USE OF STROBILURIN TYPE COMPOUNDS FOR COMBATING PHYTOPATHOGENIC FUNGI CONTAINING AN AMINO ACID SUBSTITUTION F129L IN THE MITOCHONDRIAL CYTOCHROME B PROTEIN CONFERRING RESISTANCE TO QO INHIBITORS IV

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. (canceled)

2. The method according to claim 7, wherein in formula I 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 method according to claim 7, wherein in formula I R.sup.3 is selected from C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-monohaloalkyl, C.sub.1-C.sub.2-dihaloalkyl, C.sub.3-C.sub.4-cycloalkyl and —O—C.sub.1-C.sub.2-alkyl.

4. The method according to claim 7, wherein in formula I R.sup.4 is selected from C.sub.1-C.sub.4-alkyl, —C(═O)—C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.4-haloalkyl and —(C.sub.1-C.sub.2-alkyl)-O—(C.sub.1-C.sub.2-alkyl).

5. The method according to claim 7, wherein in formula I R.sup.a is selected from is selected from 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, 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.

6. The method according to claim 7, wherein the phytopathogenic fungi are soybean rust (Phakopsora pachyrhizi and/or P. meibomiae).

7. A method for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors, comprising: treating curatively and/or preventively the plants or the plant propagation material of said plants that are at risk of being diseased from the said phytopathogenic fungi, and/or applying to the said phytopathogenic fungi with an effective amount of at least one compound of formula I ##STR00987## 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, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.2-monohaloalkyl, C.sub.1-C.sub.2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C.sub.3-C.sub.6-cycloalkyl and —O—C.sub.1-C.sub.4-alkyl; R.sup.4 is selected from C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, —C(═O)—C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-haloalkenyl, —(C.sub.1-C.sub.2-alkyl)-O—(C.sub.1-C.sub.2-alkyl) and —CH.sub.2-cyclopropyl; 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, 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 or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

8. A compound of formula I ##STR00988## wherein R.sup.2 is selected from CH and N; R.sup.3 is selected from halogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.2-monohaloalkyl, C.sub.1-C.sub.2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C.sub.3-C.sub.6-cycloalkyl and —O—C.sub.1-C.sub.4-alkyl; R.sup.4 is selected from C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-haloalkenyl, —(C.sub.1-C.sub.2-alkyl)-O—(C.sub.1-C.sub.2-alkyl) and —(C.sub.1-C.sub.2-alkyl)-O—(C.sub.1-C.sub.2-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, 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; n is an integer selected from 0, 1, 2, 3, 4 and 5; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

9. The compound according to claim 8, wherein R.sup.2 is N.

10. The compound according to claim 8, wherein R.sup.3 is selected from C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-monohaloalkyl, C.sub.1-C.sub.2-dihaloalkyl, C.sub.3-C.sub.4-cycloalkyl and —O—C.sub.1-C.sub.2-alkyl.

11. The compound according to claim 8, wherein R.sup.4 is selected from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl and —(C.sub.1-C.sub.2-alkyl)-O(C.sub.1-C.sub.2-alkyl).

12. The compound according to claim 8, wherein n is 1, 2 or 3.

13. The compound according to claim 8, wherein R.sup.a is selected from halogen, CN, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkyl, —O—C.sub.1-C.sub.4-alkyl, —O—C.sub.1-C.sub.4-haloalkyl, —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, 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, 2 or 3 heteroatoms selected from N, 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 the cyclic moieties of R.sup.a are unsubstituted or carry 1, 2 or 3 identical or different groups R.sup.b selected from halogen, CN, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, —O—C.sub.1-C.sub.2-alkyl and —O—C.sub.1-C.sub.2-haloalkyl.

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

15. A method for combating phytopathogenic fungi comprising: treating curatively and/or preventively the plants or the plant propagation material of said plants that are 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 8.

