EP1856121A1 - 5,6-dialkyl-7-amino-azolopyrimidines, 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-azolopyrimidines of formula (I), in which the substituents are defined as follows: R1 represents haloalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl; R2 represents alkyl, alkoxyalkyl, alkenyl or alkynyl, where R1 and/or R2 can be substituted as per the description; A represents N or CH; and R3 represents CH3 and if A represents CH additionally hydrogen. The invention also relates to a method and intermediate products for producing said compounds, to agents containing the latter and to the use of the compounds for controlling plant pathogenic fungi.

Description

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

description

The present of the formula I

in which the substituents have the following meanings:

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 ; or d-Cu-alkyl, C-ι-Ci2-alkoxy-Ci-Ci2-alkyl, C ₁ -C 6 alkoxy-C ₂ -C ₂ -alkenyl or C ₆ - alkoxy-C2-Ci2-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

Which R ^b may carry C3-C6-cycloalkyl one to four identical or different groups; R ^{b is} C ₁ -C ₄ -alkyl, cyano, nitro, hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, C ₃ -

Ce-alkenyloxy, C ₃ -C ₆ -alkynyloxy and NR ¹¹ R ¹² R ¹¹ , R ^{12 is} hydrogen or C ₁ -C ₆ -alkyl; wherein the carbon chains of the groups R ^{a may in} turn be halogenated;

R ² Ci-Ci2-alkyl, Ci-C ₂ alkoxy-Ci-Ci ₂ -alkyl, C ₂ -C ₂ -alkenyl or C ₂ -Ci2-alkynyl, wherein the carbon chains ^c by one to three groups R may be substituted : R ^c is halogen, cyano, nitro, hydroxy, C ₁ -C ₆ -alkoxy, _C-ι-C6 alkylthio, C3-C ₁₂ -

Alkenyloxy, C ₃ -C ¹² alkynyloxy, NR ¹¹ R ¹² ; or C ₃ -C ₆ -cycloalkyl which ne oval to four identical or different groups C-ι-C4 alkyl, halogen, cyano, nitro, hydroxy, C-ι-C ₆ alkoxy, Ci-C ₆ -alkylthio , C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, NR ¹¹ R ¹² ;

A is N or CH; and

R ³ CH ₃ , when A is CH additionally hydrogen.

In addition, the invention relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi. GB 1 148 629 generally suggests 5,6-dialkyl-7-amino-triazolo- and -pyrazolopyrimidines. EP-A 141 317 discloses individual fungicidally active 5,6-dialkyl-7-amino-triazolo- and -pyrazolopyrimidines. 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 formula I differ from those of the abovementioned publications by the specific embodiment of the substituent in the 6-position of the azolopyrimidine 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-ketoesters of the formula II with an aminoazole of the formula III to give 7-hydroxyazolopyrimidines of the formula IV. The variables in formulas II and IV have the meanings as for formula I and the group R in formula II means CrC ₄ -

al

Il III IV

The compounds of formula IV are new.

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 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, 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 metals. metal hydrides, organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, and also organic bases, for example tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethyl-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 ⁰ C, preferably at 50 to 180 ° C when operating in solution [cp. EP-A 770 615; Adv. Het. Chem. Vol. 57, p. 81ff. (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 with chlorinating agents such as phosphorus oxychloride, thionyl onylchlorid or sulfuryl chloride is preferably carried out at 50 ° C to 150 ⁰ C, preferably in excess phosphorus oxytrichloride at reflux temperature. After evaporation of the excess Phosphoroxitrichlorids the residue is treated with ice water optionally with the addition of a water-immiscible solvent. The organic from the overall dry phase is optionally isolated after evaporation of the inert solvent chlorination is generally very pure and is then reacted with ammonia in inert solvents at 100 ⁰ C to 200 ⁰ C to give the 7-aminoazolo [1, 5-a] - Implemented pyrimidines. 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 formula II can be prepared as in Organic Synthesis Coli. Vol. 1, p. 248, or are commercially available. The intermediates of formula V are new.

