STROBILURIN TYPE COMPOUNDS AND THEIR USE FOR COMBATING PHYTOPATHOGENIC FUNGI

Abstract

The present invention relates to the use of strobilurin type compounds of formula (I) and the N-oxides and the salts thereof for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein (also referred to as F129L mutation in the mitochondrial cytochrome b gene) conferring resistance to Qo inhibitors, and to methods for combating such fungi. The invention also relates to novel compounds, processes for preparing these compounds, to compositions comprising at least one such compound, and to seeds coated with at least one such compound.

Claims

1. A compound of formula I ##STR00064## wherein R.sup.1 is selected from O and NH; R.sup.2 is selected from CH and N; R.sup.3 is selected from halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, —O—C.sub.1-C.sub.4-alkyl, —O—C.sub.1-C.sub.4-haloalkyl, —O—C.sub.3-C.sub.6-cycloalkyl, —C.sub.1-C.sub.2-alkyl-C.sub.3-C.sub.6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, provided that such heterocycloalkyl and heteroaryl cannot contain 2 contiguous atoms selected from O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound directly or via an oxygen atom or via a C.sub.1-C.sub.2-alkylene linker, and wherein said phenyl and heteroaryl are unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from halogen, CN, NH.sub.2, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, —O—C.sub.1-C.sub.4-alkyl and —O—C.sub.1-C.sub.4-haloalkyl; R.sup.a is selected from halogen, CN, —NR.sup.5R.sup.6, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, —O—C.sub.1-C.sub.4-alkyl, —C(═N—O—C.sub.1-C.sub.4-alkyl)-C.sub.1-C.sub.4-alkyl, —C(═O)—C.sub.1-C.sub.4-alkyl, —O—CH.sub.2-C(═N—O—C.sub.1-C.sub.4-alkyl)-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, —C.sub.1-C.sub.2-alkyl-C.sub.3-C.sub.6-cycloalkyl, —O—C.sub.3-C.sub.6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, provided that such heterocycloalkyl, heterocycloalkenyl and heteroaryl cannot contain 2 contiguous atoms selected from O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C.sub.1-C.sub.2-alkylene linker, and wherein the aliphatic and cyclic moieties of R.sup.a are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups R.sup.b: R.sup.b is selected from halogen, CN, NH.sub.2, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, —O—C.sub.1-C.sub.4-alkyl and —O—C.sub.1-C.sub.4-haloalkyl; R.sup.5, R.sup.6 are independently of each other selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl and C.sub.2-C.sub.4-alkynyl; n is an integer selected from 0, 1, 2, 3, 4 and 5; and in form of stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

2. The compound according to claim 1, wherein in R.sup.1 is selected from O and NH; and R.sup.2 is selected from CH and N, provided that R.sup.2 is N in case R.sup.1 is NH.

3. The compound according to claim 2, wherein R.sup.2 is N.

4. The compound according to claim 1, wherein R.sup.3 is selected from CN, halogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.3-C.sub.4-cycloalkyl, —O—C.sub.1-C.sub.2-alkyl and —O—C.sub.1-C.sub.2-halalkyl.

5. The compound according to claim 4, wherein R.sup.3 is selected from the group consisting of halogen, C.sub.1-C.sub.2-alkyl, and C.sub.1-C.sub.2-haloalkyl.

6. The compound according to claim 1, wherein n is 0, 1 or 2.

7. The compound according to claim 1, wherein R.sup.a is selected from the group consisting of C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.3-alkenyl, C.sub.2-C.sub.3-alkynyl, —O—C.sub.1-C.sub.3-alkyl, —C(═N—O—C.sub.1-C.sub.2-alkyl)-C.sub.1-C.sub.2-alkyl, —O—CH.sub.2—C(═N—O—C.sub.1-C.sub.2-alkyl)-C.sub.1-C.sub.2-alkyl, C.sub.3-C.sub.4-cycloalkyl, —C.sub.1-C.sub.2-alkyl-C.sub.3-C.sub.4-cycloalkyl, —O—C.sub.3-C.sub.4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, provided that such heterocycloalkyl and heteroaryl cannot contain 2 contiguous atoms selected from O and S, wherein said phenyl and heteroaryl are bound directly or via an oxygen atom or via a methylene linker, and wherein the aliphatic and cyclic moieties of R.sup.a are unsubstituted or carry 1, 2 or 3 of identical or different groups R.sup.b which independently of one another are selected from halogen, CN, methyl and C.sub.1-haloalkyl.