Description

EXAMPLES

Synthetic Process

Example 1: Methyl (2E)-2-[2-[[(E)-3-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

[0189] ##STR00015##

Step 1: 1-(2-Fluorophenyl)ethanone oxime

[0190] 1-(2-fluorophenyl)ethenone (10 g, 1.0 eq) was taken in methanol (300 ml) and hydroxyl amine hydrochloride (7.54 g, 1.8 eq) was added. Pyridine (33.45 g, 2 eq) was added drop wise at 25° C. Reaction mixture was stirred at 50° C. for 2 hr. Reaction was monitored using LCMS & TLC. Methanol was evaporated under vacuum. Crude mass was diluted with water (200 ml) and it was extracted with ethyl acetate (3×100 ml). Combined organic layer was again washed with water and brine. Organic layer was dried over sodium sulphate and concentrated under vacuum. Crude compound was purified by flash column chromatography. Pure compound was eluted with 0% to 20% ethyl acetate (EtOAc) in heptane. Evaporation of solvent afforded 8 g title compound as white solid (Yield 72%). .sup.1H NMR 300 MHz, DMSO-dδ: δ 11.4 (s, 1H), 7.46-7.41 (m, 2H), 7.27-7.23 (m, 2H), 2.14 (s, 3H).

Step 2: Ethyl (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (Ex. 2)

[0191] 1-(2-fluorophenyl)ethanone oxime (0.3 g, 3 eq) was taken in dimethyl formamide (DMF, 5 ml) and Cs.sub.2CO.sub.3 (3.27 g, 2.0 eq) was added. The reaction mixture was stirred for 30 minutes at room temperature (RT; at about 25° C.) and then added methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.6 g, 3.02 eq). The reaction mixture was stirred at RT for 32 hr and monitored by TLC and LCMS. Reaction was quenched with water (45 ml) and the product was extracted in ethyl acetate (3×35 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 35-20% EtOAc in heptane. Evaporation of solvent afforded an off-white solid title compound (0.328 g, 45% yield). .sup.1H NMR (300 MHz, DMSO-d6): δ 7.56-7.36 (m, 2H), 7.33-7.32 (m, 4H), 7.03 (dd, J=6.2, 2.8 Hz, 3H), 5.00 (s, 2H), 3.93 (s, 3H), 3.64 (s, 3H), 2.42 (s, 3H), 2.08 (d, J=2.5 Hz, 3H).

Example 2: (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0192] ##STR00016##

[0193] Methyl (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (ex. 1; 8 g, 1 eq) was taken in THF (80 ml) and methylamine (40% aqueous) solution (16 ml, 2 vol) was added. The reaction mixture was stirred at 25° C. for 5 hr and monitored by TLC and LCMS. Reaction was quenched with water (200 ml) and the product was extracted in ethyl acetate (3×150 ml). The combined organic layer was washed with brine (150 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 30-40% EtOAc in heptane. Evaporation of solvent afforded white solid title compound (7 g, 87.7% yield). .sup.1H NMR (500 MHz, DMSO-d6): δ 8.20 (q, J=4.7 Hz, 1H), 7.44 (ddt, J=7.8, 5.6, 2.0 Hz, 2H), 7.37-7.14 (m, 4H), 6.95 (dd, J=7.1, 2.0 Hz, 1H), 5.01 (s, 2H), 3.86 (s, 3H), 2.65 (d, J=4.8 Hz, 3H), 2.42 (s, 3H), 2.09 (d, J=2.6 Hz, 3H).

Example 3: Methyl (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

[0194] ##STR00017##

Step 1: 1-(3,5-dichlorophenyl)ethanone oxime

[0195] 3-(3,5-Dichlorophenyl)ethanone (3.0 g, 3 eq) was taken in methanol (30 ml) and NH.sub.2OH (0.735 g, 2 eq) followed by pyridine (3.04 g, 2.5 eq) were added. Reaction mixture was heated to 70° C. and stirred for 3 hr. Reaction was monitored using LCMS & TLC. Solvent was evaporated and the residue was diluted with water (50 ml). The product was extracted in with ethyl acetate (3×30 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 15-20% EtOAc in heptane. Evaporation of solvent afforded white solid compound 1-(3,5-dichlorophenyl)ethanone oxime (1 g, 92.6% yield).

