Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds

Abstract

The present invention relates to substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds of formula I as defined in the description, and the N-oxides, and salts thereof, their preparation and intermediates for preparing them. The invention also relates to the use of these compounds for combating harmful fungi and seed coated with at least one such compound and also to compositions comprising at least one such compound.

Claims

1. (canceled)

2. A compound of formula I ##STR00074## wherein: R is CF.sub.3; R.sup.1 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl, or C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl; R.sup.2 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl, phenyl, phenyl-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.2-C.sub.4-alkenyl or phenyl-C.sub.2-C.sub.4-alkynyl; wherein the aliphatic groups R.sup.1 and/or R.sup.2 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R.sup.a which independently of one another are selected from the group consisting of halogen, CN, nitro, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-halogenalkoxy; wherein the cycloalkyl and/or phenyl moieties of R.sup.1 and/or R.sup.2 may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups R.sup.b which independently of one another are selected from the group consisting of halogen, CN, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-halogenalkyl and C.sub.1-C.sub.4-halogenalkoxy; R.sup.3 is halogen, CN, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenalkyl, C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-halogenalkoxy n is an integer and is 0, 1, 2 or 3; R.sup.4 is halogen, CN, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-halogenalkyl, C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-halogenalkoxy m is an integer and is 0, 1, 2, 3, 4 or 5; and an N-oxide or an agriculturally acceptable salt thereof.

3. The compound according to claim 2, wherein R.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, C.sub.2-C.sub.6-alkynyl, cyclopropyl, phenyl, benzyl, phenylethenyl or phenylethynyl.

4. The compound according to claim 2, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, propargyl or benzyl.

5. The compound according to claim 2, wherein m is 1, 2 or 3 and R.sup.4 is selected from F and Cl.

6. The compound according to claim 2, wherein: n=0, R.sup.2 is hydrogen, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from the group consisting of H, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CCCH.sub.3, CH.sub.2CCH, isopropyl, cyclopropyl and CF.sub.3, n=0, R.sup.2 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from H, CH.sub.3, CH.sub.2CH.sub.3, isopropyl and cyclopropyl; n=0, R.sup.2 is H, R.sup.4.sub.m is 2,4-Cl.sub.2 and R.sup.1 is H; n=0, R.sup.2 is H, R.sup.4.sub.m is 4-F and R.sup.1 is CH.sub.3; n=0, R.sup.1 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CHCH.sub.2; or n=0, R.sup.1 is methyl-propargyl, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CCH.

7. A process for preparing compounds of formula I as defined in claim 2, which comprises reacting a compound of formula IIIa ##STR00075## in presence of a catalyst with isopropylmagnesium halide followed by a reaction with R.sup.1COCl; reacting the resulting compound of formula VIII ##STR00076## under basic conditions with a compound of formula II ##STR00077## reacting the resulting compound of formula Va ##STR00078## with trimethylsulf(ox)onium halide; reacting the resulting compound of formula IX ##STR00079## under basic conditions with 1H-1,2,4-triazole; and optionally derivatizing the resulting compound of formula I.A ##STR00080## under basic conditions with R.sup.2-LG, wherein LG is a nucleophilically replaceable leaving group, to obtain compounds of formula I.

8. A process for preparing compounds of formula I as defined in claim 2, which comprises reacting a compound of formula IX ##STR00081## under acidic conditions with R.sup.2OH, reacting the resulting compound of formula X ##STR00082## with a halogenating agent or sulfonating agent; and reacting the resulting compound of formula XI ##STR00083## wherein LG is a nucleophilically replaceable leaving group with 1H-1,2,4-triazole to obtain compounds I.

9. A compound of formulae IVa, Va, VI, VII or IX ##STR00084## wherein R.sup.3, R.sup.4, m and n and R.sup.1, if applicable, are as defined in claim 1 and wherein X.sup.1 is I or Br, and wherein R in formulae VI, Va, VII and IX is C.sub.1-C.sub.2-halogenalkyl, with the proviso that in formula Va if R.sup.1 is hydrogen and R is CF.sub.3 and n=0, R.sup.4.sub.m is not 3-CF.sub.3 or 3-CF.sub.3-4-Cl; and wherein in formula IVa R is selected from 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 and pentafluoroethyl, with the proviso that in formula IVa if X.sup.1 is Br, R is CF.sub.3 and n is 0, then m is not 0 and R.sup.4.sub.m is not 4-Br, 3-CF.sub.3, 4-F or 2-Cl.

10. An agrochemical composition comprising an auxiliary and at least one compound of formula I, as defined in claim 2, an N-oxide or an agriculturally acceptable salt thereof.

11. The composition according to claim 10, comprising an active substance additional to the compound of formula I.

12. A method for combating phytopathogenic fungi, comprising: treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I as defined in claim 2.

13. The method of claim 12, wherein R.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, C.sub.2-C.sub.6-alkynyl, or cyclopropyl.

