Substituted oxadiazoles for combating phytopathogenic fungi

Abstract

The present invention relates to novel trifluoromethyloxadiazoles of the formula I, or the N-oxides, or the agriculturally useful salts thereof; and to their use for controlling phytopathogenic fungi; and to a method for combating phytopathogenic harmful fungi, which process comprises treating the fungi, the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; and to agrochemical compositions comprising at least one compound of the formula I; and to agrochemical compositions further comprising seeds. ##STR00001##

Claims

1. A compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof; ##STR00013## wherein: R.sup.A is independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; n is 0, 1 or 2; L is —(C═S)—; R.sup.1 is C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy; wherein any of the aliphatic groups are unsubstituted or substituted with 1, 2, 3, 4, 5 or up to the maximum possible number of identical or different radicals selected from the group consisting of hydroxy, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy and C.sub.3-C.sub.8-cycloalkyl; 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.1-C.sub.6-alkoxy, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkyl, phenyl, C(═O)—(C.sub.1-C.sub.6-alkyl) or C(═O)—(C.sub.1-C.sub.6-alkoxy); and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, hydroxy, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy and C.sub.3-C.sub.8-cycloalkyl; R.sup.3, R.sup.4 independently of each other are selected from the group consisting of hydrogen, halogen, cyano, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkenyl, C.sub.1-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl and C.sub.1-C.sub.4-alkoxy; or R.sup.3 and R.sup.4 together with the carbon atom to which they are bound form a saturated 3- to 7-membered carbocycle or a saturated 3- to 6-membered heterocycle; wherein the saturated heterocycle includes beside carbon atoms 1, 2 or 3 heteroatoms independently selected from the group consisting of N, O and S as ring member atoms; and wherein said N ring member atom is substituted with the group R.sup.N; wherein R.sup.N is hydrogen, C.sub.1-C.sub.6-alkyl or halogen; and wherein said S ring member atom is unsubstituted or substituted with 1 or 2 oxo radicals; and wherein one or two CH.sub.2 groups of the saturated carbocycle or of the saturated heterocycle may be replaced by one or two groups independently selected from —C(═O)— and —C(═S)—; and wherein the carbon ring member atoms of the saturated carbocycle or of the saturated heterocycle are unsubstituted or substituted with a total number of 1, 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy and C.sub.3-C.sub.8-cycloalkyl; with the exception of compounds of the formula I wherein R.sup.3 and R.sup.4 both are hydrogen.

2. The compound of claim 1 having formula I.1, or an N-oxide, or an agriculturally acceptable salt thereof ##STR00014## wherein n is 0 or 1.

3. The compound of claim 1, wherein n is 0.

4. The compound of claim 1, wherein R.sup.3 and R.sup.4 are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl; or R.sup.3 and R.sup.4 together with the carbon atom to which they are bound form a cyclopropyl ring; with the exception of compounds of the formula I wherein R.sup.3 and R.sup.4 both are hydrogen.

5. The compound of claim 1, wherein R.sup.3 is hydrogen and R.sup.4 is methyl or trifluoromethyl.

6. The compound of claim 1, wherein R.sup.3 and R.sup.4 together with the carbon atom to which they are bound form a cyclopropyl ring.

7. The compound of claim 1, wherein R.sup.1 is C.sub.1-C.sub.6-alkyl; unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of C.sub.1-C.sub.6-alkoxy and C.sub.3-C.sub.8-cycloalkyl.

8. The compound of claim 1, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl or phenyl; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1, 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-alkoxy.

9. The compound of claim 1, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkenyl, ethynyl, propargyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl or phenyl; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1, 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen and C.sub.1-C.sub.6-alkyl; and R.sup.1 is C.sub.1-C.sub.6-alkyl.

10. An agrochemical composition, which comprises an auxiliary and at least one compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof, as defined in claim 1.

11. The agrochemical composition of claim 10, wherein the auxiliary is selected from the group of ionic or non-ionic surfactants.

12. Seed treated with the composition of claim 10, wherein the amount of the compound of the formula I, or an N-oxide, or an agriculturally acceptable salt thereof, is from 0.1 g to 10 kg per 100 kg of seed.

13. A method for combating phytopathogenic harmful fungi, which process comprises treating the fungi, the plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula I, or an N-oxide, or an agriculturally acceptable salt thereof, as defined in claim 1.

14. The method of claim 13, wherein the compound of formula I is a compound of formula I.1, or an N-oxide, or an agriculturally acceptable salt thereof ##STR00015## wherein n is 0 or 1.