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 an aminoazole 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, propionic acid 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 new 7-amino-azolo [1, 5-a] -pyrimidines are optionally isolated after evaporation of the solvent or dilution with water as crystalline compounds.

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 CRCI ₄ haloalkyl, _Ci-Ci2 haloalkoxy Cr Ci2-alkyl, CrCl ₂ alkoxy-Ci-C ₂ haloalkyl, C ₂ -C ₂ haloalkenyl or C ₂ -C ₂ - haloalkynyl, are by halogenation of corresponding azolopyrimidines of the formula

In formula VII R ₁₄ alkyl, CrCl ₂ alkoxy-Ci-Ci ₂ -alkyl, C ₂ -C ₂ -alkenyl, C ₂ to Ci-C - C alkynyl _2, wherein the carbon chains of one to three groups R ^a can carry. The halogenation is usually carried out at temperatures of from ⁰ ° C. to 200 ^° C., preferably from 20 ^° C. to 110 ^° C., in an inert organic solvent in the presence of a free-radical initiator (for example dibenzoyl peroxide or azobisisobutyronitrile or under UV light). 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 in equimolar amounts with each other. It may be advantageous for the yield to use the halogenating agent in an excess based on VII.

As the halogenating agent, there are used, for example, elemental halogens (e.g., CI 2, Br 2, J 2), N-bromo-succinimide, N-chloro-succinimide or dibromodimethylhydrantoin. The halogenating agents are generally used in equimolar amounts, in excess or, if appropriate, as solvents.

The azolopyrimidines of the formula VII required for the preparation of the compounds I described above are known in some cases 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, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for use or in use (e.g., under light, acid, or base action). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.

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, for example C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methyl pentyl, 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), in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above: in particular C 1 -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, e.g. C2-C6 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-Bu- tenyl, 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-bu benzyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-centenyl, 1,3-dimethyl 3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3- Dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1 - propenyl and 1-ethyl-2-methyl-2-propenyl;

Alkoxyalkyl: saturated, straight-chain or mono-, di- or tri-branched hydrocarbon chain which is interrupted by an oxygen atom, for. B. C5-C ₁₂ - alkoxyalkyl: hydrocarbon chain as hereinbefore described 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, heptyloxy-ethyl , 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-methylbutoxy) -pentyI;

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), wherein in these groups, the hydrogen atoms partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine could be;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6, 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-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-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 _. Use of the azolopyrimidines of the formula I are the following meanings of the substituents, in each case alone or in combination, particularly preferably:

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.

In one embodiment of the compounds I according to the invention, R ^{1 is} C ₁ -C 14 -haloalkyl, C ₁ -C 12 -haloalkoxy-C ₁ -C 12 -alkyl, C ₁ -C 12 -alkoxy-C ₁ -C 12 -haloalkyl, C ₂ -C 12 -haloalkenyl or C ₂ -C 12 -alkoxyalkyl Ci2-haloalkynyl, which groups one or two halo have logen atoms. Here, d-Cg-haloalkoxy-propyl and d-Cg-alkoxy-halopropyl groups are preferred.

, Haloalkyl, haloalkoxy CrCi2-Ci-Ci ₂ alkyl C-ι-Ci2-alkoxy-Ci-C ₂ haloalkyl, C2-CI2 - In another embodiment of the compounds I, R ¹ represents a group C ₁ -C ₁₄ Haloalkenyl or C 2 -C 12 -haloalkynyl, which groups contain a halogen atom, preferably the halogen atom is present on the α-terminal carbon atom.

In addition, preference is given to compounds of the formula I in which R ^{1 is} a group (CH ₂ ) n CF ₃ or CH (CH ₃ ) (CH ₂ ) m CF 3, in which n is a number from 0 to 13 and m is a number from 0 to 11 , stands.

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-chlorononyl , 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, n-propyl or n-butyl, preferably methyl or ethyl, in particular ethyl. Halogen atoms in the groups R ¹ and / or R ² are preferably on the α-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 .