Step 2: Methyl (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate

[0196] 3-(3,5-Dichlorophenyl)ethanone oxime (0.4 g, 1 eq) was taken in acetonitrile (10 ml) and Cs.sub.2CO.sub.3 (1.8 g, 2.5 eq) was added. The reaction mixture was stirred for 30 min at RT and then added methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.65 g, 1.05 eq). The reaction mixture was stirred at RT for 3 hr and monitored by TLC and LCMS. Reaction was quenched with water (50 ml) and the product was extracted in ethyl acetate (3×30 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 20-25% EtOAc in heptane. Evaporation of solvent afforded an off-white solid title compound (0.6 g, 68% yield). .sup.1H NMR (500 MHz, DMSO-d6): δ 7.66 (t, J=1.9 Hz, 1H), 7.61 (d, J=1.9 Hz, 2H), 7.36-7.23 (m, 2H), 7.05-6.98 (m, 1H), 5.04 (s, 2H), 3.91 (s, 3H), 3.70 (s, 3H), 2.43 (s, 3H), 2.30 (s, 3H).

Example 4: (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0197] ##STR00018##

[0198] Methyl (2E)-2-[2-[[(E)-3-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (ex. 3; 0.6 g, 1 eq) was taken in THF (6 ml) and methyl amine (40% aq.) solution (1.2 ml, 2 v) was added. The reaction mixture was stirred at RT for 3 hr and monitored by TLC and LCMS. Reaction was quenched with water (25 ml) and the product was extracted in ethyl acetate (3×20 ml). The combined organic layer was washed with brine (25 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 40-45% EtOAc in heptane. Evaporation of solvent afforded white solid title compound (example 2, 0.53 g, 85% yield). .sup.1H NMR (500 MHz, DMSO-d6): δ 8.24 (d, J=4.8 Hz, 1H), 7.69-7.58 (m, 3H), 7.37-7.15 (m, 2H), 6.95 (dd, J=7.1, 1.9 Hz, 1H), 5.05 (s, 2H), 3.86 (s, 3H), 2.68 (d, J=4.7 Hz, 3H), 2.42 (s, 3H), 2.11 (s, 3H).

Example 5: Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetate

[0199] ##STR00019##

Step 1: 1-(p-tolyl)ethanone oxime

[0200] To a solution of 1-(p-tolyl)ethanone (1.0 g, 4.45 mmol, 3 eq.) in methanol (10 mL) was added hydroxylamine hydrochloride (0.77 g, 11.17 mmol, 1.5 eq) followed by addition of sodium acetate (1.82 g, 15 mmol, 2 eq.) at RT under nitrogen atmosphere. Reaction mixture was refluxed for 2 hrs. Reaction was monitored by TLC. Reaction mixture was concentrated on rotavapor. To this crude residue was added water (20 mL) and stirred for 0.5 hr. Solid material filtered and dried to obtain pure title compound (1.1 g, yield 98%) as white solid. MS: [M+H].sup.+ 150.

Step 2: Methyl (2E)-2-methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetate

[0201] To a stirred solution of 1-(p-tolyl)ethanone oxime (0.15 g, 1.0 mmol, 1 eq) in acetonitrile (2 mL) was added Cs.sub.2CO.sub.3 (0.66 g, 2.0 mmol, 2 eq). The reaction mixture was stirred at 25° C. for 30 min. Then, methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.33 g, 1.1 mmol, 1.1 eq) was added. The mixture was stirred at 25° C. for 6 h. Reaction was monitored by TLC and LCMS. To this reaction mixture was added water (30 mL) and extracted with EtOAc (3×30 mL). Combined organic layer was washed with H.sub.2O (2×25 mL), followed by brine wash 15 (2×20 mL). Organic layer was dried over Na.sub.2SO.sub.4 and Concentrated to afford crude compound which was further purified by flash column chromatography using 0-20% EtOAc in heptane as the eluent to obtain pure title compound as white solid (0.37 g, Yield 96%). .sup.1H NMR (500 MHz, chloroform-d): δ 7.42 (d, J=8.2 Hz, 2H), 7.26-7.19 (m, 3H), 7.07 (d, J=8.0 Hz, 2H), 6.94 (dd, J=7.2, 1.8 Hz, 2H), 5.03 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.41 (s, 3H), 2.27 (s, 3H), 2.06 (s, 3H). MS: [M+H].sup.+ 369.

