyl, 1-chloro-undecyl, 1-fluoro-undecyl, 11-chloro-decyl, 11-fluoro-undecyl, 11,11,11-trifluorundecyl, 1-chlorododecyl, 1-fluorododecyl, 12-chlorododecyl , 12-fluorododecyl or 12,12,12-trifluorododecyl.

In a further embodiment of the compounds I, R ^{1 is} C ₂ -C ₁₂ -alkenyl or C ₂ -C ₁₂ -alkynyl, where the carbon chains are unsubstituted or carry one to three identical or different groups R ^a and / or R ^b .

In a preferred embodiment of the compounds of the formula I, there is no group R ^a .

Compounds I are particularly preferred in which carbon chains of R ¹ and R ² together have not more than 14 carbon atoms.

In one embodiment of the compounds I according to the invention, R ^{2 is} methyl, ethyl, isopropyl, n-propyl or n-butyl, preferably methyl, ethyl, iso- or n-propyl, in particular methyl or ethyl.

Halogen atoms in the groups R ¹ are preferably at the α or Ω carbon atom.

Cyano groups in R ¹ and / or R ² are preferably on the terminal carbon atom.

In a further preferred embodiment of the compounds of the formula I, there is no group R ^b .

In particular, with regard to their use, the compounds I compiled in the following tables are preferred. The groups mentioned in the tables for a substituent also individually, independently of the combination in which they are mentioned, represent a particularly preferred embodiment of the relevant substituent.

Table 1

Compounds of the formula I in which R ¹ for each compound corresponds to one line of Table A and R ^{2 is} methyl Table 2

Compounds of the formula I in which R ^{1 is} a compound of one line in each case

Table A and R ^{2 is} ethyl

Table 3

Compounds of the formula I in which R ¹ for each compound corresponds to one line of Table A and R ^{2 is} n-propyl

Table 4 Compounds of the formula I in which R ¹ for a compound corresponds in each case to one row of Table A and R ² iso-propyl

Table 5

Compounds of the formula I in which R ¹ for a compound corresponds in each case to one row of Table A and R ^{2 is} n-butyl

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in particular from the class of the Oomycetes. They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are of particular importance for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, wine, fruit and ornamental plants and vegetables. plants such as cucumbers, beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases: Alternaria species on vegetables and fruits, Bipolaris and Drechslera A anen on cereals, rice and grass, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Bremia lactucae on lettuce, • Erysiphe cichoracearum and Sphaerotheca fullginea on cucurbits, Fusarium and Verticillium A anen on various plants, Mycosphaerella species on cereals, bananas and peanuts, Peronospora A anen on cabbage and bulbous plants, Phakopsora pachyrhizi and P. meibomiae on soya, • Phytophthora infestans on potatoes and tomatoes, Phytophthora capsici on peppers, Plasmopara viticola on vines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, • Pseudoperonospora species on hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae on rice, pythium aphanidermatum on lawn, rhizoctonia on cotton, Rei s and turf, • Septoria tritici and Stagonospora nodorum on wheat, Uncinula necatoran vines, Ustilago arias on cereals and sugarcane, and Venfur / a species (scab) on apples and pears.

In particular, they are suitable for controlling harmful fungi from the class Oomycetes, such as Peronospora Acten, Phytophthora species, Plasmopara viticola and Pseudoperonospora A e.

The compounds I are also suitable for controlling harmful fungi such as Pecilomyces variotii in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are in the protection of materials, for example 0.O01 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 application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma Butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used, - carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose. The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations are: 1. Products for dilution in water

A Water Soluble Concentrates (SL)

10 parts by weight of a compound of the invention in water or a dissolved water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.

B Dispersible Concentrates (DC) 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.

C Emulsifiable Concentrates (EC) 15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Dilution in water results in an emulsion. D Emulsions (EW, EO) 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E suspensions (SC, OD)

20 parts by weight of a compound according to the invention are comminuted with the addition of dispersants and wetting agents and water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.

F Water-dispersible and Water-soluble Granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.

G Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. 2. Products for direct application

H dusts (DP)

5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dust.

I Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention are finely ground and combined with 95.5% excipients. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J ULV solutions (UL)

10 parts by weight of a compound of the invention are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. be applied in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, Oldispersionen, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring. The forms of application depend entirely on the intended use; 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 (spray powders, old dispersions) by adding water. For the preparation of emulsions, pastes or old dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives. To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10: 1.

The agents according to the invention, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.

The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

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 cyprodinil,

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,

• Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propynazole, prochloraz, prothioconazole, simeconazole, tebuconazole , Tetraconazole, triadimefon, triadimol, triflumizol, triticonazole,

Dicarboximides such as iprodione, myclozoline, procymidone, vinclozoline, dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thi am, Ziram, Zineb,

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamide, probenazole, proquinazide, pyrifenox, Pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine,

Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,

Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl, phenylpyrroles, such as fenpiclonil or fludioxonil,

• sulfur, Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorotriazole, cyflufenamide, cymoxanil, diclomethine, diclocymet, diethofencarb, edfenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluaziamine, phosphorous acid , Fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozeene, zoxamide,

• strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxime-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.

synthesis Examples

The instructions given in the Synthesis Examples below were used with appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the following table with physical data.

Example 1: Preparation of

6- (3-Bromopropyl) -5-ethyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine [1-1]

A solution of 495 mg (1.7 mmol) of 5-ethyl-6- (3-pentyloxypropyl) - [1, 2,4] triazolo [1,5-a] pyrimidin-7-ylamine (preparation analogous to EP-A 141 317) in 5 ml of glacial acetic acid was added at 20 to 25 ° C 0.60 ml of 48% aq. Hydrobromic acid, then re-fluxed for 20 h. After cooling, the reaction mixture was freed from the volatiles, the residue taken up in CH ₂ Cl ₂ / H ₂ O and the aqueous phase with sat. NaHCO ₃ sol. washed neutral. The organic phase was separated, washed with water, dried and freed from the solvent. From the residue, after chromatography on RP18 phase (MPLC isocratic, acetonitrile-water mixture), 0.21 g of the title compound were obtained in the form of white crystals.

Example 2: Preparation of 7-amino-6- (5-cyanopentyl) -5-ethyl- [1,2,4] triazolo [1,5-a] pyrimidine

2.a) 4,9-Dicyanononan-3-one

To a solution of 6.8 g of 1,6-dicyanohexane and 11.2 g of 95% potassium tert-butylate in 100 ml of anhydrous. Dimethylformamide (DMF) was added dropwise 5.6 g of ethyl propionate. After completion of the addition, the mixture was stirred at 20 to 25 ° C for 17 hours, then the reaction mixture diluted with water and washed with Tertiärbutylmethylether (MTBE). After acidification with conc. HCI was the aqueous phase with MTBE extra- hiert. This ether phase was washed with water, freed from the solvent after drying. There remained 7.1 g of the title compound as an oil which was reacted without further purification.

2.b) 7-Amino-6- (5-cyanopentyl) -5-ethyl-triazolo (1,5-a) -pyrimidine [I-3]

4.76 g of 4,9-dicyanononan-3-one, 2.5 g of 3-amino-1 H-1, 2,4-triazole and 0.94 g of p-toluenesulfonic acid were added in 25 ml of mesitylene for four hours 170 ^C C stirred, with distilling off some mesitylene continuously. Then, the solvent was distilled off and the residue was taken up in dichloromethane and water. After separating insoluble constituents, the organic phase was washed with water, saturated NaHCO ₃ solution and saturated NaCl solution, then dried and freed from volatiles. The residue was digested in MTBE. After removal of the solvent remained 2.0 g of the title compound as colorless crystals of mp. 158 - 160 ° C back.