One embodiment of the compounds according to the invention relates to compounds I in which A corresponds to CH Formula 1.1:

Another embodiment of the compounds according to the invention relates to compounds I in which A for formula I.2:

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 1.1, in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} methyl and R ^{3 is} hydrogen

Table 2

Compounds of the formula 1.1, in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} ethyl and R ^{3 is} hydrogen

Table 3

Compounds of the formula 1.1, in which R ^{1 is} a compound of one line each of the compounds

Table A corresponds, R ^{2 is} n-propyl and R ^{3 is} hydrogen

Table 4

Compounds of the formula 1.1, in which R ¹ for a compound corresponds in each case to one row of Table A, R ² isopropyl and R ^{3 is} hydrogen Table 5

Compounds of the formula 1.1 in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} n-butyl and R ^{3 is} hydrogen

Table 6

Compounds of the formula 1.1, in which R ^{1 is} a compound of one line each of the compounds

Table A corresponds and R ² and R ^{3 are} methyl

Table 7

Compounds of the formula 1.1, in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} ethyl and R ^{3 is} methyl

Table 8 Compounds of the formula 1.1 in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} n-propyl and R ^{3 is} methyl

Table 9

Compounds of the formula 1.1, in which R ¹ for each compound corresponds to one line of Table A, R ² isopropyl and R ^{3 is} methyl

Table 10

Compounds of the formula 1.1 in which R ¹ for each compound corresponds to one line of Table A, R ^{2 is} n-butyl and R ^{3 is} methyl

Table 11

Compounds of the formula 1.2, in which R ^{1 is} a compound of one row each of the

Table A and R ^{2 is} methyl

Table 12

Compounds of the formula 1.2, in which R ¹ for a compound corresponds in each case to one row of Table A and R ^{2 is} ethyl

Table 13 Compounds of the formula 1.2, in which R ¹ for a compound corresponds in each case to one row of Table A and R ² denotes n-propyl

Table 14

Compounds of the formula 1.2 in which R ¹ for each compound corresponds to one line of Table A and R ^{2 is} isopropyl Table 15

Compounds of the formula 1.2, in which R ^{1 is} a compound of one row each of the

Table A and R ^{2 is} n-butyl

Table A

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 in part systemically effective and can be used in crop protection as foliar and soil fungicides. They are particularly important for the control of a variety of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases: Alternaria species on vegetables, rapeseed, sugar beets and fruits and rice

(e.g., A. so / an / or A. alternataan potato and other plants), - Aphanomyces species of sugar beet and vegetables,

Bipolaris and Drechsler species on corn, cereals, rice and turf

(e.g., D. teresan barley, D. tritci-repentis on wheat),

Blumeria graminis (powdery mildew) on cereals,

Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

Bremia lactucae on salad,

Cercospora species on corn, soybeans, rice and sugar beet (e.g., C. beticula on sugar beet),

Cochliobolus species on corn, cereals, rice (e.g., Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice),

Colletotricum species on soybeans, cotton and other plants

(e.g., C. acutatum on various plants),

Exserohilum species on corn,

Erysiphe cichoracearurmnd Sphaerotheca fuliginea on cucurbits, Fusarium and Verticillium species (e.g., V. dahliae) on various plants

(e.g., F. graminearum to wheat),

Gaeumanomyces graminis on cereals,

Gibberella species on cereals and rice (e.g., Gibberella fujikuroiau rice),

Grainstaining complexan rice, Helminthosporium species (e.g., H. graminicolä) on corn and rice,

Michrodochium nivale on cereals,

Mycosphaerella species on cereals, bananas and peanuts (M. graminicolä ax \

Wheat, M. fijiesis to banana, /

Phakopsara pachyrhizi and Phakopsara meibomiae ax \ soybeans, - Phomopsis species on soybeans, sunflowers and vines (P. viticola an

Grapevines, P. helianthii ^' on sunflowers ^

Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on vines,

Podosphaera leucotricha on apple, - Pseudocercosporella herpotrichoides on cereals,

Pseudoperonospora species on hops and cucurbits (eg P. cubenis on cucumber), Puccinia species on cereals, corn and asparagus {P. triticina and P. striformis

Wheat, P. asparagian asparagus),

Pyrenophora species on cereals,

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.atumuatum, Entyloma oryzae on rice,