15. The method of claim 13, wherein R.sup.3 and R.sup.4 are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl; or R.sup.3 and R.sup.4 together with the carbon atom to which they are bound form a cyclopropyl ring; with the exception of compounds of the formula I wherein R.sup.3 and R.sup.4 both are hydrogen.

16. The method of claim 13, wherein R.sup.3 is hydrogen and R.sup.4 is methyl or trifluoromethyl.

17. The method of claim 13, wherein R.sup.3 and R.sup.4 together with the carbon atom to which they are bound form a cyclopropyl ring.

18. The method of claim 13, wherein R.sup.1 is C.sub.1-C.sub.6-alkyl; unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different radicals selected from the group consisting of C.sub.1-C.sub.6-alkoxy and C.sub.3-C.sub.8-cycloalkyl.

19. The method of claim 13, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl or phenyl; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1, 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen, cyano, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-alkoxy.

20. The method of claim 13, wherein R.sup.2 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkenyl, ethynyl, propargyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl or phenyl; and wherein any of the aliphatic or cyclic groups are unsubstituted or substituted with 1, 2, 3, 4 or up to the maximum possible number of identical or different radicals selected from the group consisting of halogen and C.sub.1-C.sub.6-alkyl; and R.sup.1 is C.sub.1-C.sub.6-alkyl.

Description

I. SYNTHESIS EXAMPLES

(1) The compounds of the formula I can be prepared according to the methods outlined below.

I.1) Preparation of 4-(methylaminomethyl)benzonitrile

(2) To a solution of 4-(bromomethyl)benzonitrile (49 g, 1 eq.) in tetrahydrofurane (500 mL) methylamine (194 g of a 40% solution by weight, 10 eq.) was added. The mixture was stirred overnight at room temperature. After removing the solvent under reduced pressure, an aqueous solution of sodium chloride was added and the aqueous mixture was extracted with ethyl acetate. The combined organic layer was dried with magnesium sulfate and freed from solvent.

(3) The title compound (35.6 g) was used directly without further purification.

I.2) Preparation of N-[(4-cyanophenyl)methyl]-N-methyl-propanamide

(4) To a solution of 4-(methylaminomethyl)benzonitrile (4.5 g, 1 eq.) in tetrahydrufurane (50 mL) propionyl chloride (3.1 g, 1.1 eq.) was added. After stirring for one minute ethyl diisopropyl-amide (6 g, 1.5 eq.) was added and the mixture was stirred an additional one hour at room temperature. The title compound was used directly without further purification.

I.3) Preparation of N-[[4-[(Z)—N′-hydroxycarbamimidoyl]phenyl]methyl]-N-methyl propanamide

(5) A solution of N-[(4-cyanophenyl)methyl]-N-methyl-propanamide (6.2 g, 1 eq.), hydroxylamine hydrochloride (3.2 g, 1.5 eq.), potassium carbonate (2.8 g, 0.7 eq.), water (15 mL) and ethanol (30 mL) was stirred overnight at room temperature. The organic solvent was removed under reduced pressure, 40 mL toluol was added, stirred and removed again. The title compound was used directly without further purification.

I.4) Preparation of N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide

(6) To a solution of N-[[4-[(Z)—N′-hydroxycarbamimidoyl]phenyl]methyl]-N-methyl-propanamide (7.2 g, 1 eq.) in tetrahydrofurane (100 mL) and N,N-dimethylformamide (20 mL) gradually trifluoroacetic anhydride (12 mL) was added. The mixture was stirred at 50° C. until HPLC indicated complete conversion of the starting material. In case the conversion was not complete more trifluoroacetic anhydride was added. The solvent was removed under reduced pressure, water was added and the aqueous layer was extracted with etylacetate. The organic layer was poured into dichloromethane and washed with an aqueous solution of hydrochloric acid (1N solution) followed by an aqueous solution of sodium hydrogen carbonate. The organic layer was dried with magnesium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (cyclohexane: ethyl acetate) to afford the desired product as a colorless solid (5 g, 52%). Melting point: 30° C., LC/MS: Retention time (R.sub.t) 1.146 min, .sup.1H NMR (400 MHz, CDCl.sub.3): δ [ppm]=8.1 (2H), 7.4 (2H), 4.7 (2H), 3.0 (3H), 2.5 (2H), 1.2 (3H).