8. An agrochemical composition comprising an auxiliary and at least one compound of formula I as defined in claim 1 or in the form of a stereoisomer and tautomer thereof or an agriculturally acceptable salt or N-oxide thereof.

9. (canceled)

10. (canceled)

11. (canceled)

12. A method for combating phytopathogenic fungi comprising: treating curatively and/or preventively a plant or plant propagation material of said plant that is at risk of being diseased from the said phytopathogenic fungi, and/or applying to the said phytopathogenic fungi, at least one compound of formula I as defined in claim 1.

13. The method according to claim 12, wherein the phytopathogenic fungi contain an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

14. The method according to claim 12, wherein the phytopathogenic fungi are selected from Phakopsora pachyrhizi and P. meibomiae.

Description

EXAMPLES

Synthetic Process

Example 33: Methyl (2E)-2-[2-[[(E)-[4-fluoro-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

Step 1: (1E)-4-fluoro-2-(trifluoromethyl)benzaldehyde oxime

[0160] ##STR00015##

[0161] To a solution of 4-fluoro-2-(trifluoromethyl)benzaldehyde (1 g, 5.2 mmol) in MeOH/H.sub.2O (10 mL/2 mL), hydroxylamine hydrochloride (729 mg, 10.42 mmol), NaOH aq. (4N in water, 3.25 mL, 13 mmol) were added under N.sub.2. The mixture was stirred for 4 h at 80° C. under N.sub.2. Thin layer chromatography (TLC) (petroleum Ether (PE):ethyl acetate (EtOAc)=5:1) showed the reaction was completed. The reaction mixture was concentrated, then dissolved in EtOAc (10 mL) and H.sub.2O (10 mL). The aqueous phase was extracted with EtOAc (2×8 mL), washed with brine (20 mL), dried over Na.sub.2SO.sub.4 and concentrated to give (1E)-4-fluoro-2-(trifluoromethyl) benzaldehyde oxime (450 mg, 42.05%) as white solid.

[0162] .sup.1H NMR (400 MHz, CHCl.sub.3-d): δ 8.45 (d, J=2.0 Hz, 1H), 8.04 (dd, J=5.5, 8.8 Hz, 1H), 7.46 (s, 1H), 7.41 (dd, J=2.5, 8.8 Hz, 1H), 7.30 (br d, J=2.5 Hz, 1H).

Step 2: Methyl (2E)-2-[2-[[(E)-[4-fluoro-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

[0163] ##STR00016##

[0164] To a solution of (1E)-4-fluoro-2-(trifluoromethyl)benzaldehyde oxime (450 mg, 2.17 mmol) in DMF (6 mL), methyl (2E)-2[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (652 mg, 2.17 mmol) and CS.sub.2CO.sub.3 (1.172 g, 5.43 mmol) were added. The mixture was stirred for 5 h at about 15° C. TLC (PE:EtOAc=5:1) showed the reaction was completed. The mixture was quenched with H.sub.2O (15 mL), extracted with EtOAc (2×20 mL), and the organic phase was washed with brine (50 mL), dried over Na.sub.2SO.sub.4, concentrated and purified by Prep-HPLC to give the title compound (520 mg, 56.16%) as yellow solid. .sup.1H NMR (400 MHz, CHCl.sub.3-d) δ 8.30 (q, J=2.0 Hz, 1H), 8.03 (dd, J=5.5, 8.8 Hz, 1H), 7.38-7.29 (m, 3H), 7.27-7.21 (m, 1H), 7.04 (dd, J=1.3, 7.2 Hz, 1H), 5.13 (br s, 2H), 4.03-4.03 (m, 3H), 3.83-3.82 (m, 3H), 2.49 (s, 3H).