Pyricularia grisea on lawn and cereals,

Pythium spp. on grass, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants,

Rhizoctonia species (e.g., R. solanf) on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and other plants,

Sclerotinia species (e.g., 5. sclerotiorum) on oilseed rape, sunflowers and others

Plants, - Septoria tritici and Stagonospora nodorum on wheat,

Erysiphe (syn. Uncinulanecator) on grapevine, - Setospaeria species on maize and turf,

Sphacelotheca reilinia on corn,

Thievaliopsis species on soybeans and cotton,

Tilletia species of cereals,

Ustilago species on cereals, maize and sugar beet and - Venturia species (scab) on apple and pear (e.g., V. inaequalis on apple).

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

The compounds I are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sciophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., P / e ^ / - rotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and zygomycetes such as Mucor spp., moreover, in the protective material, the following yeasts: Candida spp. and Saccharomyces cerevisae.

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, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

- water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin liquors and methyl cellulose.

Suitable surface-active substances are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfonated Furthermore, 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, alkyl arylpolyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite liquors 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, such as 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, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content. B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E Suspensions (SC, OD, FS) 20 parts by weight of the active compounds are comminuted with the addition of 10 parts by weight of dispersing and wetting agents and 70 parts by weight of 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. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing 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. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H Gel Formulations In a ball mill 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are used. mulling agent to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil 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. However, it is also possible to prepare wetting, adhesion, dispersing or emulsifying agents from effective substance and solvent or oil concentrates are prepared 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: 100 to 100: 1, preferably 1:10 to 10: 1.

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®.

The agents according to the invention may also be present in the form of use as fungicides 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 with one or more further active compounds, in particular fungicides, for example, in many cases, the spectrum of activity can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.

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.

strobilurins

Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate; carboxamides

- Carboxylic acid anilides: Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazol-5-carboxylic acid

(4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluoro-biphenyl-2-yl) -amide , 3-Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5-carbon - acid (2-cyano-phenyl) -amide; - Carboxylic acid morpholides: Dimethomorph, Flumorph;

Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino 3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-pheπyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl- butyramide;

azoles

- triazoles: bitertanol, bromuconazoles, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetracona - zole, triadimenol, triadimefon, triticonazole;

- imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - Other: Ethaboxam, Etridiazole, Hymexazole;

Nitrogen-containing heterocyclyl compounds

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine; Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;

- piperazines: triforins;

- Pyrroles: fludioxonil, fenpiclonil;

- Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph; Dicarboximides: iprodione, procymidone, vinclozolin;

- Other: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazid, pyroquilon, quinoxyfen, tϊicyclazole, 5-chloro-7- ( 4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6- iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide; Carbamates and dithiocarbamates

Dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram;

Carbamates: diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester, N- (1 - (1 - (4- cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester;

Other fungicides - guanidines: dodine, iminoctadine, guazatine;

- Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A;

Organometallic compounds: fentin salts;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;

Organochlorine compounds: thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;

Nitrophenyl derivatives: binapacryl, dinocap, dinobuton;

- Inorganic active substances: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur;

- Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenone.

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 2-acetyl-hex-4-in-nitrile

A solution of 9.0 g (97 mmol) hex-5-in-nitrile and 13.9 g (97 mmol) of acetic acid isobutyl ester in 150 ml of dimethylformamide (DMF) was added dropwise at 0 ⁰ C with a solution of 22.9 g ( 204 mmol) of potassium tert-butoxide in 100 ml of DMF. Subsequently stirring the reaction mixture initially 30 minutes at 0 ⁰ C, then for another hour at 20 to 25 ° C. The reaction mixture was treated with 100 ml of water and extracted with dichloromethane. The aqueous phase was extracted after acidification hydrochloric acid with methyl tert-butyl ether (MTBE). The combined organic extracts were washed with water and NaCl solution, then dried. After removal of the solvent, the residue was distilled in vacuo (0.2 mbar, 70-72 ⁰ C). This gave 7.9 g of the title compound as a pale yellow liquid. Example 2: Preparation of 6-But-2-ynyi-2,5-dimethylpyrazolo [1,5-a] pyrimidin-7-ylamine

A solution of 0.24 g of the ketonitrile (2 mmol) from Example 1, 0.2 g (5 mmol) of 5-methyl-pyrazol-3-amine and 0.07 g (0.4 mmol) of p-toluenesulfonic acid in 5 ml of mesitylene was refluxed for six hours. Thereafter, the solvent was separated with MTBE and the residue taken up in methanol. The crude product was purified by column chromatography (eluent: ethyl acetate). There remained 0.07 g of the title compound as white crystals, m.p. 215-219 ⁰ C back.

