EP1856119A1

EP1856119A1 - 5,6-dialkyl-7-amino-azolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds

Info

Publication number: EP1856119A1
Application number: EP06708583A
Authority: EP
Inventors: Peter Schäfer; Udo HÜNGER; Maria Scherer; Harald Köhle; Helmut Schiffer; Thomas Grote; Jochen Dietz; Wassilios Grammenos; Jan Klaas Lohmann; Bernd Müller; Joachim Rheinheimer; Frank Schieweck; Anja Schwögler
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-03-01
Filing date: 2006-03-01
Publication date: 2007-11-21
Also published as: JP2008536805A; WO2006092412A1; CN101128466A; TW200700419A; BRPI0607502A2; US20080171657A1

Abstract

The invention relates to 5,6-dialkyl-7-amino-azolopyrimidines of formula (I), in which the substituents are defined as follows: R1 represents alkyl, alkoxymethylene or alkoxyethylene, where the aliphatic groups can be substituted as per the description; R2 represents n-propyl or n-butyl; A represents N or CH; and R3 represents methyl 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} Ce-Cg-alkyl, C ₄ -C 18 -alkoxymethylene or C ₃ -Cio-alkoxyethylene, where the aliphatic groups may be substituted by one to three of the following groups:

Cyano, nitro, hydroxy, C3-C6-cycloalkyl, Ci-Cβ-alkylthio, Cs-Ci2-alkynyl or NR ^a R ^b ; R ^a , R ^{b are} hydrogen or C ₁ -C ₆ -alkyl;

R ^{2 is} n-propyl or n-butyl;

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 the formula I differ from those mentioned above by the specific embodiment of the substituent in the 6-position of the azolopyrimidine skeleton. 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 C 1 -C ₄ -alkyl, for practical reasons, methyl, ethyl or propyl is preferred therein.

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 metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, also organic bases, for example tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-di Methyl-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 temperature between 50 and 300 ⁰ C, preferably at 50 to 180 ⁰ C, when working in solution [cp. 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 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. Particularly suitable solvents are 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, Dibutylformaimid, 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-aminoazolo [1, 5-a] -pyrimidines of formula I are optionally isolated after evaporation of the solvent or dilution with water as crystalline compounds.

The substituted alkyl cyanides of formula VI required for the preparation of the 7-amino-azolo [1,5-a] -pyrimidines are known in part or may 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).

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;

Alkyl: saturated, straight-chain or mono- or di-branched hydrocarbon radicals having 1 to 4 or 5 to 9 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, n-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-methyl-propyl; Alkoxymethylene and alkoxyethylene: saturated, straight-chain or mono-, di- or trisubstituted hydrocarbon chain which is bonded via a methyleneoxy or ethylene-oxy group, eg. B. hydrocarbon chain as described above having 3 to 11 carbon atoms, such as propoxy-ethyl, butoxy-ethyl, pentoxy-ethyl, hexoxy-loxy-ethyl, heptyloxy-ethyl, octyloxy-ethyl, nonyloxy-ethyl, 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;

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 azolopyrimidines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

The alkyl groups in R ¹ in formula I are preferably unbranched or mono-, di- or trisubstituted alkyl groups, the alkyl groups preferably carrying no substituents.

In addition, preference is given to compounds of the formula I which have one described in R ¹ on the α-carbon atom:

in which R is C ₃ -Cio-alkyl or C ₅ -C ₀ alkoxyalkyl and R ¹² Ci-C ₄ alkyl, especially methyl, ¹¹ wherein R ¹¹ and R ¹² together do not have more than 12 carbon atoms and are unsubstituted or as R ¹ may be substituted in formula I.

If R ^{1 represents} a cyano-substituted alkyl group, the cyano group is preferably on the terminal carbon atom.

In one embodiment of the compounds I according to the invention, R ^{1 is} Ce-Cg-alkyl, C ₄ -C 5 -alkoxy-methylene or C 3 -C -alko-oxyethylene. C ₄ -C ₀ for these groups - preferably alkoxy.

Particularly preferred are compounds I in which R ^{1 is} hexyl, 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 or 1-ethyl-2-methylpropyl.

In addition, compounds of the formula I are preferred in which R ^{1 is} n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, n-nonyl, 1-methyloctyl and 3,5,5-trimethyl-hexyl.

