The efficacy of the active components can often be improved by addition of other (active) ingredients. The observed efficacy of the combination of ingredients can sometimes be significantly higher than that would be expected from the amounts of the indi- vidual ingredients used, thus indicating synergism from the com- ponents of the combination.

The usual components of formulations such as carriers and inert ingredient (e. g. organic solvents, suspension agents, emulsion agents, wetting agnets, solubilizing agents) which do not them- selves possess pesticidal activity, however, do not usually lead to an unexpected increase in efficacy.

International Patent Application WO 95/01722 discloses pesticidal formulations containing non-ionic surface-active agents which can be selected, inter alia, from liquid polyalkoxylated aliphatic alcohols. However, the addition of these agents is directed to improving the storage stability of the formulations, and there is no report of enhancing the activity of fungicides used in the formulations.

U. S. Patent 4,851,421 discloses the use of polyalkylene-type non- ionic surface active agents derived from the alkoxylation of fatty alcohols with alkyleneoxides, polyoxyalkylene mono-or dialkylphenyether or polyoxyalkylene sorbitan fatty acid esters.

It is an object of this invention to provide methods for further enhancement of the efficacy of said fungicidal triazolopyrimidi- nes. It is another object of this invention to provide fungicidal compositions of said triazolopyrimidines and adjuvants, as well as methods for their use in the control of phytopathogenic fungi.

-There is ongoing research to identify suitable adjuvants which combination with the active fungicidal ingredient provide a means to lower the dose of active fungicidal agent required for effec- tive disease control. This goal is desirable from both an econo- mic and an environmental standpoint.

EP-A 71 792 and EP-A 550 113 disclose fungicidal triazolopyrimi- dine compounds. EP-A 943 241 describes the enhancement of the fungicidal efficacy of said triazolopyrimidines by the addition of selected adjuvants from he liqid polyalkoxylated aliphatic al- cohol class.

It has now been found that the effective amounts of fungicidal triazolopyrimidines of formula I in which R1 and R2 independently denote hydrogen or Cl-Clo-alkyl, C2-Clo-alkenyl, C2-C1o-alkynyl, or C4-C1o-alkadienyl, C3-C1O-cycloalkyl, phenyl, naphthyl, or 5-or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5-or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or where R1 and R2 radicals may be unsubstituted or may carry one to three groups Ra, Ra is cyano, nitro, hydroxyl, Cl-C6-alkyl, C1-C6-haloal- kyl, C3-C6-cycloalkyl, Cl-C6-alkoxy, Cl-C6-haloalkoxy, Cl-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino,

C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy and Cl-C4-alkylenedioxy ; or R1 and R2 together with the interjacent nitrogen atom represent a 5-or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted by one to three Ra radicals; R3 represents halogen or Cl-C6-alkyl or Cl-C6-alkoxy ; n represents an integer from 0 to 5; and Hal represents halogen; which must be applied can be lowered considerably with respect to the amounts usually employed to achieve the same fungicidal effect, if these fungicidal compounds or their formulations are applied in combination with one or more adjuvants selected from the groups consisting of a) non-ionic water-soluble mixed polyalkoxylated aliphatic alco- hol surfactants, b) non-ionic water soluble ethoxylated aliphatic alcohol surfactants, c) amine ethoxylates, and d) micronized polymeric waxes.

The biological activity of the active ingredient of formula I can be increased by including any of these adjuvants in the spray di- lution or directly in the formulation. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation or can be added to the spray tank together with the formulation con- taining the active ingredient. The water-soluble mixed polyalk- oxylated or ethoxylated aliphatic alcohols are particularly use- ful for liquid formulations, in particular for aqueous suspension concentrates (SC). The mixed polyalkoxylated adjuvants are con- tainable by alkoxylation of fatty alcohols having 8-18 C-atoms, with alkylene oxides having 2-6, preferably with a mixture of ethylene oxide and propylene oxide. The aliphatic moieties of the said fatty alcohols may be straight-chained or branched. The ethoxy to propoxy ratio is from 50: 50 to 90: 10. Preferred water

soluble non-ionic surfactants of the mixed alkoxylated aliphatic alcohol class are mixed random or block oligomers of formula II H2n+lCn-0- (CH2CH20) x (CH2CH (CH3) 0) yH (II) wherein n is an integer from 8 to 18; x is an integer from 3 to 10; and y is an integer from 1 to 3.

Of particular interest are those water soluble mixed polyalkoxy- lated aliphatic alcohols which are commercially available under the trademark PlurafacX LF (Tensid-Chemie, Koln/BASF AG, Ludwigshafen). In particular PlurafacX LF 300 has been proven to be especially advantageous.