¹ H-NMR [500 MHz] δ: 1.7 ppm (s, 3H); 2.3 ppm (s, 3H); 2.4 ppm (s, 3H); 3.5 ppm (s, 2H); 6.0 ppm (s, 1H); 7.3 ppm (s, 2H).

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.

Comparative Experiment - Efficacy against barley spot blight caused by Pyrenophora teresbe \ 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslern] teres, the causative agent of net blotch disease. Subsequently, the test plants were grown in a greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative air moisture. After 6 days, the extent of disease development was determined visually as% of total leaf area.

The comparison with the closest prior art showed the following results:

Use Example 2 Activity Against the Causative Agent of the Pyricularia oryzae Rice Sting in the Microtiter Test

The active ingredients were formulated separately as stock solution with a concentration of 10,000 ppm in DMSO.

The stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Pyricularia oryzae. The plates were placed in a steam-saturated chamber at temperatures of 18 ° C. With an absorption photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

The measured parameters were compared with the growth of the active substance-free control variant and the fungus-free and active ingredient-free blank value in order to determine the relative growth in% of the pathogens in the individual active substances.

In this assay, the growth of pathogens was inhibited by 125 ppm of drug I-3 to 23%.

Claims

34Patentansprüche

1. Azolopyrimidines of the formula I.

in which the substituents have the following meanings:

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 ; or

Ci-C-ι ₄ alkyl, _Ci-C12 alkoxy-Ci-Ci ₂ -alkyl, Ci-C ₆ -alkoxy-C ₂ -Ci2-alkenyl or Ci-C6-alkoxy-C2-Ci2-alkynyl, wherein the carbon ^chains carry one to three identical or different groups R ^a ;

R ^{a is} halogen, cyano, nitro, hydroxy, Ci-C ₆ alkylthio, C ₃ -C ₂ alkenyloxy,

C ₃ -C ¹² alkynyloxy, NR ¹¹ R ¹² , or

C3-C6-cycloalkyl which is one to four identical or different

Groups R ^b can carry;

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

R ¹¹ , R ^{12 are} hydrogen or C ₁ -C ₆ -alkyl; wherein the carbon chains of the groups R ^{a may in} turn be halogenated;

R ² Ci-Ci2-alkyl, Ci-C ₂ alkoxy-C-ι-Ci2-alkyl, C ₂ -C ₂ -alkenyl or C ₂ -C ₂ alkynyl, wherein the carbon chains ^c by one to three groups R substituted could be:

R ^c is halogen, cyano, nitro, hydroxy, Ci-C ₆ alkoxy, Ci-C ₆ alkylthio, C ₃ - Ci2 alkenyloxy, C ₃ -C alkynyloxy _2, NR ¹¹ R ^12; or C ₃ -C ₆ -cycloalkyl which has one to four identical or different C ₁ -C ₄ -alkyl groups,

Halogen, cyano, nitro, hydroxy, Ci-Cβ-alkoxy, Ci-Cβ-alkylthio, C ₃ -CΘ-alkenyloxy, C ₃ -C ₆ -alkynyloxy or NR ¹¹ R ¹² can carry;

A is N or CH; and

R ³ CH ₃ , when A is CH additionally hydrogen.