14. The method of claim 12, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, propargyl or benzyl.

15. The method of claim 12, wherein m is 1, 2 or 3 and R.sup.4 is selected from F and Cl.

16. The method of claim 12, wherein: n=0, R.sup.2 is hydrogen, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from the group consisting of H, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CCCH.sub.3, CH.sub.2CCH, isopropyl, cyclopropyl and CF.sub.3, n=0, R.sup.2 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from H, CH.sub.3, CH.sub.2CH.sub.3, isopropyl and cyclopropyl, and the compound wherein n=0, R.sup.2 is H, R.sup.4.sub.m is 2,4-Cl.sub.2 and R.sup.1 is H; n=0, R.sup.2 is H, R.sup.4.sub.m is 4-F and R.sup.1 is CH.sub.3, and the compounds wherein n=0, R.sup.1 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CHCH.sub.2; or n=0, R.sup.1 is methyl-propargyl, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CCH.

17. Seed coated with at least one compound of formula I as defined in claim 2, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

18. The seed of claim 17, wherein R.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, C.sub.2-C.sub.6-alkynyl, or cyclopropyl.

19. The seed of claim 17, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl, allyl, propargyl or benzyl.

20. The seed of claim 17, wherein m is 1, 2 or 3 and R.sup.4 is selected from F and Cl.

21. The seed of claim 17, wherein: n=0, R.sup.2 is hydrogen, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from the group consisting of H, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CCCH.sub.3, CH.sub.2CCH, isopropyl, cyclopropyl and CF.sub.3; n=0, R.sup.2 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.1 is selected from H, CH.sub.3, CH.sub.2CH.sub.3, isopropyl and cyclopropyl; n=0, R.sup.2 is H, R.sup.4.sub.m is 2,4-Cl.sub.2 and R.sup.1 is H, and the compound wherein n=0, R.sup.2 is H, R.sup.4.sub.m is 4-F and R.sup.1 is CH.sub.3; n=0, R.sup.1 is CH.sub.3, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CHCH.sub.2; or n=0, R.sup.1 is methyl-propargyl, R.sup.4.sub.m is 4-Cl and R.sup.2 is selected from CH.sub.2CH.sub.3, and CH.sub.2CCH.

Description

I. SYNTHESIS EXAMPLES

[0675] With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I. The resulting compounds, together with physical data, are listed in Table I below.

Example 1

Preparation of 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1-[1,2,4]triazol-1-yl-propan-2-ol (compound I-2)

[0676] Step 1: 4-Fluoro-2-(trifluoromethyl)-acetophenone (35 g, 170 mmol), 4-chlorophenol (21.8 g, 170 mmol), potassium carbonate (28.1 g, 203 mmol) and DMF (284 g, 300 ml) were stirred together at about 115 C. for about five hours. After cooling, the mixture was added to a brine solution and extracted three times with MTBE. The organic phases were combined, washed twice with 10% aqueous LiCl solution and dried. Evaporation of the solvents gave the intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (51.4 g, 87%; HPLC R.sub.t=3.721 min*(conditions A see below)).

[0677] Step 2: DMSO (154 g, 140 ml, 1.97 mol) was added to a mixture of sodium hydride (0.831 g, 33 mmol) in THF (53 g, 6 0 ml) and cooled to about 5 C. Trimethylsulf(ox)onium iodide (6.42 g, 31.5 mmol) in DMSO (80 ml) was then added dropwise and the mixture was stirred at about 5 C. for a further hour. The intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (5.0 g, 14.3 mol) in DMSO (40 ml) was then added dropwise over a period of about five minutes. The mixture was then stirred for 15 min, quenched with saturated ammonium chloride solution (150 ml) and extracted three times with MTBE. The organic phases were combined, washed with water and dried. Evaporation of the solvent gave 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-methyl-oxirane as a yellow oil (4.4 g, 89%, HPLC R.sub.t=3.839 min*(conditions A see below)).

[0678] Step 3: A mixture of 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-methyl-oxirane (1.92 g, 4.96 mmol), 1,2,4-triazole (1.715 g, 24.8 mmol), NaOH (0.496 g, 12.41 mmol) and N-methyl pyrrolidone (48 ml) was stirred at about 110 C. for about one hour, followed by further four hours at about 130 C. After cooling to room temperature, saturated ammonium chloride solution was added and the organic phases extracted three times with MTBE. The organic phases were combined, washed twice with 10% LiCl solution and dried. Evaporation of the solvents followed by precipitation from diisopropyl ether gave the final product 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1-[1,2,4]triazol-1-yl-propan-2-ol as a white solid (1.55 g, 75%, m.p. 121-122 C., HPLC R.sub.t=3.196 min*(conditions A see below)).

Example 1a

Preparation of 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1-[1,2,4]triazol-1-yl-propan-2-ol (compound I-2)

[0679] Step 1:

[0680] 4-Fluoro-2-(trifluoromethyl)-acetophenone (622.0 g, 3.02 mol), 4-chlorophenol (426.7 g, 3.32 mol), potassium carbonate (542.1 g, 3.92 mol) and DMF (2365 ml) were stirred together at about 120 C. for about five hours then at 140 C. for 5 hours. After cooling, the mixture was added to a brine solution and extracted three times with MTBE. The organic phases were combined, washed twice with 10% aqueous LiCl solution and dried. Evaporation of the solvents gave the intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (884.7 g, 88%; .sup.1H-NMR (CDCl.sub.3; 400 MHz) (ppm)=2.60 (s, 3H); 6.98 (d, 2H); 7.10 (d, 1H); 7.30 (s, 1H); 7.35 (d, 2H); 7.50 (d, 1H).