In one embodiment of the compounds I according to the invention R ^{2 is} n-propyl.

In a further embodiment of the compounds I according to the invention R ^{2 is} n-butyl.

In a preferred embodiment of the compounds of the invention R ^{3 is} methyl.

One embodiment relates to compounds I in which A is CH. These compounds correspond to formula 1.1:

Another embodiment of the compounds according to the invention relates to compounds I in which A is 1:

In particular, with regard to their use, the compounds I summarized 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 and R ^{2 is} n-propyl and R ^{3 is} hydrogen

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

Table 4

Table A and R ^{2 is} n-butyl and R ^{3 is} methyl

Table 5

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-propyl and R ^{3 is} methyl

Table 6

Compounds of the formula I.2, in which R ^{1 is} a compound of one line each of

Table A and R ^{2 is} n-butyl and R ^{3 is} methyl

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 partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are particularly important for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and pumpkins, 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. solani or A. alternata on potato and other plants),

- Aphanomyces species of sugar beet and vegetables,

Bipolaris and Drechslera species on maize, cereals, rice and turf (e.g., D. teres sn 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 maize, soybeans, rice and sugar beet (for example C. beticula on sugar beets),

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 sn various plants), - Exserohilum species on maize,

Erysiphe cichoracearumunύ Sphaerotheca fuliginea on cucurbits, Fusarium and Verticillium species (eg K dahliae) on various plants (eg F. graminearum on wheat), Gaeumanomyces gram / n / s on cereals,

Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice), - Grainstaining complex on rice,

Helminthosporium species (for example A. graminicola) on maize and rice, Michrodochium nivale on cereals,

- Mycosphaerella species on cereals, bananas and peanuts fM graminicolä on wheat, M fijiesis on banana, ⁾ , - Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,

Phomopsis species on soybeans, sunflowers and vines (P. viticola on vines, P. he / ianthi / 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 (e.g., P. cubenis on cucumber),

- Puccinia species on cereals, maize and asparagus (P. triticina and P. striformis on wheat, P. asparagi on 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., P », so / anf) on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and other plants,

Sclerotinia species (e.g., S. sclerotiorum) on oilseed rape, sunflowers and other plants,

- Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (syn. Uncinulanecator) on grapevine,

- Setospaeria species on corn and turf, Sphacelotheca reilinia on maize, - Thievaliopsis species on soya beans and cotton,

Tilletia species of cereals,

Ustilago species on cereals, corn and sugar beet and Venturia species (scab) on apple and pear (e.g., K inaequalis on apple).

In particular, they are suitable for controlling harmful fungi from the class Oomycetes, such as Peronospora Aύen, Phytophthora species, Plasmopara viticola and Pseudoperonospora species. The compounds I are also suitable for controlling harmful fungi in the protection of materials (eg 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 / et / rotus spp., Porta spp., Serpula spp. and 7y / o / 77yces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as M / ccvspp., moreover, in the material contactor, 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 customary formulations, for example 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, for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, Lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, 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 ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. In the 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 ground 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 are usually used (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). 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 purposes of 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, oil dispersions) by addition of 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 concentrates which are active substance, adhesion, dispersant or emulsifier and, if appropriate, 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: 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 can also be present in the application form as fungicides together with other active substances, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixing the compounds I, or the agents containing them with one or more other active ingredients, in particular fungicides, for example, in many cases, the spectrum of activity widened or resistance developments 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-thiazole-5-carboxylic acid (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2 -methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-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-carboxylic 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-phenyl) -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, proquinazide, pyroquilon, quinoxyfen, tricyclazole, 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-methylindol-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. 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, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing on the basis of ethoxylated alkylphenol Ie) in the volume ratio solvent-emulsifier from 99 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.

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-pentanolyl-octane-nitrile

A solution of 10.0 g (80 mmol) of octanenitrile in 50 ml of dimethylformamide (DMF) was added dropwise at 30 ⁰ C with a solution of 17.92 g (160 mmol) of potassium tert.butanolat in 50 ml of DMF. Subsequently Valeriansäureethyles- ter added dropwise and stirred overnight at 20-25 ⁰ C 10.40 g (mmol 30). After distilling off the solvent in vacuo, the residue was dissolved in water and extracted with cyclohexane. The organic phase was discarded, the aqueous phase is acidified with conc. HCl and extracted with methyl tert-butyl ether (MTBE). The combined organic extracts were washed with water, then dried. After removal of the solvent, 10.59 g of the title compound were obtained as a brown oil, which was further reacted directly.