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

R ¹ CRCI ₄ haloalkyl, CrCi2-haloalkoxy-Ci-Ci2-alkyl, Ci-C ₂ alkoxy-Ci- _Ci2 haloalkyl, _C2 -Ci2 alkenyl, C2-Ci2-haloalkenyl, C2-Ci2 alkynyl o the C ₂ -C ₂ -haloalkynyl, where the carbon chains can carry one to three groups R ^a :

R ^a is cyano, nitro, hydroxy, CrC ₆ alkoxy, Ci-C ₆ alkylthio, C ₃ -C ₂ - alkenyloxy, C ₃ -C alkynyloxy _2, NR ¹¹ R ^12, or C3-C6-cycloalkyl, which is a until four identical or different groups R ^b can carry;

R ^b _Ci-C4 alkyl, cyano, nitro, hydroxy, C _r C ₆ alkoxy, Ci-C ₆ - alkylthio, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ -alkynyloxy and NR ¹¹ R ¹²

R ¹¹ , R ^{12 is} hydrogen or C ₁ -C 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 ^{1 is} C ₂ -C ₂ -alkenyl or C ₂ -C ₂ alkynyl, wherein the carbon chains are ated unsubstitu- or one to three identical or different groups R ^a and / or

Wear R ^b ; means.

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

R ² Ci-Ci ₂ -alkyl, C ₂ -Ci2 alkenyl or C ₂ -C ₂ alkynyl, wherein the carbon chains may be substituted by one to three groups R ^c: R ^c is cyano, nitro, hydroxy, Ci-C ₆ alkoxy, -C ₆ -alkylthio, C ₃ -C ₂ -alkenyl oxy, C ₃ -C alkynyloxy _2, NR ¹¹ R ^12; or C ₃ -C ₆ -cycloalkyl which has one to four identical or different C ₁ -C ₄ -alkyl groups, halogen,

Cyano, nitro, hydroxy, Ci-C ₆ alkoxy, CrC ₆ alkylthio, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy or NR ¹¹ R ¹² can carry.

5. Compounds of formula I according to any one of claims 1 to 4, wherein R ¹ and R ² together have not more than 14 carbon atoms.

6. Compounds of formula I according to any one of claims 1 to 5, wherein R ^{2 is} methyl, ethyl or n-propyl.

7. Compounds of formula I according to any one of claims 1 to 6, wherein A is CH.

8. Compounds of formula I according to claim 1: 6-hex-5-enyl-2,5-dimethyl-pyrazolo [1,5-a] pyrimidin-7-ylamine; 6-But-2-ynyl-2,5-dimethyl-pyrazolo [1,5-a] pyrimidin-7-ylamine; 2,5-Dimethyl-6- (5,6,6-trifluoro-hex-5-enyl) -pyrazolo [1,5-a] pyrimidin-7-ylamine.

9. A process for the preparation of compounds of the formula I according to one of the An¬

in which R is C 1 -C ₄ -alkyl, with an aminoazole of the formula

to 7-hydroxyazolopyrimidines of the formula IV

which converts to compounds of the formula V,

in the Hal for chlorine or bromine, are halogenated, and V is reacted with ammonia.

10. Compounds of formulas IV and V according to claim 9.

11. Process for the preparation of compounds of the formula I according to one of claims 1 to 8, characterized in that acyl cyanides of the formula VI,

with an aminoazole of formula III according to claim 9.

12. A process for the preparation of compounds of the formula I according to claim 1, in which R ¹ is halogen-substituted C ₁ -C ₄ -alkyl, C ₁ -C ₂ -alkoxy-C ₁ -C ₂ -alkyl, C ₂ -C 12 -alkenyl or C ₂ -C 12 -cycloalkyl, Alkynyl, by halogenation of Azolopyrimi- dinen of formula VII, in which R ^2, R ³ and A have the meaning according to claim 1 and R CrCl ₄ - alkyl, Ci-Ci2-alkoxy-Ci-Ci2-alkyi, _C2-Ci2 alkenyl, _C2-Ci2 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 a

Acid.

13. A composition comprising a solid or liquid carrier and a compound of the formula I according to one of claims 1 to 8.

14. Composition according to claim 12, containing a further active ingredient.

15. Seed containing a compound of formula I according to any one of claims 1 to 8 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 from fungal attack materials, plants, the soil or seeds with an effective amount of a compound of formula I according to any one of claims 1 to 8.