I.5) Preparation of N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanethioamide (Ex-7, Example not According to the Invention)

(7) To a solution of N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-propanamide (0.20 g, 1 eq.) in 3.7 mL toluene was added diphosphorus pentasulfide (156 mg, 1.1 eq.). The mixture was heated for 4 hours at 110° C. Water was added and the aqueous phase was extracted with ethyl acetate. The separated organic layer was washed with saturated sodium chloride solution and dried with magnesium sulfate. Then the solvent was removed under reduced pressure and the crude product was purified by column chromatography (cyclohexane, ethyl acetate) to afford the desired product as a colorless solid (152 mg, 69%). LC/MS: Retention time (R.sub.t) 1.298 min, .sup.1H NMR (500 MHz, CDCl.sub.3): δ [ppm]=8.05-8.18 (2H), 7.27 & 7.43 (2H), 5.45 & 4.95 (2H), 3.48 & 3.25 (3H), 2.89 (2H), 1.38 (3H).

I.6) Preparation of N′-hydroxy-4-(methylaminomethyl)benzamidine

(8) To a solution of 4-(methylaminomethyl)benzonitrile (61.4 g, 1 eq.) and trimethylamine (106 g, 2.5 eq.) in ethanol (500 mL) hydroxylamine hydrochloride (58.4 g, 2 eq.) was added. The mixture was heated overnight at 80° C. After cooling to room temperature, the solvent was removed under reduced pressure. The title compound was used directly without further purification.

I.7) Preparation of N-methyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine

(9) A solution of N′-hydroxy-4-(methylaminomethyl)benzamidine (25.5 g, 1 eq.) in dichloromethane (200 mL) was treated with trifluoroacetic anhydride (119 g, 4 eq.). The resulting mixture was stirred overnight at ambient temperature, before it was diluted with water and washed with dichloromethane. The combined organic layer was washed with an aqueous solution of sodium hydrogencarbonate, dried with magnesium sulfate and freed from solvent. The residue (dark oil) was used directly without further purification (42.4 g).

I.8) Preparation of N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]ethanesulfonamide (Ex-18, Example not According to the Invention)

(10) To a solution of N-methyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (400 mg, 1.0 eq.) in dichloromethane (2 mL) was added trimethylamine (377 mg, 2.4 eq.) and ethanesulfonyl chloride (240 mg, 1.2 eq.) dropwise. The mixture was stirred at room temperature until HPLC indicated complete conversion of the starting material. After washing with an aqueous solution of hydrochloric acid (1N) the organic layer was dried with magnesium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (cyclohexane:ethyl acetate) to afford the desired product as a colorless solid (130 mg, 24%). Melting point: 53° C., LC/MS: Retention time 1.163 min., .sup.1H NMR (400 MHz, CDCl.sub.3): δ [ppm]=8.1 (2H), 7.5 (2H), 4.4 (2H), 3.1 (2H), 2.8 (3H), 1.4 (3H).

I.9) Preparation of 4-[1-(methylamino)ethyl]benzonitrile

(11) To a solution of 4-(1-bromoethyl)benzonitrile (3.2 g, 1 eq.) in tetrahydrofurane (50 mL) methylamine (11.8 g of a 40% solution by weight, 10 eq.) was added. The mixture was stirred overnight at room temperature. After removing the solvent under reduced pressure, an aqueous solution of sodium chloride was added and the aqueous mixture was extracted with ethyl acetate. The combined organic layer was dried over magnesium sulfate and freed from solvent. The title compound (2.2 g) was used directly without further purification.

I.10) Preparation of N′-hydroxy-4-[1-(methylamino)ethyl]benzamidine

(12) A solution of 4-[1-(methylamino)ethyl]benzonitrile (2.2 g, 1 eq.), hydroxylamine hydrochloride (1.5 g, 2 eq.), triethylamine (2.8 g, 2.5 eq.) and ethanol (40 mL) was stirred overnight at room temperature. The organic solvent was removed under reduced pressure. The title compound (2.1 g) was used directly without further purification.

I.11) Preparation of N-methyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanamine

(13) A solution of N′-hydroxy-4-[1-(methylamino)ethyl]benzamidine (2.1 g, 1 eq.) in dichloromethane (30 mL) was treated with trifluoroacetic anhydride (8.1 g, 5 eq.). The resulting mixture was stirred overnight at ambient temperature, before it was diluted with water and washed with dichloromethane. The combined organic layer was washed with an aqueous solution of sodium hydrogencarbonate, dried with magnesium sulfate and freed from solvent. The residue (2.46 g) was used directly without further purification.