[0681] Step 2:

[0682] DMSO (140 mL) was added to a mixture of sodium hydride (0.831 g, 33 mmol) in THF (53 g, 60 mL) and cooled to about 5 C. Trimethylsulfonium iodide (6.42 g, 31.5 mmol) in DMSO (80 ml) was then added dropwise and the mixture was stirred at about 5 C. for a further hour. The intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (5.0 g, 14.3 mol) in DMSO (40 ml) was then added dropwise over a period of about five minutes. The mixture was then stirred for 15 min, quenched with saturated ammonium chloride solution (150 ml) and extracted three times with MTBE. The organic phases were combined, washed with water and dried. Evaporation of the solvent gave 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-methyl-oxirane as a yellow oil (4.4 g, 89%). .sup.1H-NMR (CDCl.sub.3; 400 MHz) (ppm)=1.65 (s, 3H); 2.95-3.05 (d, 2H); 6.95 (d, 2H); 7.10 (d, 1H); 7.25 (s, 1H); 7.35 (d, 2H); 7.65 (d, 1H).

[0683] Step 3:

[0684] A mixture of 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-methyl-oxirane (1.92 g, 4.96 mmol), 1,2,4-triazole (1.715 g, 24.8 mmol), NaOH (0.496 g, 12.41 mmol) and N-methyl pyrrolidone (48 ml) was stirred at about 110 C. for about one hour, followed by further four hours at about 130 C. After cooling to room temperature, saturated ammonium chloride solution was added and the organic phases extracted three times with MTBE. The organic phases were combined, washed twice with 10% LiCl solution and dried. Evaporation of the solvents followed by precipitation from diisopropyl ether gave the final product 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1-[1,2,4]triazol-1-yl-propan-2-ol as a white solid (1.55 g, 75%, m.p. 121-122 C., HPLC Rt=3.196 min*(conditions A see below)).

Example 2

Preparation of 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1[1,2,4]triazol-1-yl-butan-2-ol (compound I-3)

[0685] Step 1: Bromine (29.6 g, 185 mmol) was added dropwise over three minutes to a solution of the 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]ethanone intermediate of step 1 of example 1, (61.4 g, 185 mmol), in diethyl ether (700 ml). The mixture was stirred at room temperature for about 90 min, after which a mixture of ice-cold water (11) and saturated sodium bicarbonate solution (300 ml) was added slowly under stirring until pH 7 to 8 was reached. The organic phases were extracted twice with MTBE and washed with LiCl solution. Drying and evaporation of the solvents gave the intermediate 2-bromo-1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone as a brown oil (76 g, 83%, HPLC R.sub.t=3.196 min*(conditions A see below)).

[0686] Step 2: 1,2,4-Triazole (3.76 g, 53 mmol) was added slowly and portionwise to a mixture of sodium hydride (1.28 g, 53 mmol) in THF (150 ml), and the mixture stirred at room temperature for about 30 min. To this mixture the intermediate 2-bromo-1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (20.0 g, 40.7 mmol) in THF (100 ml) was added dropwise and stirred at room temperature for about 150 min. The reaction mixture was cooled to about 10 C. and added slowly to a mixture of ice-cold water and saturated ammonium chloride solution, and the organic components extracted three times with ethyl acetate. The organic phases were combined, dried and the solvents evaporated. Recrystallisation from diisopropyl ether gave the intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-[1,2,4]triazol-1-yl-ethanone as a white solid (14.5 g, 84%; HPLC R.sub.t=3.225 min*(conditions A see below)).

[0687] Step 3: Magnesium bromide diethyl etherate (2.65 g, 10.3 mmol) was added to a solution of 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-[1,2,4]triazol-1-yl-ethanone (2.0 g, 5.1 mmol) in dichloromethane (DCM, 20 ml) and the mixture stirred at room temperature for 90 min. This mixture was then cooled to about 10 C. and ethylmagnesium bromide (10.3 ml of a 1M solution in THF, 10.3 mmol) was added dropwise. After stirring for about two hours, the mixture was allowed to warm to room temperature and was then quenched by addition of a saturated ammonium chloride solution. The organic components were extracted three times with DCM, the organic phases combined, washed again with saturated ammonium chloride solution, dried and the solvents evaporated. Addition of diisopropyl ether resulted in precipitation of the unreacted starting material, which was filtered off. The filtrate was then purified using reverse phase chromatography, to give the final product 2-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-1[1,2,4]triazol-1-yl-butan-2-ol as a light brown coloured solid (130 mg, 5.8%; HPLC R.sub.t=3.366 min*(conditions A see below); HPLC Rt=1.21 min, masse=412 **(conditions B see below).

Example 3

Preparation of 1-[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-methoxy-propyl]-1,2,4-triazole (compound I-10)

[0688] To a solution of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (33.35 g, 83 mmol) in 400 mL of THF was added sodium hydride (2.54 g, 100.5 mmol) at room temperature. The reaction mixture was then stirred for 30 min followed by the addition of methyliodide (14.24 g, 100.3 mmol) and stirred at 90 C. for 2 hours. After addition of an aq. solution of sodium chloride, the mixture was extracted with dichloromethane, dried, evaporated. The crude residue was purified by recrystallization in heptane/ethyl acetate (1:2) to give the title compound as a colorless solid (34.0 g, 98%; HPLC-MS R.sub.t=1.26 min; masse=412 **(conditions B see below)).