Example 6: (2E)-2-Methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetamide

[0202] ##STR00020##

[0203] To a stirred solution of methyl (2E)-2-methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetate in THF (5 mL), methyl amine solution in water (5.0 mL, 40%) was added at RT. Reaction was continued for 1 hr. Reaction was monitored by TLC. Reaction mixture was evaporated on rotavapor, residue was diluted with EtOAc (20 mL) and washed with 1 N HCl (3×20 mL), followed by brine wash (2×20 mL). Organic layer was dried over Na.sub.2SO.sub.4 and Concentrated to afford crude compound which was further purified by flash column chromatography using 0-50% EtOAc in heptane as the eluent to afford pure title compound as white solid (0.200 g, Yield 88%). .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ 8.20 (d, J=5.0 Hz, 1H), 7.54-7.48 (m, 2H), 7.31-7.22 (m, 2H), 7.19 (d, J=8.0 Hz, 2H), 6.95 (dd, J=6.9, 2.1 Hz, 1H), 4.99 (s, 2H), 3.86 (s, 3H), 2.69 (d, J=4.7 Hz, 3H), 2.43 (s, 3H), 2.31 (s, 3H), 2.08 (s, 3H). MS: [M+H].sup.+ 368.

Example 7: (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-[3,3,3-trifluoro-1-[3-(trifluoromethyl)phenyl]propylidene]amino]oxymethyl]phenyl]acetamide

[0204] ##STR00021##

[0205] 3,3,3-Trifluoro-1-[3-(trifluoromethyl)phenyl]propan-1-one (0.5 g, 1 eq), prepared in analogy to prior art process (Chem Commun, 2016, 52, 13668-13670), was taken in THF (10 ml) and (2E)-2-[2-(aminooxymethyl)-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (0.98 g, 2 eq) followed by Ti(OEt).sub.4 (1.33 g, 3 eq) were added. The mixture was heated to 70° C. and stirred for 12 hr. The reaction was monitored by TLC and LCMS. The reaction was quenched with water (25 ml) followed by EtOAc (25 ml). The emulsion formed was filtered through celite and washed with EtOAc (50 ml). The layers were separated and the aqeuous layer was extracted in EtOAc (2×25 ml). The combined organic layer was washed with brine (25 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 40-45% EtOAc in heptane. Evaporation of solvent followed by crystallization in heptane afforded an off-white solid (0.34 g, 35% yield). .sup.1H NMR (500 MHz, DMSO-d6): δ 8.27 (q, J=4.7 Hz, 1H), 8.07-8.00 (m, 2H), 7.85-7.79 (m, 1H), 7.68 (t, J=7.8 Hz, 1H), 7.35-7.24 (m, 2H), 6.97 (dd, J=7.3, 1.7 Hz, 1H), 5.12 (s, 2H), 4.03-3.96 (q, J=10 Hz, 2H), 3.86 (s, 3H), 2.67 (d, J=4.7 Hz, 3H), 2.43 (s, 3H).

[0206] The following examples in Table S were synthesized as per general Scheme 1 described above (except Ex. 7 and 212 which were synthesized as per scheme 2) and characterized by LCMS as described in Table L.