The water soluble polyethoxylated adjuvants are obtainable in si- milar fashion and are straight chained or branched C10-25 alcohols ethoxylated with 10 to 25 ethoxy groups. Particularly preferred is Lubrol@ 17A17, commercially available from Uniqema, Everberg, Belgium.

The amine ethoxylate adjuvants are tertiary amine ethoxylates ba- sed on primary amines such as oleyl amine and tallow amine. Par- ticularly preferred are those comercially available under the trademark Berol 381@ and Berol 303@ (Ethomeen@ S22) from Akzo Nobel Surface chemistry, Sweden.

A particularly preferred micronized polymeric wax is a modified polyethylene wax commercially available under the trademark XCe- ridust 9615A from Clariant GmbH, Augsburg, Germany.

The enhancement in efficacy by addition of the said adjuvants can be abserved for the fungicidal triazolopyrimidines of formula I, preferably, wherein R1 and R2 together with the adjacent nitrogen atom represent an optionally substituted 6-membered heterocyclic ring, or whe- rein R1 represents a Cl_6-alkyl, a Cl_6-haloalkyl, in particu- lar Cl_6-fluoroalkyl, or a C3_8-cycloalkyl group and R2 repre- sents a hydrogen atom or a Cl_6-alkyl group and/or wherein

represents wherein L1 represents a halogen atom, preferably fluorine or chlorine and L2 and L3 each independently represents a hydro- gen atom or a halogen atom, preferably fluorine and/or whe- rein Hal represents a chlorine atom.

In a particularly preferred embodiment the triazolopyrimidine is 5-chloro-6- (2-chloro-6-fluorophenyl)-7-N- (4-methylpiperid-1-yl)- [1, 2,4] triazolo [1, 5-a] pyrimidine coded compound IA, and 5-choro-6- (2,4,6-trifluoro-phenyl)-7- (2,2,2,-trifluoro-1-methyl- amino) [1, 2,4] triazolo [1, 5-a] pyrimidine coded compound IB.

The adjuvants of the present invention can be included in the formulation or added in a suitable formwith the preparation of the spray mix (tank mix). In this latter case, they are added preferably as a separate preparation with the other components such as a dispersing agent or an antifoam and, where desirable, with further adjuvants so as to ensure that they are homogenously dispersed in the spray mix.

The present invention also relates to fungicidal formulatioms with at least mone compound of formula I, adjuvants and/or carrier substances characterised by their containing, in addition to the conventional adjuvants and carriers, one ore more adjuvants selected form the group consisting of a) non ionic water-soluble mixed polyalkoxylated aliphatic alco- hol surfactants, b) non-ionic water soluble ethoxylated aliphatc alcohol surfactants, c) amine ethoxylates, and d) micronized polymeric waxes.

The fungicidal compounds can be applied as normal commercial for- mulations with adjuvants accoring to the invention, and where de- sirable, with additional components such as antioxidants and emulsion agents.

The appropiate relative amounts of active ingredientand the wa- ter-soluble adjuvant lie, in accordance with the invention, between 100: 75 and 100 : 100,000, preferably between 100: 90 and 100: 50,000 and, more preferably, between 100: 125 and 100: 5,000.

In general and within certain limits, the fungicidal efficacy can be enhanced to a higher degree by the addition of larger amounts of the adjuvant.

In a preferred embodiment the adjuvant is added to the tank mix together with the triazolopyrimidine as a formulation.

The present invention also relates to a kit for the preparation of a spray mixture consisting of two separate containment: 1) a containment which comprises at least one fungicide of for- mula I and conventional inert ingredients and carriers; 2) a containment which comprises at least one adjuvant selected from the group consisting of a) non-ionic water-soluble mixed polyalkoxylated aliphatic alcohol surfactants, b) non-ionic water soluble ethoxylated aliphatic alcohol surfactants, c) amine ethoxylates, and d) micronized polymeric wax.

In a preferred embodiment said kit will consist of two bottles with dispensing means which allow the easy and correct addition of the active ingredient (1) and the adjuvant (2) to the tank mix.

Recommended doses for various applications are known for the fun- gicidal compounds of formula I where the efficacy can be enhanced in accordance with the invention. Addition of the adjuvants sug- gested here can (depending on the active ingredient, the adjuvant and their amounts)'reduce the amount of active ingredient per hectare required in these recommendations by half or more, whe-

reby it becomes possible to control additional diseas-es at reaso- nable doses.