I.12) Preparation of N-methyl-N-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]propanamide

(14) To a solution of N-methyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanamine (0.35 g, 1 eq.) in dichloromethane (5 mL) and triethylamine (0.2 g, 2.2 eq.) gradually propionyl chloride (0.91 g, 1.1 eq.) was added. The mixture was stirred at room temperature until HPLC indicated complete conversion of the starting material. The solvent was removed under reduced pressure, water was added and the aqueous layer was extracted with ethyl acetate. The organic layer was poured into dichloromethane and washed with an aqueous solution of hydrochloric acid (1N solution) followed by an aqueous solution of sodium hydrogen carbonate. The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to afford the desired product as a colorless oil (0.23 g, 78%). LC/MS: Retention time (R.sub.t) 1.19 min, .sup.1H NMR (400 MHz, CDCl.sub.3): δ [ppm]=8.1 (2H), 7.4 (2H), 6.14 (1H), 2.7 (3H), 2.4 (2H), 1.6 (1H), 1.5 (2H) 1.2 (3H).

I.13) Preparation of N-methyl-N-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]propanethioamide (Ex-8)

(15) To a solution of N-methyl-N-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]-propanamide (0.20 g, 1 eq.) in 3.6 mL toluene was added diphosphorus pentasulfide (149 mg, 1.1 eq.). The mixture was heated for 4 hours at 110° C. Water was added and the aqueous phase was extracted with ethyl acetate. The separated organic layer was washed with saturated sodium chloride solution and dried with magnesium sulfate. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (cyclohexane, ethyl acetate) to afford the desired product as a colorless solid (167 mg, 95%). LC/MS: Retention time (R.sub.t) 1.35 min, .sup.1H NMR (500 MHz, CDCl.sub.3): δ [ppm]=8.18 (d, 2H), 7.49 (d, 2H), 7.46 (q, 1H), 2.80-3.21 (5H), 1.31-1.78 (6H).

I.14) Preparation of N-[1-(4-cyanophenyl)ethyl]methanesulfonamide

(16) To a solution of 4-(1-aminoethyl)benzonitrile (400 mg, 1.0 eq.) in ethanol (5 mL) was added trimethylamine (553 mg, 2 eq.) and methanesulfonyl chloride (313 mg, 1 eq.) dropwise. The mixture was stirred at room temperature until HPLC indicated complete conversion of the starting material. After washing with an aqueous solution of hydrochloric acid (1N) the organic layer was dried with magnesium sulfate and the solvent was removed under reduced pressure. The title compound (0.61 g) was used directly without further purification.

I.15) Preparation of N′-hydroxy-4-[1-(methanesulfonamido)ethyl]benzamidine

(17) A solution of N-[1-(4-cyanophenyl)ethyl]methanesulfonamide (0.40 g, 1 eq.), hydroxylamine hydrochloride (0.25 g, 2 eq.), triethylamine (0.36 g, 2 eq.) and ethanol (5 mL) was stirred overnight at room temperature. The organic solvent was removed under reduced pressure. The title compound (0.46 g) was used directly without further purification.

I.16) Preparation of N-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]methanesulfonamide (Ex-30)

(18) A solution of N′-hydroxy-4-[1-(methanesulfonamido)ethyl]benzamidine (450 mg, 1.0 eq.) in methylene chloride (10 mL) was treated with trifluoroacetic anhydride (1.1 g, eq.). The resulting mixture was stirred overnight at ambient temperature, before it was diluted with water and washed with dichloromethane. The combined organic layer was washed with an aqueous solution of sodium hydrogencarbonate, dried with magnesium sulfate and freed from solvent. The and the crude product was purified by column chromatography (0.10 g, 16%) to afford the desired product. L/MS: Retention time 1.09 min., .sup.1H NMR (400 MHz, CDCl.sub.3): δ [ppm]=8.15 (d, 2H), 7.51 (d, 2H), 4.75 (q, 1H),4.64 (s, 1H), 2.75 (s, 3H), 1.56 (d, 3H).

(19) Compounds Ex-1 to Ex-47 in Table I were prepared in analogy to the procedures described above.