TABLE-US-00005 TABLE L LCMS Methods Method details Device details LCMS Method A Column: Agilent Eclipse Plus C18 LCMS2020 (Shimadzu) (50 mm × 4.6 mm × 3 μm particles) Ionization source: ESI Mobile Phase: Mass range: 100-800 amu A: 10 mM Ammonium formate in water. Polarity: Dual (positive and B: 0.1% Formic acid in acetonitrile negative simultaneous scan) Gradient: 10% B to 100% B in 1.5 min. Mode: Scan Hold 1 min 100% B. 1 min 10% B. Run LC System: Nexera High pressure time: 3.50 or 3.75 min. gradient system, Binary pump Flow: 1.2 ml/min; Detector: PDA Column oven: 30° C./40° C. Scanning wavelength: 220 nm/max plot LCMS Method B Column: Luna-C18 LCMS DELIVER-220 (Shimadzu) (30 mm × 2.0 mm × 3 μm particles) Ionization source: ESI Mobile Phase: Mass range: 100-1000 amu A: 0.037% Trifluoroacetic acid in water. Polarity: Positive B: 0.018% Trifluoroacetic acid in HPLC Mode: Scan grade acetonitrile LC System: Nexera High pressure Gradient: 5-95% B in 3.00 min .5% B in gradient system, Binary pump 0.01 min, 5-95% B (0.01-1.60 min), Detector: DAD 95-100% B (1.60-2.50 min), 100-5% Scanning wavelength: 220 nm/max plot (2.50-2.52 min) with a hold at 5% B for 0.48 min. Flow: 0.8 mL/min; Column oven: 40° C. LCMS Method C Column: Xbridge Shield RP18 Agilent (50 mm × 2.1 mm, 5 μm particles) Ionization source: ESI Mobile Phase: Mass range: 100-1000 amu A: H.sub.2O + 10 mM NH.sub.4HCO.sub.3 Polarity: Positive B: Acetonitrile Mode: Scan Gradient: 5% B in 0.40 min and 5-95% B LC System: Nexera High pressure at 0.40-3.40 min, hold on 95% B for 0.45 gradient system, Binary pump min, and then 95-5% B in 0.01 min. Detector: DAD Flow: 0.8 ml/min; Scanning wavelength: 220 nm/max plot Column oven: 40° C. LCMS Method D Column: Agilent Eclipse Plus C18 LCMS 2020 (Shimadzu) (50 mm × 4.6 mm × 3 μm particles) Ionization source: ESI Mobile Phase: Mass range: 100-800 amu A: 10 mM NH.sub.4(HCOO) in water Polarity: Dual (positive and negative B: Acetonitrile simultaneous scan) Gradient: 10% B to 100% B in 5 min, Mode: Scan hold on 100% B for 3 min, 2 min 10% B. LC System: Nexera High pressure Run time: 10 min. gradient system, Binary pump Flow: 1.2 ml/min; Detector: PDA Column oven: 40° C. Scanning wavelength: 220 nm/max plot
Used LCMS Method in Table S to be found in Column LCMS.