Example 2: Preparation of 5-butyl-6-hexyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine

A solution of 1.20 g of the ketonitrile (5.7 mmol) from Ex. 1, 0.55 g (5.7 mmol) of 5-methyl-pyrazol-3-amine and 0.21 g (1.1 mmol) p-Toluenesulfonic acid in 10 ml of mesitylene was heated at 180 ^° C. for three hours. Thereafter, the solvent was distilled off in vacuo, the residue taken up in dichloromethane and washed with water and NaHCO ₃ - solution. The organic phase was dried, the solvent was removed in vacuo and the residue triturated with pentane. There remained 1, 32 g of the title compound as light brown crystals of mp 134-136 ⁰ C back. Table I - Compounds of the formula

Example of use - Protective activity against Puccinia recondita on wheat (wheat brown rust)

Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust {Puccinia recondita). Subsequently, the plants were placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. On the following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 ° C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

In this test, the plants treated with 250 ppm of the active compounds I-2, 1-3 or I-4 showed a maximum of 1% infestation, while the untreated plants were 90% infected.

Claims

claims

1. Azolopyrimidines of the formula

in which the substituents have the following meanings:

R ¹ Cβ-Cg-alkyl, C ₄ -C r alkoxymethylene or C ₃ -C 10 -alkoxyethylene, where the aliphatic groups may be substituted by one to three of the following groups: cyano, nitro, hydroxy, C ₃ -C ₆ -cycloalkyl, Ci -C ₆ alkylthio, C ₅ -C ₂ alkynyl, or NR ^a R ^b; R ^a , R ^{b are} hydrogen or C ₁ -C ₆ -alkyl;

R ^{2 is} n-propyl or n-butyl;

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 A is CH.

3. Compounds of the formula I according to claim 1 or 2, in which R ^{1 represents} an unsubstituted, unbranched or mono-, di- or trisubstituted alkyl chain having up to 9 carbon atoms.

4. Compounds of formula I according to any one of claims 1 to 3, wherein R ^{2 is} n-propyl.

5. Compounds of formula I according to any one of claims 1 to 3, wherein R ^{2 is} n-butyl.

6. Compounds of formula I according to claim 1: 6-hexyl-2-methyl-5-propyl-pyrazolo [1, 5-a] pyrimidin-7-ylamine; 6-heptyl-2-methyl-5-propyl-pyrazolo [1,5-a] pyrimidin-7-ylamine; 2-methyl-6-octyl-5-propyl-pyrazolo [1,5-a] pyrimidin-7-ylamine;

2-methyl-6-nonyl-5-propyl-pyrazolo [1,5-a] pyrimidin-7-ylamine;

5-Butyl-6-hexyl-2-methyl-pyrazolo [1,5-a] pyrimidin-7-ylamine;

5-butyl-6-heptyl-2-methyl-pyrazolo [1,5-a] pyrimidin-7-ylamine;

5-butyl-2-methyl-6-octyl-pyrazolo [1,5-a] pyrimidin-7-ylamine; 5-Butyl-2-methyl-6-nonyl-pyrazolo [1,5-a] pyrimidin-7-ylamine.

7. Process for the preparation of compounds of the formula I according to one of claims 1 to 5, characterized in that β-ketoesters of the formula II,

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

to 7-hydroxyazolopyrimidines of the formula IV

which converts to compounds of the formula V,

Hal

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

8. Process for the preparation of compounds of the formula I according to one of claims 1 to 6, characterized in that acyl cyanides of the formula VI,

with an aminoazole of the formula IM according to claim 7.

9. A composition containing a solid or liquid carrier and a compound of the formula I according to one of claims 1 to 6.

10. A composition according to claim 9 containing a further active ingredient.

11. Seed containing a compound of formula I according to any one of claims 1 to 6 in amounts of 1 to 1000 g per 100 kg.

12. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected against 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 6.