(20) TABLE-US-00002 TABLE I Compounds Ex-1 to Ex-47 of formula I.Ex, wherein the meaning of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and L is as defined in each line. Melting HPLC R.sub.t point Ex. no R.sup.1 R.sup.2 R.sup.3/R.sup.4 L (min)** (° C.) Ex-1 CH.sub.3 CH.sub.3 H/CH.sub.3 —C(═S)— 1.28 62 Ex-2 iso-propyl CH.sub.3 H/CH.sub.3 —C(═S)— 1.42 77  Ex-3* ethyl iso-propyl H/H —C(═S)— 1.38 — Ex-4 propyl CH.sub.3 H/CH.sub.3 —C(═S)— 1.41 —  Ex-5* propyl CH.sub.3 H/H —C(═S)— 1.36 —  Ex-6* 2-butyl CH.sub.3 H/H —C(═S)— 1.42 —  Ex-7* ethyl CH.sub.3 H/H —C(═S)— 1.30 63 Ex-8 ethyl CH.sub.3 H/CH.sub.3 —C(═S)— 1.35 —  Ex-9* tert-butyl iso-propyl H/H —C(═S)— 1.49 — Ex-10* iso-propyl CH.sub.3 H/H —C(═S)— 1.33 73 Ex-11* 3-pentyl CH.sub.3 H/H —C(═S)— 1.47 71 Ex-12* CH.sub.3 allyl H/H —C(═S)— 1.32 — Ex-13* CH.sub.3 CH.sub.3 H/H —C(═S)— 1.22 86 Ex-14* CH.sub.3 iso-propyl H/H —SO.sub.2— 1.22 — Ex-15* propyl iso-propyl H/H —SO.sub.2— 1.34 — Ex-16* ethyl iso-propyl H/H —SO.sub.2— 1.29 — Ex-17* CH.sub.3 CH.sub.3 H/H —SO.sub.2— 1.11 — Ex-18* ethyl CH.sub.3 H/H —SO.sub.2— 1.16 53 Ex-19* propyl CH.sub.3 H/H —SO.sub.2— 1.25 91 Ex-20* propyl ethyl H/H —SO.sub.2— 1.27 83-88 Ex-21* CH.sub.3 ethyl H/H —SO.sub.2— 1.17 64-67 Ex-22* iso-propyl CH.sub.3 H/H —SO.sub.2— 1.22 124-129 Ex-23* ethyl ethyl H/H —SO.sub.2— 1.22 96 Ex-24* iso-propyl iso-propyl H/H —SO.sub.2— 0.98 137 Ex-25* CH.sub.3 3-pentyl H/H —SO.sub.2— 1.32 — Ex-26* CH.sub.3 cyclopropyl H/H —SO.sub.2— 1.18 88-89 Ex-27* ethyl cyclopropyl H/H —SO.sub.2— 1.22 87 Ex-28* propyl cyclopropyl H/H —SO.sub.2— 1.28 89 Ex-29* 2-butyl CH.sub.3 H/H —SO.sub.2— 1.30 88 Ex-30  CH.sub.3 H H/CH.sub.3 —SO.sub.2— 1.09 — Ex-31  ethyl H H/CH.sub.3 —SO.sub.2— 1.13 — Ex-32  3-pentyl H H/CH.sub.3 —SO.sub.2— 1.29 — Ex-33* 2,2,2- CH.sub.3 H/H —SO.sub.2— 1.27 113-115 trifluoroethyl Ex-34* 2,2- CH.sub.3 H/H —SO.sub.2— 1.26 93 difluoropropyl Ex-35* 2,2,2- CH.sub.3 H/H —SO.sub.2— 1.29 110 trifluoro-1- methyl-ethyl Ex-36* 2,2- CH.sub.3 H/H —SO.sub.2— 1.23 92 difluoroethyl Ex-37* 2,2,2- ethyl H/H —SO.sub.2— 1.30 97 trifluoroethyl Ex-38* 2,2,2- ethyl H/H —SO.sub.2— 1.32 110 trifluoro-1- methyl-ethyl Ex-39* 2,2- ethyl H/H —SO.sub.2— 1.26 76 difluoroethyl Ex-40* 2,2- ethyl H/H —SO.sub.2— 1.30 88 difluoropropyl Ex-41* 2,2,2- cyclopropyl H/H —SO.sub.2— 1.32 108 trifluoroethyl Ex-42* 2,2,2- cyclopropyl H/H —SO.sub.2— 1.34 83 trifluoro-1- methyl-ethyl Ex-43* 2,2- cyclopropyl H/H —SO.sub.2— 1.25 62 difluoroethyl Ex-44* 2,2- cyclopropyl H/H —SO.sub.2— 1.28 90 difluoropropyl Ex-45* 2,2,2- CH.sub.3 H/CH.sub.3 —SO.sub.2— 1.27 124 trifluoroethyl Ex-46* 2,2- CH.sub.3 H/CH.sub.3 —SO.sub.2— 1.26 96 difluoroethyl Ex-47* 2,2,2- allyl H/H —SO.sub.2— 1.33 73 trifluoroethyl *compound not according to the invention **HPLC: High Performance Liquid Chromatography; HPLC-column Kinetex XB C18 1.7μ (50 × 2.1 mm); eluent: acetonitrile/water + 0.1% trifluoroacetic acid (gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray Ionisation, 80 V (positive mode). R.sub.t: retention time in minutes.