Example 3: Preparation of

5-Ethyl-6- (5,6,6-trifluoro-hex-5-enyl) - [1, 2,4] triazolo [1,5-a] pyrimidin-7-ylamine [I-5]

3a) 7,8,8-trifluoro-2-propionyl-oct-7-enoic acid methyl ester

To a solution of 3.30 g (23 mmol) of ethyl propionyl acetate in 2.5 ml of methanol was added 5.40 g of methanolic potassium methylate solution. (30%, 23 mmol) was added dropwise at 20 to 25 ^C C. After stirring at this temperature for 1 h, then at 40 ° C. for 30 min, 5.00 g (23 mmol) of 6-bromo-1,1,2-trifluoro-1-hexene were added dropwise at 40 ° C. over a period of 5 min. The reaction mixture was then stirred for 15 h at this temperature. The resulting suspension was taken up in methyl tert-butyl ether (MTBE) and filtered through silica gel. The eluate was washed with water, then with sat. NaCl solution. washed, then dried and freed from the solvent. There remained 2.34 g of the title compound as a colorless oil.

3b) 5-ethyl-6- (5,6,6-trifluoro-hex-5-enyl) - [1,2,4] triazoio [1,5-a] pyrimidin-7-ol

A mixture of 5.28 mmol of 7,8,8-trifluoro-2-propionyl-oct-7-enoic acid methyl ester, 0.86 g (10.2 mmol) of 3-amino-1, 2,4-triazole and 10 ml of propionic acid refluxed for about 15 hours. The propionic acid was then distilled off and the residue was chromatographed on silica gel (cyclohexane / ethyl acetate mixture). There remained 0.6 g of the title compound as yellow crystals. 3c) 7-chloro-5-ethyl-6- (5,6,6-trifluoro-hex-5-enyl) - [1, 2,4] triazolo [1,5-a] pyrimidine

0.60 g (2 mmol) of the compound from Ex. 3b) in 20 ml of phosphoryl chloride were refluxed for 15 hours. Then the volatiles were distilled off, the residue taken up in CH ₂ Cl ₂ , the solution with NaHCO ₃ -Lsg. washed neutral, dried and freed from the solvent. From the residue was obtained after chromatography on silica gel (ethyl acetate / methanol mixture) 0.38 g of the title compound as a yellow oil.

3d) 5-ethyl-6- (5,6,6-trifluoro-hex-5-enyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine

A solution of 0.35 g (1.1 mmol) of the compound of Ex. 3c) in 2 ml of methanol was treated with 10 ml of a 7M methanolic NH ₃ solution. 48 hrs. At 20 to 25 ° C stirred. The solution was freed from the volatiles, the residue slurried with water in an ultrasonic bath, filtered off, then dried. There remained 0.21 g of the title compound in the form of white crystals, mp. 199 ° C back.

Table I - Compounds of the formula I

Examples of the effect against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:

The active compounds were prepared as a stock solution with 25 mg of active ingredient with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent emulsifier of 99 was made up to 1 ad 10 ml. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below. Use Example 1 - Efficacy against vine peronospora caused by Plasmopara viticola

Leaves of pot fry were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The following day, the undersurfaces of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. Thereafter, the vines were first placed for 48 hours in a water vapor-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a humid chamber for 16 hours to accelerate the sporangiopathic outbreak. Then the extent of infestation on the undersides of the leaves was visually determined.

In this test, the plants treated with 250 ppm of the compound I-7 showed no attack, while the untreated plants were 90% infected.

Use Example 2: Activity against late blight on tomatoes caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were treated with an aqueous suspension of

Active ingredients sprayed until dripping wet. Four days after application, the leaves were infected with an aqueous sporangium suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ° C. After 6 days the infestation was determined visually in%.

In this test, the plants treated with 250 ppm of Compound I-7 showed no infestation, while the untreated plants were 100% infested.