Example 4

Preparation of 1-[2-allyloxy-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)-phenyl]propyl]-1,2,4-triazole (compound I-18)

[0689] To a solution of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (40.0 g, 100.5 mmol) in 500 mL of THF was added sodium hydride (3.05 g, 120.6 mmol) at room temperature. The reaction mixture was then stirred for 30 min followed by the addition of allyl bromide (14.63 g, 120.9 mmol) and stirred at room temperature for 10 hours. After addition of an aq. solution of sodium chloride, the mixture was extracted with dichloromethane, dried, evaporated. The crude residue was purified on silica gel to give the title compound as a yellowish oil (43.5 g, 95%; HPLC-MS R.sub.t=1.36 min; masse=438**(conditions B see below)).

Example 5

Preparation of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)pent-3-yn-2-ol (compound I-6)

[0690] Step 1:

[0691] 1-Bromo-4-fluoro-2-(trifluoromethyl)benzene (2.04 g, 15.9 mmol) was mixed with potassium carbonate (4.18 g) in dimethylformamide and the reaction mixture heated to 110 C. Then 4-chloro-phenol (3.68 g, 15.14 mmol) was added and the resulting mixture was stirred for 5 hours at 110 C. After cooling and a water/DCM extraction, the organic layers were washed with an aqueous solution of lithium chloride and then sodium hydroxide, dried, filtrated and evaporated to give 3.14 g of 1-bromo-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzene as an oil. .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=6.80 (d, 1H); 6.95 (d, 2H); 7.35 (d, 2H); 7.55 (d, 1H); 7.80 (s, 1H).

[0692] Step 2:

[0693] To a solution of 1-bromo-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzene (100.0 g, 0.28 mol, 1.0 eq.) in 500 mL of THF was added dropwise isopropyl magnesium chloride lithium chloride complex (284 mL, 1.3 M in THF) at room temperature and stirred for 2 hours. This mixture was then added dropwise to a solution of acetyl chloride (29.0 g, 0.37 mmol) in 500 mL of THF at room temperature. The resulting reaction mixture was then stirred for 150 min and quenched with a sat. solution of ammonium chloride. After a water/MTBE extraction, the organic solvents were dried and evaporated to give 96.6 g of 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)-phenyl]ethanone as yellowish oil. .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=2.6 (s, 3H); 7.0 (d, 2H); 7.10 (d, 1H); 7.30 (s, 1H); 7.37 (d, 2H); 7.50 (d, 1H).

[0694] Step 3:

[0695] Bromine (29.6 g, 185 mmol) was added dropwise over three minutes to a solution of 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (61.4 g, 185 mmol), in diethyl ether (700 ml). The mixture was stirred at room temperature for about 90 min, after which a mixture of ice-cold water (1 L) and saturated sodium bicarbonate solution (300 ml) was added slowly under stirring until pH 7 to 8 was reached. The organic phases were extracted twice with MTBE and washed with LiCl solution. Drying and evaporation of the solvents gave the intermediate 2-bromo-1 [4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone as a brown oil (76 g, 83%). .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=4.35 (s, 2H); 7.0 (d, 2H); 7.12 (d, 1H); 7.34 (s, 1H); 7.38 (d, 2H); 7.55 (d, 1H).

[0696] Step 4:

[0697] 1,2,4-Triazole (3.76 g, 53 mmol) was added slowly and portionwise to a mixture of sodium hydride (1.28 g, 53 mmol) in THF (150 ml), and the mixture stirred at room temperature for about 30 min. To this mixture 2-bromo-1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-ethanone (20.0 g, 40.7 mmol) in THF (100 ml) was added dropwise and stirred at room temperature for about 150 min. The reaction mixture was cooled to about 10 C. and added slowly to a mixture of ice-cold water and saturated ammonium chloride solution, and the organic components extracted three times with ethyl acetate. The organic phases were combined, dried and the solvents evaporated. Recrystallization from diisopropyl ether gave the intermediate 1-[4-(4-chloro-phenoxy)-2-trifluoromethyl-phenyl]-2-[1,2,4]triazol-1-yl-ethanone as a white solid (14.5 g, 84%). .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=5.42 (s, 2H); 7.05 (d, 2H); 7.15 (d, 1H); 7.38 (s, 1H); 7.42 (d, 2H); 7.60 (d, 1H); 8.0 (s, 1H); 8.25 (s, 1H).

[0698] Step 5:

[0699] 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-(1,2,4-triazol-1-yl)ethanone (0.5 g, 1.31 mmol) was dissolved in THF (5.0 mL) with a solution of LaCl.sub.3.2LiCl (2.4 mL, 0.6M in THF) and stirred for 30 min at room temperature. The resulting solution was added dropwise to 1-propynylmagnesium bromide (1.5 mL, 0.5M in THF) at room temperature. After 30 min at room temperature, the resulting mixture was quenched with a 10% aqueous solution of HCl and extracted with MTBE. The organic phase was washed with brine, dried and evaporated to give after purification on reverse phase chromatography 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)pent-3-yn-2-ol as solid (25 mg, HPLC-MS R.sub.t=1.21 min, masse=422 **(conditions B see below), m.p=137 C.).