Example 34: (2E)-2-[2-[[(E)-[4-fluoro-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0165] ##STR00017##

[0166] To a solution of methyl (2E)-2-[2-[[(E)-[4-fluoro-2-(trifluoromethyl)phenyl]methyleneamino]-oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (310 mg, 0.728 mmol) in THF (4 mL), MeNH.sub.2 (282 mg, 3.638 mmol) was added and the mixture was stirred for 16 h at about 15° C. TLC (PE:EtOAc=5:1) showed that the reaction was completed. The mixture was quenched with H.sub.2O (10 mL), extracted with EtOAc (3×15 mL), the organic phase was washed with brine (50 mL), dried over Na.sub.2SO.sub.4 and concentrated to give the title compound (305 mg, 98.7%) as yellow solid.

[0167] .sup.1H NMR (400 MHz, CHCl.sub.3-d) δ 8.31 (br d, J=2.0 Hz, 1H), 8.04 (dd, J=5.6, 8.7 Hz, 1H), 7.39-7.27 (m, 3H), 7.26-7.21 (m, 1H), 7.04 (d, J=7.3 Hz, 1H), 6.75 (br d, J=4.1 Hz, 1H), 5.12 (s, 2H), 3.94 (s, 3H), 2.90 (d, J=5.0 Hz, 3H), 2.48 (s, 3H).

Example 35: Methyl (2E)-2-[2-[[(E)-[4-bromo-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

Step 1: (1E)-4-bromo-2-(trifluoromethyl)benzaldehyde oxime

[0168] ##STR00018##

[0169] To a solution of 4-bromo-2-(trifluoromethyl)benzaldehyde (1 g, 3.968 mmol) in THF (10 mL); HONH.sub.2.Math.HCl (556 mg, 7.937 mmol) and NaOH aq. (4N in water, 2.5 mL, 9.92 mmol) were added. The mixture was stirred for 4 h at about 80° C. under N.sub.2. TLC (PE:EtOAc=5:1) showed that the reaction was completed. The reaction mixture was quenched with H.sub.2O 15 mL), extracted with EtOAc (2×10 mL). The organic phase was washed with brine (25 mL), dried over Na.sub.2SO.sub.4 and concentrated to give (1E)-4-bromo-2-(trifluoromethyl)benzaldehyde oxime (1 g, 94.34%) as white solid. .sup.1H NMR: (400 MHz, CHCl.sub.3-d) δ 8.44 (br d, J=1.9 Hz, 1H), 7.90 (d, J=8.5 Hz, 1H), 7.84 (d, J=1.4 Hz, 1H), 7.73-7.66 (m, 2H).

Step 2: Methyl (2E)-2-[2-[[(E)-[4-bromo-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

[0170] ##STR00019##

[0171] To a solution of (1E)-4-bromo-2-(trifluoromethyl)benzaldehyde oxime (1.18 g, 4.42 mmol) in DMF (15 mL), methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (1.32 g, 4.42 mmol) and Cs.sub.2CO.sub.3 (3.6 g, 11.08 mmol) were added. The mixture was stirred for 4 h at about 20° C. TLC (PE: EtOAc=4:1) showed that the reaction was completed. The reaction mixture was quenched with H.sub.2O (25 mL), extracted with EtOAc (2×20 mL). The organic phase was washed with brine (15 mL), dried over Na.sub.2SO.sub.4, concentrated and purified by silica gel column (PE: EtOAc=100:0 to 80:20) to give the title compound (1.98 g, yield: 92.1%) as a white solid. .sup.1H NMR (CDCl.sub.3 Varian_D_400 MHz): δ 8.28 (d, J=2.19 Hz, 1 H) 7.90 (d, J=8.55 Hz, 1 H) 7.79 (d, J=1.97 Hz, 1 H) 7.66 (dd, J=8.44, 2.08 Hz, 1 H) 7.31-7.36 (m, 1 H) 7.27-7.31 (m, 1 H) 7.03 (dd, J=7.34, 1.21 Hz, 1 H) 5.13 (br s, 2 H) 4.03 (s, 3 H) 3.82 (s, 3 H) 2.49 (s, 3 H).