In a preferred embodiment the adjuvants in combination with the fungicide of formula I are applied at rates of 40 to 4000 ml/ha, preferably 50 to 3000 ml/ha, in particular 60 to 2000 ml/ha.

An important advantage is the rapid onset and the high persi- stency of activity on use of the new additives. This enlarges the periad for application of the fungicide and, hence, makes it more useful.

The fungicidal formulations according to the present invention can be used in combination with said additives prophylactically and curatively.

The adjuvants according to the invention, the compounds of for- mula I, and usual adjuvants and carriers can be processed to the preferably fluid or dispersible solid formulations known in the art, for example, as solutions, emulsions, wettable powders (WPs), suspension concentrates (SCs), emulsion concentrates (ECs), low volume or ultra low volume preparations and water dis- persible granules (WGs).

As well as fluid and/or solid carries or solubilising agents such as organig solvents like ketones, alcohols, fluid aliphatic, aliphatic or aromatic compounds, fine natural or synthetic sili- cates or carbonates, the preparations usually contain ionic and/ or non-ionic surfactants which function as emulsion, dispersing or wetting agents. Antifoam and antifreeze agents may also be ad- ded. Suitable adjuvant and carriers substances are described in the literature and well known to the persons skilled in the art.

A composition according to the invention preferably contains from 0.5 % to 95 % by weight (w/w) of active ingredient.

A carrier in a composition according to the invention is any ma- terial with which the active ingredient is formulated to facili- tate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solied or a liquid, including material which is normally a gas but which has been compressed to form a liquid.

Aqueous dispersions and emulsions, for example compositions ob- tained by diluting the formulated product according to the inven- tion with water, also lie within the scope of the invention.

Of particular interest in enhancing the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protec- ted.

Examples of formulations according to the invention are shown in the following formulations A and B: Formulation A: Suspension concentrate (SC) Component |Amount [g/l] |Ingredient activeingredient 200. 0 Compound IA dispersant 30.0 Morwet# D4251 dispersant 15. 0 Pluronic@PE 105002 antifoamagent 2. 0 Rhodorsil0 426 R3 structureagent 1. 0 RhodopolOO233 preservative 2. 0 ProxelX GXL4 structure agent 5. 0 Veegum T5 antifreeze agent 40. 0 propylene glycol water to 1000 ml 1 Witco Corporation, Houston, USA 2 Tensid-Chemie, Koln/BASF AG, Ludwigshafen, Germany 3 Rhodia GmbH, Frankfurt, Germany 4 Zeneca GmbH, Frankfurt, Germany 5 Vanderbilt, Norwalk, USA The SC formulation described above is mixed before applcation with water to give a spray mix with the desired concentration of active ingredient. A non-ionic surface-active agent selected from the water-soluble mixed polyalkoxylated aliphatic alcohol class, in particular Plurafac@ LF300 (250 g/1), is added to the resulting tank mix.

Formulation B: Suspension Concentrate (SC)

Component Amount Eg/11 ingredient activeingredient 200. 0 Compound IA dispersant 30. 0 MorwetE 34251 dispersant 15. 0 PluronicX PE 105002 preservative 2. 0 Proxel@ GXL3 antifoamagent 5. 0 SAG 2201 structureagent 0. 8 Rhodopol0 234 structureagent 5. 0 Vegum Pros water to 1000 ml Witco Corporation, Houston, USA 2 Tensid-Chemie, Koln/BASF AG, Ludwigshafen, Germany 3 Zeneca GmbH, Frankfurt, Germany 4 Rhodia GmbH, Frankfurt, Germany 5 Vanderbilt, Norwalk, USA The SC formulation described above is mixed before application with water to give a spray mix with the desired concentration of active ingredient. A non-ionic surface-active agent selected from the water-soluble mixed polyalkoxylated aliphatic alcohols, in particular PlurafacX LF 300 (150 g/1) and additionally a non-ionic surface-active agent selected from the water soluble polyethoxy- lated aliphatic alcohol class, in particular Lubrol 17A17 (150 g/1) is added to the resulting tank mix.

It is also an object of the invention to suggest a method for the control of phytopathogenic fungi, characterised by the use of the compounds of formula I, in particular formular IA in combination with one or more adjuvants selected from the groups consisting of a) non-ionic water-soluble mixed polyalkoxylated aliphatic alco- hol surfactants, b) non-ionic water soluble ethoxylated aliphatic alcohol surfactants, c) amine ethoxylates, and d) micronized polymeric waxes.