Example 6

Preparation of 1-[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-methoxy-butyl]-1,2,4-triazole (compound I-9)

[0700] To a solution of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)butan-2-ol (4.0 g, 9.71 mmol) in 20 mL of THF was added sodium hydride (294 mg, 11.64 mmol) at room temperature. The reaction mixture was then stirred for 30 min followed by the addition of methyliodide (1.67 g, 11.78 mmol) and stirred at room temperature for 10 hours. After addition of an aq. solution of sodium chloride, the mixture was extracted with dichloromethane, dried, evaporated. The crude residue was purified by flash chromatography on silica gel to give the title compound as a colorless oil (2.42 g, 54%; HPLC-MS R.sub.t=1.32 min; masse=426**(conditions B see below)).

Example 7

Preparation of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1,2,4-triazol-1-yl)butan-2-ol (compound I-7)

[0701] Step 1:

[0702] To a solution of 1-bromo-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzene (450.0 g, 1.15 mol) in 500 mL of THF was added dropwise to isopropyl magnesium chloride lithium chloride complex (1.152 L, 1.3 M in THF) at room temperature and stirred for 1 hour. The reaction mixture was then added dropwise over 1.5 hours at 10 C. to a solution of isopropyl carbonyl chloride (187.9 g, 1.73 mol), LiCl (3.30 g, 0.08 mol), AICl.sub.3 (4.61 g, 0.03 mol), CuCl (3.42 g, 0.03 mol) in THF (4 L). After 1 hour at room temperature, the resulting mixture was quenched with an aqueous solution of ammonium chloride at 10 C. and extracted with MTBE. The organic phase was washed with an aqueous solution of ammoniac then ammonium chloride, dried and evaporated to give after distillation (b.p.=150-155 C., P=0.25 mbar) 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-methyl-propan-1-one as yellowish oil (227.0 g, 52%). .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=1.20 (d, 6H); 3.20 (m, 1H); 7.0 (d, 2H); 7.10 (d, 1H); 7.34 (s, 1H); 7.38 (d, 2H); 7.41 (d, 1H).

[0703] Step 2:

[0704] DMSO (120 ml) was added to a mixture of sodium hydride (4.43 g, 175.24 mmol) in THF (130 ml) and cooled to about 5 C. Trimethylsulfonium iodide (34.97 g, 167.9 mmol) in DMSO (12 ml) was then added dropwise and the mixture was stirred at about 5 C. for a further hour. The intermediate 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-methyl-propan-1-one (25.0 g, 72.9 mmol) in DMSO (60 ml) was then added dropwise over a period of about five minutes. The mixture was then stirred overnight at room temperature, then quenched with saturated ammonium chloride solution and extracted three times with MTBE. The organic phases were combined, washed with an aqueous solution of ammonium chloride, filtrated and dried. Evaporation of the solvent gave after purification on silica gel 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-isopropyl-oxirane as a yellowish oil (24.2 g, 84%, HPLC-MS: R.sub.t=1.540 min; masse=356**(conditions B see below)).

[0705] Step 3:

[0706] To 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-isopropyl-oxirane (173.0 g, 0.41 mol) dissolved in N-methyl-2-pyrrolidon (1 L) was added sodium hydroxide (41.2 g, 1.03 mol) and triazole (145.2 g, 2.06 mol) at room temperature. The mixture was then stirred for 12 hours at 125 C. A solution of ammonium chloride and ice water was then added, the mixture extracted with MTBE and washed with an aqueous solution of lithium chloride. The crude residue was purified by recrystallization (Heptane/MTBE, 1:1) to give 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1,2,4-triazol-1-yl)butan-2-ol as a colorless solid (110 g, m.p.=114 C.; HPLC-MS R.sub.t=1.27 min; masse=426**(conditions B see below)).

Example 8

Preparation of 1-[2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-methoxy-3-methyl-butyl]-1,2,4-triazole (compound I-11)

[0707] To a solution of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1,2,4-triazol-1-yl)butan-2-ol (3.0 g, 6.69 mmol) in 15 mL of THF was added sodium hydride (0.24 g, 9.37 mmol) at room temperature. The reaction mixture was then stirred for 30 min followed by the addition of methyliodide (1.33 g, 9.37 mmol) and stirred at room temperature for 10 hours. After addition of an aq. solution of sodium chloride, the mixture was extracted with dichloromethane, dried, evaporated. The crude residue was purified by flash chromatography on silica gel to give the title compound as a yellowish oil (HPLC-MS R.sub.t=1.33 min; masse=440**(conditions B see below)).

Example 9

Preparation of 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2-(1,2,4-triazol-1-yl)ethanol (compound I-8)

[0708] Step 1:

[0709] To a solution of 1-bromo-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzene (70.0 g, 199 mmol, 1.0 eq.) in 700 mL of THF was added dropwise isopropyl magnesium chloride lithium chloride complex (199.1 mL, 1.3 M in THF) at room temperature and stirred for 2 hours. The reaction mixture was then added dropwise to a solution of cyclopropane carbonyl chloride (27.05 g, 258 mmol), LiCl (0.5 g, 11.9 mmol), AlCl.sub.3 (0.79 g, 5.9 mmol), CuCl (0.59 g, 5.9 mmol) in THF (700 mL). After 30 min at room temperature, the resulting mixture was quenched with an aqueous solution of ammonium chloride at 10 C. and extracted with MTBE. The organic phase was washed with an aqueous solution of ammoniac, dried and evaporated to give [4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-cyclopropyl-methanone as a brownish oil (66.8 g). .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=1.10 (m, 2H); 1.30 (m, 2H); 2.32 (m, 1H); 7.0 (d, 2H); 7.15 (d, 1H); 7.32 (s, 1H); 7.37 (d, 2H); 7.60 (d, 1H).