Example 36: (2E)-2-[2-[[(E)-[4-bromo-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0172] ##STR00020##

[0173] To a solution of methyl (2E)-2-[2-[[(E)-[4-bromo-2-(trifluoromethyl)phenyl]methyleneamino]-oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (360 mg, 0.74 mmol) in THF (5 mL), MeNH.sub.2 (239 mg, 3.2 mmol) was added. The mixture was stirred for 16 h at about 20° C. TLC (PE: EtOAc=1:1) showed that the reaction was completed. The reaction mixture was quenched with NHCl.sub.4 aq. (15 mL) and extracted with EtOAc (15×2 mL). The organic phase was washed with brine (15 mL), dried over Na.sub.2SO.sub.4 and concentrated to give the title compound (566 mg, yield: 94.3%) as white solid. .sup.1H NMR (CDCl.sub.3 Bruker_J_400 MHz): δ 8.29 (d, J=1.88 Hz, 1 H) 7.91 (d, J=8.50 Hz, 1 H) 7.79 (d, J=1.50 Hz, 1 H) 7.66 (br d, J=8.50 Hz, 1 H) 7.27-7.37 (m, 2 H) 7.03 (d, J=7.25 Hz, 1 H) 6.74 (br d, J=4.13 Hz, 1 H) 5.13 (s, 2 H) 3.94 (s, 3 H) 2.90 (d, J=5.00 Hz, 3 H) 2.48 (s, 3 H).

Example 37: Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-[4-methyl-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]phenyl]acetate

[0174] ##STR00021##

[0175] To a solution of methyl (2E)-2-[2-[[(E)-[4-bromo-2-(trifluoromethyl)phenyl]methyleneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (1.24 g, 2.55 mmol) in dioxane (25 mL) under Nitrogen, methyl boronic acid (740 mg, 12.75 mmol), K.sub.2CO.sub.3 (880 mg, 6.38 mmol) and Pd (PPh.sub.3).sub.4 (143 mg, 0.13 mmol) were added. The reaction mixture was stirred for 6 hat about 100° C. TLC (PE:EtOAc=3:1) showed that the reaction was completed. The reaction mixture was quenched with H.sub.2O (30 mL) and extracted with EtOAc (2×20 mL). The organic phase was washed with brine (20 mL), dried over Na.sub.2SO.sub.4, concentrated and purified by silica gel column (PE:EtOAc=100:0 to 85:15) to give the title compound (0.8 g, yield: 74.3%) as white solid. .sup.1H NMR (CDCl.sub.3 Varian_D_400 MHz):δ 8.33 (d, J=2.19 Hz, 1 H) 7.91 (d, J=7.89 Hz, 1 H) 7.45 (s, 1 H) 7.27-7.36 (m, 3 H) 7.03 (dd, J=7.34, 1.43 Hz, 1 H) 5.12 (s, 2 H) 4.03 (s, 3 H) 3.82 (s, 3 H) 2.50 (s, 3 H) 2.41 (s, 3 H).

Example 38: (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-[4-methyl-2-(trifluoromethyl)-phenyl]methyleneamino]oxymethyl]phenyl]acetamide

[0176] ##STR00022##

[0177] To a solution of methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-[4-methyl-2-(trifluoromethyl)-phenyl]methyleneamino]oxymethyl]phenyl]acetate (400 mg, 0.95 mmol) in THF (3 mL), MeNH.sub.2 (˜33% in water, 368 mg, 4.8 mmol) was added. The mixture was stirred for 16 h at about 20° C. TLC (PE:EtOAc=5:1) showed that the reaction was completed. The mixture was quenched with NHCl.sub.4 aq (15 mL) and extracted with EtOAc (2×10 mL). The organic phase was washed with brine (10 mL), dried over Na.sub.2SO.sub.4 and concentrated to give the title compound (280 mg, yield: 70%) as yellow solid. .sup.1H NMR (CDCl.sub.3 Bruker_K_400 MHz):δ 8.34 (d, J=2.13 Hz, 1 H) 7.90 (d, J=8.00 Hz, 1 H) 7.45 (s, 1 H) 7.29-7.36 (m, 2 H) 7.27 (s, 1 H) 7.00-7.08 (m, 1 H) 6.72 (br d, J=4.25 Hz, 1 H) 5.13 (s, 2 H) 3.94 (s, 3 H) 2.89 (d, J=5.00 Hz, 3 H) 2.48 (s, 3 H) 2.41 (s, 3 H).

[0178] The following examples in Table S1 and S2 were synthesized as described above and characterized by LCMS as described in Table L or by .sup.1H-NMR.