II. BIOLOGICAL EXAMPLES FOR FUNGICIDAL ACTIVITY

(21) The fungicidal action of the compounds of formula I was demonstrated by the following experiments: The spray solutions were prepared in several steps: The stock solution were prepared by mixing 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. This mixture 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.

II.1) Curative Control of Soy Bean Rust on Soy Beans Caused by Phakopsora pachyrhizi

(22) Leaves of pot-grown soy bean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure the success of 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 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23 to 27° C. and a relative humidity between 60 and 80%. Then the plants 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. Then the trial plants were cultivated for 14 days in a greenhouse chamber at 23 to 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.

(23) In this test, the plants which had been treated with 32 ppm of the active compounds Ex-1, Ex-2, Ex-3, Ex-4, Ex-5, Ex-6, Ex-7, Ex-10, Ex-11, Ex-12 and Ex-13 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 90% diseased leaf area.

(24) In this test, the plants which had been treated with 32 ppm of the active compounds Ex-14, Ex-16, Ex-17, Ex-18 and Ex-19 showed a diseased leaf area of at most 2%, whereas the untreated plants showed 100% diseased leaf area.

(25) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-20, Ex-21, Ex-22, Ex-23, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-35, Ex-36, Ex-37, Ex-39, Ex-40, Ex-41, Ex-43, Ex-44 and Ex-46 showed a diseased leaf area of at most 16%, whereas the untreated plants showed 90% diseased leaf area.

II.2) Protective Control of Soy Bean Rust on Soy Beans Caused by Phakopsora pachyrhizi

(26) 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 2 day in a greenhouse chamber at 23 to 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 hours. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23 to 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.

(27) In this test, the plants which had been treated with 32 ppm of the active compounds Ex-1, Ex-2, Ex-3, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-10, Ex-11, Ex-12, Ex-13 Ex-14, Ex-15, Ex-16, Ex-17, Ex-18 and Ex-19 showed a diseased leaf area of at most 5%, whereas the untreated plants showed 100% diseased leaf area.

(28) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-20, Ex-21, Ex-22, Ex-23, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-43, Ex-44, Ex-45 and Ex-46 showed a diseased leaf area of at most 7%, whereas the untreated plants showed 90% diseased leaf area.

II.3) Curative Control of Brown Rust on Wheat Caused by Puccinia recondita

(29) The first two developed leaves of pot-grown wheat seedling were dusted 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 hours. The next day the plants were cultivated for 3 days in a greenhouse chamber at 20 to 24° C. and a relative humidity between 65 and 70%. Then the plants 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. Then the trial plants were cultivated for 8 days in a greenhouse chamber at 20 to 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.

(30) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-1, Ex-2, Ex-3, Ex-5, Ex-6, Ex-7, Ex-8, Ex-10, Ex-11, Ex-13, Ex-14, Ex-17 and Ex-18 showed a diseased leaf area of at most 15%, whereas the untreated plants showed 90% diseased leaf area.

(31) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-21, Ex-22, Ex-23, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-36 and Ex-39 showed a diseased leaf area of at most 9%, whereas the untreated plants showed 90% diseased leaf area.

II.4) Preventative Control of Brown Rust on Wheat Caused by Puccinia recondita

(32) 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 hours. 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.

(33) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-14, Ex-16, Ex-17, Ex-18 and Ex-19 showed a diseased leaf area of at most 5%, whereas the untreated plants showed 80% diseased leaf area.

(34) In this test, the plants which had been treated with 63 ppm of the active compounds Ex-20, Ex-21, Ex-22, Ex-23, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-36, Ex-37, Ex-39, Ex-40 and Ex-43 showed a diseased leaf area of at most 15%, whereas the untreated plants showed 90% diseased leaf area.