[0710] Step 2:

[0711] To a solution of sodium hydride (10.77 g, 448 mmol) in THF (750 mL) and dry DMSO (250 mL) was added under argon drop wise at 5 C. a solution of trimethylsulfonium iodide (87.62 g, 429 mmol) in dry DMSO (800 mL). The mixture was stirred 1 hour at 5 C. followed by a dropwise addition of [4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-cyclopropyl-methanone (66.5 g, 195 mmol) in DMSO (500 mL). The resulting mixture was then warmed to room temperature overnight and quenched with an aqueous solution of ammonium chloride and iced water, and then extracted with MTBE. The organic solvents were washed with water, dried and evaporated to give 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-cyclopropyl-oxirane as an oil (66.0 g). .sup.1H-NMR (CDCl.sub.3; 400 MHz) * * (ppm)=0.38-0.50 (m, 4H); 1.40 (m, 1H); 2.90-3.0 (dd, 2H); 6.90 (d, 2H); 7.15 (d, 1H); 7.29 (s, 1H); 7.35 (d, 2H); 7.50 (d, 1H).

[0712] Step 3:

[0713] To 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-2-cyclopropyl-oxirane (866.0 g, 186 mmol) dissolved in N-methyl-2-pyrrolidon (820 mL) was added sodium hydroxide (18.6 g, 465 mmol) and 1,2,4-triazole (64.2 g, 930 mmol) at room temperature. The mixture was then stirred for 12 hours at 125 C. A solution of ammonium chloride and ice water was then added, the mixture extracted with MTBE and washed with an aqueous solution of lithium chloride. The crude residue was purified by flash chromatography on silica gel to give 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2-(1,2,4-triazol-1-yl)ethanol as an oil (64.5 g, HPLC-MS Rt=1.24 min; masse=424**(conditions B see below)).

[0714] The compounds I listed in Table I and Table I continued have been prepared in an analogous manner.

TABLE-US-00005 TABLE I HPLC* ex.-no. R R.sup.1 R.sup.2 R.sup.3.sub.n R.sup.4.sub.m R.sub.t (min) m.p. ( C.) I-1 CF.sub.3 H H 4-Cl 3.086 I-2 CF.sub.3 CH.sub.3 H 4-Cl 3.196 121-122 I-3 CF.sub.3 CH.sub.2CH.sub.3 H 4-Cl 3.366 I-4 CF.sub.3 CH.sub.2CH.sub.2CH.sub.3 H 4-Cl 3.516 I-5 CF.sub.3 CCH H 4-Cl 3.166 I-6 CF.sub.3 CCCH.sub.3 H 4-Cl 3.248 when referring to R.sup.3.sub.n means that n is zero; when referring to R.sup.4.sub.m means that m is zero; m.p. = melting point. *(conditions A): HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50 mm 4.6 mm with Eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA)/water + 0.1% TFA (gradient from 5:95 to 95:5 in 5 min at 40 C., flow of 1.8 ml/min) HPLC** ex.-no. R R.sup.1 R.sup.2 R.sup.3.sub.n R.sup.4.sub.m R.sub.t (min) I-7 CF.sub.3 CH(CH.sub.3).sub.2 H 4-Cl 1.27 I-8 CF.sub.3 C.sub.3H.sub.5 (cyclopropyl) H 4-Cl 1.24 I-9 CF.sub.3 CH.sub.2CH.sub.3 CH.sub.3 4-Cl 1.32 I-10 CF.sub.3 CH.sub.3 CH.sub.3 4-Cl 1.26 I-11 CF.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 4-Cl 1.33 I-12 CF.sub.3 C.sub.3H.sub.5 (cyclopropyl) CH.sub.3 4-Cl 1.31 I-13 CF.sub.3 H H 2,4-Cl.sub.2 1.17 I-14 CF.sub.3 H CH.sub.3 4-Cl 1.25 I-15 CF.sub.3 CF.sub.3 H 4-Cl 1.23 I-16 CF.sub.3 CH.sub.3 H 4-F 1.08 I-17 CF.sub.3 CH.sub.3 CH.sub.2CH.sub.3 4-Cl 1.34 I-18 CF.sub.3 CH.sub.3 CH.sub.2CHCH.sub.2 4-Cl 1.36 I-19 CF.sub.3 CCCH.sub.3 CH.sub.2CH.sub.3 4-Cl 1.38 I-20 CF.sub.3 CCCH.sub.3 CH.sub.2CCH 4-Cl 1.32 when referring to R.sup.3.sub.n means that n is zero; when referring to R.sup.4.sub.m means that m is zero; m.p. = melting point. **(conditions B): HPLC methode Data for continued Table I: Mobile Phase: A: Water + 0.1% TFA, B: acetonitrile; Gradient: 5% B to 100% B in 1.5 min; Temperature: 60 C.; MS method: ESI positive; mass area (m/z): 10-700; Flow: 0.8 ml/min to 1.0 ml/min in 1.5 min; Column: Kinetex XB C18 1.7 50 2.1 mm; Aparatus: Shimadzu Nexera LC-30 LCMS-2020

II. EXAMPLES OF THE ACTION AGAINST HARMFUL FUNGI

[0715] The fungicidal action of the compounds of the formula I was demonstrated by the following experiments:

A) Greenhouse Tests

[0716] The active substances were formulated separately or together as a stock solution comprising 25 mg of active substance which was made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Wettol EM 31 (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. This solution was then made up to 100 ml using water. This stock solution was diluted with the solvent/emulsifier/water mixture described to the active substance concentration given below.