Plant diseases that can be combated with the fungicidal formula- tions according to the present invention diseases caused by Asco- mycete fungi, such as Erysiphales as for example Erysiphe cichoracearum or Uncinula necator, and Dothideals as for example Venturia inaequalis or Septoria tritici (Mycosphaerella gramini- cola).

For a more clear understanding of the invention, specific exam- ples thereof are set forth below.

The test results described below demonstrate the enhancement in fungicidal efficacy of triazolopyrimidines of formula I by the addition of adjuvants according to the invention.

Example 1 Greenhouse Evaluations for Curative and Residual Fungicidal Acti- vity The formulated compound (see formulation below) was prepared as an aqueous suspension using concentrations of 100,20 and 4 ppm active ingredient (a. i.) and was applied to greenhouse plants using a single-nozzle overhead rack sprayer at an application rate of 200 litre/ha. Within the 200 1/ha the compound was alter- natively in-tank mixed with 1000 ppm of adjuvant (s) (as given in tale of results). In case two adjuvants were added to the compound, the concentration of each adjuvant was 500 ppm.

Barley seedlings (var.'Golden Promise') and wheat seedlings (var.'Kanzler') were grown to the primary leaf stage (ca. 1 week old) in 6-cm-diameter pots in the greenhouse. Plants for both cu- rative and residual tests were sprayed at the same time with in- oculations of the pathogens being done in different days.

For curative tests, barley and wheat plants were inoculated 2 days prior to compound treatment by dusting with conidia of Blu- meria (Erysiphe) graminis f. sp. hordei or B. graminis f. sp. tritici to create powdery mildew diseases. Plants were kept in the greenhouse until treated. After tratment, the plants were re- turned to the greenhouse and kept there until powdery mildew di- sease symptoms/signs developed on untreated plants.

Plants were than evaluated for percent disease on the treated primary leaves. For curative rust tests, wheat plants were inocu- lated 2 days prior to compound treatment by spraying with a ure- diniospore suspension in 0. 05 % aqueous Tween 10 (1 mg spores per ml) of Puccinia recondita, kept in a moist infection chamber for one day then moved to the greenhouse until treated. After treat- ment the plants were kept in the greenhouse until disease sym- toms/signs developed on a untreated plants. Plants were then eva- luated for percent disease on the treated primary leaves.

For residual tests, plants were treated first and then kept for 4 days in the greenhouse before being inoculated with the pathogens as described for curatuve tests. Inoculated plantes were kept in the greenhouse until desease symptoms/signs develop on untreated plants. Plants were the evaluated for percent desease on the treated primary leaves.

Disease control efficacy was calculated from the percent disease values using the following formula: % infected leaf area in treated plants %disease control=100- %infected leaf area in untreated plants Table I gives the means of the efficacy (% control) of the three concentrations of compound IA used. This is accepted because the adjuvant concentrations were the same at all the compound a. i. concentrations used.

The composition of formulation R in Table I is Formulation R: Suspension Concentrate (SC) Component Amount [g/1] Ingredient active ingredient 100. 0 Compound IA dispersant 20. 0 Atlas G5000 dispersant 10. 0 SynperonicAl antifoam agent 3. 0 RhodorsilO 4262 preservative 2. 0 ProxelE GXL3 structure agent 3. 0 RhodopolX 232 antifreeze agent 50. 0 propylene glycol water to 1000 ml 1 Uniqema, Everberg, Belgium 2 Rhodia GmbH, Frankfurt, Germany 3 Zeneca GmbH, Frankfurt, Germany Table I Mean % Control Over 3 Rates (100-20-4 ppm) of Compound 1A WPM* WLR* BPM* Treatment 2 Day 4 Day 2 Day 4 Day 2 Day 4 Day Curative Residual Curative Residual Curative Residual Formulation A 16 42 48 10 21 14 Formulation A & Pluarafac LF 300 49 40 69 28 69 30 (1000 ppm) Formulation A & Lubrol 17A17 43 33 72 15 38 26 (1000 ppm) Formulation A & Pluarafac LF 700 42 40 79 33 38 28 (500ppm) + Lubrol 17A17 (500 ppm) Formulation A & Pluarafac LF 300 55 49 78 38 57 43 (500ppm) + Lubrol 17A17 (500 ppm) Formulation A & Berol 381 52 47 72 23 54 38 (1000 ppm) Formulation A & Ethimeen S 22 53 48 72 22 56 28 (1000 ppm) Formulation A & Ceridust 9615 A 29 45 62 27 35 32 * WPM = wheat powdery mildew ; WLR = wheat leaf rust, BPM = barely powdery mildew