Claims

claims

Triazolopyrimidines of the formula

in which the substituents have the following meanings:

R ^{1 is} C ₂ -C ₁₂ alkenyl or C ₂ -C ₁₂ alkynyl, wherein the carbon chains are unsubstituted or carry one to three identical or different groups R ^a and / or R ^b ; or

CrCι ₄ alkyl, dC ^ alkoxyC ^ alkyl dC, dC ₆ -alkoxy-C ₂ -C ₂ -alkenyl or C ₆ -alkoxy-C ₂ -C ₁₂ alkynyl, wherein the carbon chains of from one to three same before or carry different groups R ^a ;

R ^{a is} halogen, cyano, nitro, hydroxy, dC ₆ -alkylthio, C _{3 2} -Cι alkenyloxy, C ₃ -C ₁₂ alkynyloxy, NR ¹¹ R ^12, or C ₃ -C ₆ -cycloalkyl which one to four identical or different groups R ^b can carry;

R ^b CC ₄ alkyl, cyano, nitro, hydroxy, CC ₆ alkoxy, dC ₆ -alkylthio, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ -alkynyloxy and NR ¹¹ R ¹²

R ^11, R ¹ 'is hydrogen or C ₆ alkyl; wherein the carbon chains of the groups R ^{a may in} turn be halogenated;

C ₁ -C ₂ -alkyl, C ₂ -C ₁₂ -alkenyl or C ₂ -C ₂ -alkynyl, where the carbon chains are substituted by one to three groups R °:

R ° cyano, nitro, hydroxy, NR ¹¹ R ¹² ; or C ₃ -C ₆ -cycloalkyl which one to four identical or different groups dC alkyl, halogen, cyano, nitro, hydroxy, CC ₆ alkoxy, dC ₆ alkylthio, C ₃ -C ₆ - alkenyloxy, C ₃ - C ₆ alkynyloxy or NR ¹¹ R ¹² can carry.

2. Compounds of formula I according to claim 1, wherein

R ¹ CτC ₁₄ -haloalkyl, d-dz-haloalkoxy-d-dz-alkyl, dC - ^ -alkoxy-d-d ₂ -haloalkyl, C ₂ -C ₁₂ -alkenyl, C ₂ -C ₁₂ -haloalkenyl, C ₂ C ₁₂ -alkynyl or C ₂ -dz-haloalkynyl, wherein the carbon chains can carry one to three groups R ^a :

R ^a is cyano, nitro, hydroxy, dC ₆ alkoxy, dC ₆ alkylthio, C ₃ -C ₁₂ - alkenyloxy, C ₃ alkynyloxy -Cι _2, NR ¹¹ R ^12, or

C ₃ -C ₆ -cycloalkyl which may carry one to four identical or different groups;

R ^{b is} CC ₄ alkyl, cyano, nitro, hydroxy, CC ₆ alkoxy, CC ₆ - Alkythio, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ -AIkinyloxy and NR ¹¹ R ¹²

R ¹¹ , R ^{12 is} hydrogen or CC ₆ alkyl; wherein the carbon chains of the groups R ^{a may in} turn be halogenated;

3. Compounds of formula I according to claim 1 or 2, wherein

R ^{2 is} C ₁ -C ₁₂ -alkyl, C ₂ -C ₂ -alkenyl or C ₂ -C ₁₂ -alkynyl, where the carbon chains may be substituted by one to three groups R ^c :

R ^{c is} cyano, nitro, hydroxy, NR ¹¹ R ¹² ; or C ₃ -C ₆ -cycloalkyl which one to four identical or different groups dC alkyl, halogen, cyano, nitro, hydroxy, dC ₆ alkoxy, dC ₆ alkylthio, C ₃ -C ₆ - alkenyloxy, C ₃ - C ₆ alkynyloxy or NR ¹¹ R ¹² can carry.

4. Compounds of formula I according to any one of claims 1 to 3, wherein

R ^{1 is} C ¹ -C ₁₄ -alkyl, where the carbon chains carry one to three identical or different groups cyano or halogen; means.

5. Compounds of formula I according to any one of claims 1 to 3, wherein

R ^{1 is} C ₂ -C ₁₂ alkenyl or C ₂ -C ₂ alkynyl, wherein the carbon chains are unsubstituted or carry one to three identical or different groups R ^a and / or R ^b ; means.

6. Compounds of formula I according to any one of claims 1 to 5, wherein R ¹ and R ² together have not more than 14 carbon atoms.