Use Example 1

Preventative Fungicidal Control of Early Blight on Tomatoes (Alternaria solani)

[0717] Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension containing the concentration of active ingredient mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then, the trial plants were immediately transferred to a humid chamber. After 5 days at 20 to 22 C. and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0718] In this test, the plants which had been treated with 150 ppm of the active substance from examples I-2 and I4, respectively, showed an infection of less than or equal to 15% whereas the untreated plants were 90% infected.

Use Example 2

Preventative Control of Grey Mold (Botrytis cinerea) on Leaves of Green Pepper

[0719] Young seedlings of green pepper were grown in pots to the 2 to 3 leaf stage. These plants were sprayed to run-off with an aqueous suspension containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the treated plants were inoculated with a spore suspension of Botrytis cinerea in a 2% aqueous biomalt solution. Then, the trial plants were immediately transferred to a dark, humid chamber. After 5 days at 22 to 24 C. and a relative humidity close to 100% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 150 ppm of the active substance from examples I-2, 1-3 and 14, respectively, showed an infection of less than or equal to 15% whereas the untreated plants were 90% infected.

Use Example 3

Preventative Control of Brown Rust on Wheat Caused by Puccinia recondita

[0720] The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension containing the concentration of active ingredient as described below. The next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 22 C. for 24 h. Then, the trial plants were cultivated for 6 days in a greenhouse chamber at 22-26 C. and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 150 ppm of the active substance from examples I-2, I-3 and I-4, respectively, showed an infection of less than or equal to 15% whereas the untreated plants were 90% infected.

Use Example 4

Preventative Control of Soy Bean Rust on Soy Beans Caused by Phakopsora pachyrhizi

[0721] Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension containing the concentration of active ingredient as described below. The plants were allowed to air-dry. The next day the plants were inoculated with spores of Phakopsora pachyrhizii. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 23 to 27 C. for 24 h. Thereafter the trial plants were cultivated for 14 days in a greenhouse chamber at 23-27 C. and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0722] In this test, the plants which had been treated with 150 ppm of the active substance from examples I-2, I-3 and I-4, respectively, showed an infection of less than or equal to 15% whereas the untreated plants were 90% infected.

Use Example 5

Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici

[0723] The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension containing the concentration of active ingredient as described below. The next day the plants were inoculated with a spore suspension in water of Septoria tritici. To ensure the success the artificial inoculation, the plants were transferred for 4 days to a humid chamber with a relative humidity of 95 to 99% and 20 to 24 C. Thereafter the plants were cultivated for 4 weeks at a relative humidity of 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0724] In this test, the plants which had been treated with 150 ppm of the active substance from examples I-2, I-3 and I-4, respectively, showed an infection of less than or equal to 15% whereas the untreated plants were 90% infected.

Use Example 6

Microtest

[0725] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

M1. Activity Against Rice Blast Pyricularia oryzae in the Microtiterplate Test (Pyrior)

[0726] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. Compounds I-3, I-4 and I-10 showed a growth of 4% or less at 2 ppm.

Green House:

[0727] The spray solutions were prepared in several steps:

[0728] The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

G1. Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P7)

[0729] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. Seven days later the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

G2. Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P1)

[0730] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. The next day the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

TABLE-US-00006 Growth (%) Disease (%) Compound at 0.5 ppm at 16 ppm Structure Pyrior Septtr P7 prior art J. Agric. Food Chem, Vol 57, No 11, 2009; 82 60 compound V18 [00065] according to the invention 68 10 compound I-2, Table I Untreated control 80 Disease(%) at Compound 150 ppm Septtr P1 prior art EP 0 275 955-compound V6 60 [00066] according to the invention 0 compound I-1, Table I Untreated control 80

Use Example 7

Microtest

[0731] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

M1: Activity Against Rice Blast Pyricularia oryzae in the Microtiterplate Test (Pyrior)

[0732] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

TABLE-US-00007 Growth (%) at Compound 0.5 ppm Pyrior prior art J. Agric. Food Chem, Vol 57, No 11, 2009; 82 compound V18 [00067] according to the invention 58 compound I-3, Table I according to the invention 19 compound I-4, Table I according to the invention 68 compound I-2, Table I Growth (%) at Compound 0.5 ppm Pyrior according to the invention 37 compound I-6, Table I according to the invention 47 compound I-1, Table I

Use Example 8

Green House

[0733] The Spray Solutions were Prepared in Several Steps:

[0734] The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

G1: Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P7)

[0735] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. Seven days later the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

TABLE-US-00008 Disease (%) at Compound 16 ppm Septtr P7 prior art J. Agric. Food Chem, Vol 57, No 11, 2009; 60 compound V19 [00068] according to the invention 25 compound I-4, Table I according to the invention 0 compound I-6, Table I according to the invention 2 compound I-1, Table I untreated control 80