TABLE-US-00004 TABLE L LCMS Methods LCMS Method A LCMS Method B Column: Agilent Eclipse Plus C18 Column: Kinetex XB C18 (50 mm × 4.6 mm × 3 μ) (50 mm × 2.1 mm × 1.7 μ) Mobile Phase: Mobile Phase: A: 10 mM Ammonium formate in water. A: Water + 0.1% TFA. B: 0.1% Formic acid in acetonitrile B: Acetonitrile Gradient: 10% B to 100% B in 1.5 Gradient: 5% B to 100% B in min. Hold 1 min 100% B. 1 min 10% B. 1.5 min. Run time: 3.50 or 3.75 min. Flow: 0.8 ml/min to 1.0 Flow: 1.2 ml/min; ml/min in 1.5 min; Column oven: 30° C./40° C. Column oven: 60° C. Device details for LCMS Method A and B LCMS2020 (Shimadzu), Ionization source: ESI; Mass range: 100-800 amu; Polarity: Dual (positive and negative simultaneous scan); Mode: Scan; LC System: Nexera High pressure gradient system, Binary pump; Detector: PDA; Scanning wavelength: 220 nm/max plot

TABLE-US-00005 TABLE S1 LCMS Compound R.sub.t No. Structure [min] Mass Meth.  1 [00023] 1.254 341 B  2 [00024] 1.158 340 B  3 [00025] 2.08 408 A  4 [00026] 2.176 375 A  5 [00027] 2.17 409 A  6 [00028] 2.059 408 A  7 [00029] 2.187 375 A  8 [00030] 2.229 467 A  9 [00031] 2.101 466 A 10 [00032] 2.208 421 A 11 [00033] 2.112 359 A 12 [00034] 2.176 375 A 13 [00035] 2.048 374 A 14 [00036] 2.165 409 A 15 [00037] 2.048 374 A 16 [00038] 2.187 425 A 17 [00039] 2.091 424 A 18 [00040] 2.069 408 A 19 [00041] 2.272 443 A 20 [00042] 2.187 425 A 21 [00043] 2.165 442 A 22 [00044] 2.283 443 A 23 [00045] 2.197 442 A 24 [00046] 2.08 424 A 25 [00047] 2.16 443 A 26 [00048] 2.05 442 A 27 [00049] 2.13 355 A 28 [00050] 2.01 354 A