7. Compounds of the formula I according to one of Claims 1 to 5, in which R ^{1 is} chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1- Fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1,1-trifluoroprop-2-yl, 1-chloropropyl, 1-fluoropropyl, 3-chloropropyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 1-chlorobutyl, 1-fluorobutyl, 4-chlorobutyl, 4-fluorobutyl, 4,4,4-trifluorobutyl, 1-chloropentyl, 1-fluoropentyl, 5,5,5-trifluoropentyl, 5-chloropentyl, 5-fluoropentyl, 1-chlorohexyl, 1- Fluorohexyl, 6-chlorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl, 1-chloroheptyl, 1-fluoroheptyl, 7-chloroheptyl, 7-fluoroheptyl, 7,7,7-trifluoroheptyl, 1-chlorooctyl, 1-fluorooctyl, 8-fluorooctyl, 8,8,8-trifluorooctyl, 1-chloromonyl, 1-fluomonyl, 9-fluorononyl, 9,9,9-trifluorononyl, 9-chlorononyl, 1-fluorodecyl, 1-chlorodecyl, 10-fluorodecyl, 10,10,10-trifluorodecyl, 10-chlorodecyl, 1-chloro-undecyl, 1-fluoroo-undecyl, 11-chloro-undecyl, 11-fluoro-undecyl, 11,11, 11-trifluorundecyl, 1-chlorododecyl, 1-fluorododecyl, 12-chlorododecyl, 12-fluorododecyl or 12,12,12-trifluorododecyl.

8. Compounds of formula I according to any one of claims 1 to 7, wherein R ^{2 is} methyl, ethyl, iso-propyl, n-propyl or n-butyl.

9. 6- (3-bromopropyl) -5-ethyl- [1,2,4] triazolino [1,5-a] pyrimidin-7-ylamine; 6- (3-chloropropyl) -5-ethyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine; 6- (7-amino-5-ethyl- [1,2,4] triazolo [1,5-a] pyrimidin-6-yl) -hexanenitrile; 6- (7-amino-5-propyl- [1,2,4] triazolo [1,5-a] pyrimidin-6-yl) -hexannitril; 5-ethyl-6-hex-5-enyl | 1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine; 6-hex-5-enyl-5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine; 5-Methyl-6- (5,6,6-trifluoro-hex-5-enyl) - [1, 2,4] triazolo [1,5-a] pyrimidin-7-ylamine.

10. Process for the preparation of compounds of the formula I according to one of claims 1 to 9, characterized in that β-ketoesters of the formula II,

in which R is CC ₄ alkyl, with 3-amino-1, 2,4-triazole of the formula to 7-hydroxytriazolopyrimidines of the formula IV

which converts to compounds of the formula V,

in which shark is chlorine or bromine, halogenated, and V is reacted with ammonia.

11. Process for the preparation of compounds of the formula I according to any one of claims 1 to 9, characterized in that acyl cyanides of the formula VI,

with 3-amino-1, 2,4-triazole of the formula III according to claim 10.

12. Compounds of the formulas IV and V according to claim 10.

13. A process for the preparation of compounds of the formula I according to claim 1, wherein R ¹ is substituted by halogen CC ₁₄ alkyl, dC ₁₂ alkoxy-C C ₁₂ -alkyI, C ₂ - d ₂ alkenyl or C ₂ -C ₁₂ Alkynyl, by halogenation of triazolopyrimidines of the formula VII, in the R for dC ₁ -alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, wherein the carbon chains can carry one to three groups R ^a according to claim 1, with a halogenating agent in the presence of a radical initiator or an acid.

14. A fungicidal composition containing a solid or liquid carrier and a compound of formula I according to any one of claims 1 to7.

15. Seed containing a compound of formula I according to any one of claims 1 to 9 in an amount of 1 to 1000 g per 100 kg.

16. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected against fungal infestation materials, plants, the soil or seeds with an effective amount of a compound of formula I according to any one of claims 1 to 9 ,