Use Example 9

Green House

[0736] The Spray Solutions were Prepared in Several Steps:

[0737] The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

G1. Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P1)

[0738] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. The next day the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

TABLE-US-00009 Disease (%) at 150 pm Compound Septtr P1 prior art DE3801233 compound 2 30 [00069] according to the invention 0 compound I-14, Table I prior art J. Agric. Food Chem, Vol 57, No 11, 40 2009; compound V19 [00070] according to the invention 0 compound I-16, Table I Untreated control 90

Use Example 10

Microtest

[0739] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the described fungus in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

Fungus

[0740] M1. Activity against the grey mold Botrytis cinerea in the microtiterplate test (Botrci). Compounds I-13 and I-16 showed a growth of 2% or less at 32 ppm.

[0741] M2. Activity against rice blast Pyricularia oryzae in the microtiterplate test (Pyrior). Compounds I-13 and I-16 showed a growth of 2% or less at 32 ppm.

[0742] M3. Activity against leaf blotch on wheat caused by Septoria tritici (Septtr). Compounds I-13 and I-16 showed a growth of 6% or less at 32 ppm.

[0743] M4. Activity against early blight caused by Alternaria solani (Alteso). Compounds I-13 and I-16 showed a growth of 1% or less at 32 ppm.

[0744] M5. Activity against wheat leaf spots caused by Leptosphaeria nodorum (Leptno). Compounds I-13 and I-16 showed a growth of 1% or less at 32 ppm.

[0745] M6. Activity against net blotch Pyrenophora teres on barley in the microtiter test (Pyrnte). Compound 1-13 showed a growth of 1% at 32 ppm.

[0746] The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

Use Example 11

Green House

[0747] The Spray Solutions were Prepared in Several Steps:

[0748] The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

G1. Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P7)

[0749] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. Seven days later the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

G2. Curative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr K7)

[0750] Leaves of pot-grown wheat seedling were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. Seven days after inoculation the plants were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. Then the plants were transferred back to the chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

G3. Control of Powdery Mildew on Grape Caused by Uncinula necator (Uncine P3)

[0751] Grape cuttings were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. Three days later the treated plants were inoculated with spores of Uncinula necator by shaking heavily infestated stock plants over the treated pots. After cultivation in the greenhouse for 10 days at 21-23 C. and a relative humidity between 40 to 70% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

G4. Preventative Fungicidal Control of Early Blight on Tomatoes (Alternaria solani) (Alteso P7)

[0752] Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. Seven days later the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then the trial plants were immediately transferred to a humid chamber. After 5 days at 18 to 20 C. and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Comparison

[0753]

TABLE-US-00010 Growth Disease Disease Disease Disease Disease (%) at (%) at (%) at (%) at (%) at (%) at 0.125 16 ppm 16 ppm 16 ppm 63 ppm 16 ppm ppm Septtr Septtr Uncine Alteso Alteso Compound Botrci P7 K7 P3 P7 P7 prior art J. Agric. Food 67 60 Chem, Vol 57, No 11, 2009; compound V18 [00071] according to the invention 17 15 compound I-2, Table I prior art EP0275955 30 40 40 compound 6 [00072] according to the invention 3 0 3 compound I-1, Table I prior art DE3801233 90 80 compound 2 [00073] according to the invention 15 20 compound I-14, Table I Untreated control 90 90 100 100 90

Use Example 12

Green House

[0754] The Spray Solutions were Prepared in Several Steps:

[0755] The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

G1. Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa P1)

[0756] Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 1 day in a greenhouse chamber at 23-27 C. and a relative humidity between 60 and 80%. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24 C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27 C. and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 300 ppm of the active substance from examples I-9, I-12, I-17 and I-18, respectively, showed an infection of less than or equal to 1%, whereas the untreated plants were 80% infected.

G2. Preventative Control of Brown Rust on Wheat Caused by Puccinia recondita (Puccrt P1)

[0757] The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24 C. for 24 h. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 20-24 C. and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 300 ppm of the active substance from examples I-9, I-11, I-12, I-17, I-18, I-19 and I-20, respectively, showed an infection of less than or equal to 10% whereas the untreated plants were 80% infected.

G3. Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici (Septtr P1)

[0758] Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. At the following day the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18-22 C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18-22 C. and a relative humidity close to 70%. After 4 weeks the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 300 ppm of the active substance from examples I-9, I-11, I-12, I-17, I-18, I-19 and I-20, respectively, showed an infection of less than or equal to 7% whereas the untreated plants were 80% infected.

G4. Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper (Botrci P1)

[0759] Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with a aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24 C. and a relative humidity close to 100% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 300 ppm of the active substance from examples I-9, I-11 and I-18, respectively, showed an infection of less than or equal to 10% whereas the untreated plants were 90% infected.

G5. Preventative Fungicidal Control of Early Blight on Tomatoes (Alternaria Solani) (Alteso P1)

[0760] Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then the trial plants were immediately transferred to a humid chamber. After 5 days at 18 to 20 C. and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the plants which had been treated with 300 ppm of the active substance from examples I-12, I-17, I-18, I-19 and I-20, respectively, showed an infection of less than or equal to 10% whereas the untreated plants were 90% infected.