TABLE-US-00006 TABLE S2 No. Structure .sup.1H NMR (400 MHz, CHCl.sub.3-d) [δ] 29 [00051] 8.29 (d, J = 1.9 Hz, 1H), 7.98 (d, J = 8.5 Hz, 1H), 7.64 (d, J = 1.8 Hz, 1H), 7.52-7.48 (m, 1H), 7.32 (td, J = 7.2, 14.2 Hz, 2H), 7.04 (d, J = 7.3 Hz, 1H), 5.13 (s, 2H), 4.03 (s, 3H), 3.82 (s, 3H), 2.49 (s, 3H) 30 [00052] 8.30 (d, J = 1.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.63 (d, J = 1.3 Hz, 1H), 7.50 (br d, J = 8.4 Hz, 1H), 7.34-7.27 (m, 2H), 7.03 (d, J = 7.2 Hz, 1H), 6.74 (br d, J = 4.4 Hz, 1H), 5.13 (s, 2H), 3.94 (s, 3H), 2.90 (d, J = 4.9 Hz, 3H), 2.48 (s, 3H) 31 [00053] 8.36 (d, J = 1.6 Hz, 1H), 8.18 (d, J = 8.3 Hz, 1H), 7.91 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.37-7.29 (m, 2H), 7.04 (d, J = 7.3 Hz, 1H), 5.17 (s, 2H), 4.04 (s, 3H), 3.83 (s, 3H), 2.50 (s, 3H) 32 [00054] 8.36 (d, J = 2.0 Hz, 1H), 8.18 (d, J = 8.3 Hz, 1H), 7.90 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.35-7.28 (m, 2H), 7.04 (d, J = 7.0 Hz, 1H), 6.76 (br d, J = 4.1 Hz, 1H), 5.17 (s, 2H), 3.94 (s, 3H), 2.91 (d, J = 5.0 Hz, 3H), 2.48 (s, 3H) 33 [00055] 8.30 (q, J = 2.0 Hz, 1H), 8.03 (dd, J = 5.5, 8.8 Hz, 1H), 7.38- 7.29 (m, 3H), 7.27-7.21 (m, 1H), 7.04 (dd, J = 1.3, 7.2 Hz, 1H), 5.13 (br s, 2H), 4.03-4.03 (m, 3H), 3.83-3.82 (m, 3H), 2.49 (s, 3H). 34 [00056] 8.31 (br d, J = 2.0 Hz, 1H), 8.04 (dd, J = 5.6, 8.7 Hz, 1H), 7.39-7.27 (m, 3H), 7.26-7.21 (m, 1H), 7.04 (d, J = 7.3 Hz, 1H), 6.75 (br d, J = 4.1 Hz, 1H), 5.12 (s, 2H), 3.94 (s, 3H), 2.90 (d, J = 5.0 Hz, 3H), 2.48 (s, 3H). 35 [00057] 8.28 (d, J = 2.19 Hz, 1 H) 7.90 (d, J = 8.55 Hz, 1 H) 7.79 (d, J = 1.97 Hz, 1 H) 7.66 (dd, J = 8.44, 2.08 Hz, 1 H) 7.31-7.36 (m, 1 H) 7.27-7.31 (m, 1 H) 7.03 (dd, J = 7.34, 1.21 Hz, 1 H) 5.13 (br s, 2 H) 4.03 (s, 3 H) 3.82 (s, 3 H) 2.49 (s, 3 H). 36 [00058] 8.29 (d, J = 1.88 Hz, 1 H) 7.91 (d, J = 8.50 Hz, 1 H) 7.79 (d, J = 1.50 Hz, 1 H) 7.66 (br d, J = 8.50 Hz, 1 H) 7.27-7.37 (m, 2 H) 7.03 (d, J = 7.25 Hz, 1 H) 6.74 (br d, J = 4.13 Hz, 1 H) 5.13 (s, 2 H) 3.94 (s, 3 H) 2.90 (d, J = 5.00 Hz, 3 H) 2.48 (s, 3 H). 37 [00059] 8.33 (d, J = 2.19 Hz, 1 H) 7.91 (d, J = 7.89 Hz, 1 H) 7.45 (s, 1 H) 7.27-7.36 (m, 3 H) 7.03 (dd, J = 7.34, 1.43 Hz, 1 H) 5.12 (s, 2 H) 4.03 (s, 3 H) 3.82 (s, 3 H) 2.50 (s, 3 H) 2.41 (s, 3 H). 38 [00060] 8.34 (d, J = 2.13 Hz, 1 H) 7.90 (d, J = 8.00 Hz, 1 H) 7.45 (s, 1 H) 7.29-7.36 (m, 2 H) 7.27 (s, 1 H) 7.00-7.08 (m, 1 H) 6.72 (br d, J = 4.25 Hz, 1 H) 5.13 (s, 2 H) 3.94 (s, 3 H) 2.89 (d, J = 5.00 Hz, 3 H) 2.48 (s, 3 H) 2.41 (s, 3 H).

Biological Studies

Green House

[0179] The compound was dissolved in a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solvent-emulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml. This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.

Use Example 1. Protective Control of Soybean Rust on Soybeans Caused by Phakopsora pachyrhizi (PHAKPA P2)

[0180] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, 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 days 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. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. 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 hr. The trial plants were cultivated for up to 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, the disease level of untreated controls was usually higher than 85%.

Use Example 2. Protective Control of Soybean Rust on Soybeans Caused by Phakopsora pachyrhizi (PHAKPA P6)

[0181] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient as described below. The plants were allowed to air-dry. The trial plants were cultivated for six days 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. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. To ensure the success 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 hr. The trial plants were cultivated for up to 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, the disease level of untreated controls was usually higher than 85%.

[0182] The results of the abovementioned use examples are given in the following Tables. All test results below are given for the control of phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

TABLE-US-00007 TABLE 1 % PHAKPA Disease level Treatment with P2 at P2 at P6 at P6 at No. Structure 4 ppm 16 ppm 4 ppm 16 ppm 1 [00061] 100 96 90 83 2 [00062]  50  2 63 15 3 [00063]  36  2 83 21