TABLE-US-00006 TABLE 3 No. Structure R.sub.t [min] Mass LCMS 1 [00022] 2.08 373.7 A 2 [00023] 1.941 372 A 3 [00024] 2.252 422.9 A 4 [00025] 2.15 421.9 A 5 [00026] 2.144 369 A 6 [00027] 2.027 368 A 7 [00028] 2.123 490 A 8 [00029] 2.15 422.5 A 9 [00030] 2.19 423.5 A 10 [00031] 2.22 449.23 A 11 [00032] 2.13 448.4 A 12 [00033] 1.95 404 A 13 [00034] 2.18 435.3 A 14 [00035] 2.11 434.4 A 15 [00036] 2.05 425.2 A 16 [00037] 2.17 426.2 A 17 [00038] 1.99 447.1 A 18 [00039] 2.09 448.2 A 19 [00040] 2.06 404 A 20 [00041] 2.155 425 A 21 [00042] 2.06 408.5 A 22 [00043] 2.08 424 A 23 [00044] 2.04 458.3 A 24 [00045] 2.07 458.9 A 25 [00046] 2.07 441.05 A 26 [00047] 1.984 440 A 27 [00048] 1.97 408 A 28 [00049] 2.17 439 A 29 [00050] 2.09 438 A 30 [00051] 2.058 355 A 31 [00052] 1.963 354 A 32 [00053] 2.17 490 A 33 [00054] 2.25 456.9 A 34 [00055] 2.25 491 A 35 [00056] 2.1 446.8 A 36 [00057] 2.101 423 A 37 [00058] 2.155 422.9 A 38 [00059] 1.999 422 A 39 [00060] 2.059 422 A 40 [00061] 2.271 423.7 A 41 [00062] 2.15 422 A 42 [00063] 1.94 435.9 A 43 [00064] 2.09 436 A 44 [00065] 1.99 445.9 A 45 [00066] 2.13 397 A 46 [00067] 2.01 447 A 47 [00068] 2.08 440 A 48 [00069] 2.11 448 A 49 [00070] 2.18 441 A 50 [00071] 2.11 440.8 A 51 [00072] 2.2 441 A 52 [00073] 2.274 447.8 A 53 [00074] 2.094 379.8 A 54 [00075] 1.984 378 A 55 [00076] 2.02 396 A 56 [00077] 2.197 435.6 A 57 [00078] 2.208 446.1 A 58 [00079] 2.091 432.8 A 59 [00080] 2.26 457 A 60 [00081] 2.15 456 A 61 [00082] 2.22 437 A 62 [00083] 2.146 436 A 63 [00084] 2.099 436 A 64 [00085] 1.97 435 A 65 [00086] 2.24 437 A 66 [00087] 2.24 491 A 67 [00088] 2.15 490 A 68 [00089] 2.14 436 A 69 [00090] 2.059 440 A 70 [00091] 2.197 480 A 71 [00092] 2.091 479 A 72 [00093] 1.337 391 A 73 [00094] 1.256 390 A 74 [00095] 2.208 463 A 75 [00096] 2.101 462 A 76 [00097] 2.22 369 A 77 [00098] 2.1 368 A 78 [00099] 2.133 385 A 79 [00100] 2.005 384 A 80 [00101] 2.13 421 A 81 [00102] 2.037 420 A 82 [00103] 2.08 425 A 83 [00104] 1.92 424 A 84 [00105] 2.08 390 A 85 [00106] 2.03 372 A 86 [00107] 2.17 373 A 87 [00108] 2.08 391 A 88 [00109] 2.24 448 A 89 [00110] 2.15 449 A 90 [00111] 2.261 459 A 91 [00112] 2.155 458 A 92 [00113] 2.21 451 A 93 [00114] 2.11 450 A 94 [00115] 2.187 383 A 95 [00116] 2.22 397 A 96 [00117] 2.283 411 A 97 [00118] 2.208 431 A 98 [00119] 5.01 430 D 99 [00120] 2.08 382 A 100 [00121] 2.187 410 A 101 [00122] 2.22 403 A 102 [00123] 2.21 403 A 103 [00124] 2.08 373 A 104 [00125] 1.995 380 A 105 [00126] 2.144 396 A 106 [00127] 2.112 402 A 107 [00128] 2.123 402 A 108 [00129] 1.952 372 A 109 [00130] 2.123 402 A 110 [00131] 2.25 441 A 111 [00132] 2.2 431 A 112 [00133] 1.87 379 A 113 [00134] 2.11 430 A 114 [00135] 2.17 435 A 115 [00136] 2.113 369 A 116 [00137] 2.101 389 A 117 [00138] 2.197 423 A 118 [00139] 2.091 391 A 119 [00140] 2.12 434 A 120 [00141] 2.005 433 A 121 [00142] 2.2 431 A 122 [00143] 2.05 379 A 123 [00144] 2.04 385 A 124 [00145] 2.11 430 A 125 [00146] 1.93 378 A 126 [00147] 1.931 384 A 127 [00148] 1.984 368 A 128 [00149] 1.984 388 A 129 [00150] 2.112 391 A 130 [00151] 2.08 422 A 131 [00152] 1.984 390 A 132 [00153] 1.984 390 A 133 [00154] 2.187 439 A 134 [00155] 2.155 453 A 135 [00156] 2.29 513 A 136 [00157] 2.08 438 A 137 [00158] 2.18 383 A 138 [00159] 2.261 453 A 139 [00160] 2.155 382 A 140 [00161] 2.144 450 A 141 [00162] 2.069 452 A 142 [00163] 2.208 512 A 143 [00164] 2.197 447 A 144 [00165] 2.304 499 A 145 [00166] 2.261 463 A 146 [00167] 2.261 451 A 147 [00168] 2.24 449 A 148 [00169] 2.187 446 A 149 [00170] 2.347 498 A 150 [00171] 2.272 462 A 151 [00172] 2.261 450 A 152 [00173] 2.229 448 A 153 [00174] 2.155 389 A 154 [00175] 2.144 389 A 155 [00176] 1.995 380 A 156 [00177] 2.133 459 A 157 [00178] 2.132 388 A 158 [00179] 2.133 388 A 159 [00180] 1.941 379 A 160 [00181] 2.08 425 A 161 [00182] 162 [00183] 2.091 458 A 163 [00184] 2.229 403 A 164 [00185] 1.995 384 A 165 [00186] 2.187 382 A 166 [00187] 2.048 397 A 167 [00188] 2.219 440 A 168 [00189] 2.133 434 A 169 [00190] 2.112 409 A 170 [00191] 1.984 408 A 171 [00192] 2.29 423 A 172 [00193] 2.165 379 A 173 [00194] 2.069 422 A 174 [00195] 2.24 383 A 175 [00196] 2.261 383 A 176 [00197] 2.145 382 A 177 [00198] 2.165 391 A 178 [00199] 2.037 390 A 179 [00200] 1.888 396 A 180 [00201] 2.273 459 A 181 [00202] 2.261 426 A 182 [00203] 2.144 425 A 183 [00204] 2.251 383 A 184 [00205] 2.123 438 A 185 [00206] 2.23 462 A 186 [00207] 2.112 452 A 187 [00208] 2.027 426 A 188 [00209] 2.24 437 A 189 [00210] 2.144 436 A 190 [00211] 2.187 456 A 191 [00212] 2.229 453 A 192 [00213] 2.24 439 A 193 [00214] 2.101 402 A 194 [00215] 2.421 465 A 195 [00216] 2.144 382 A 196 [00217] 1.931 378 A 197 [00218] 2.176 458 A 198 [00219] 2.204 441 A 199 [00220] 2.144 440 A 200 [00221] 2.315 457 A 201 [00222] 2.133 439 A 202 [00223] 2.016 438 A 203 [00224] 2.283 383 A 204 [00225] 2.315 437 A 205 [00226] 2.15 490 A 206 [00227] 2.336 451 A 207 [00228] 2.229 450 A 208 [00229] 2.219 452 A 209 [00230] 2.187 450 A 210 [00231] 2.219 381 A 211 [00232] 2.091 380 A 212 [00233] 1.952 425 A 213 [00234] 2.123 391 A 214 [00235] 1.947 391 A 215 [00236] 2.357 463 A 216 [00237] 2.048 385 A 217 [00238] 2.208 395 A 218 [00239] 2.261 397 A 219 [00240] 2.101 394 A 220 [00241] 2.155 396 A 221 [00242] 2.251 410 A 222 [00243] 2.165 437 A 223 [00244] 2.048 436 A 224 [00245] 1.963 380 A 225 [00246] 1.853 379 A 226 [00247] 2.069 455 A 227 [00248] 2.187 456 A 228 [00249] 2.25 456 A 229 [00250] 2.24 437 A 230 [00251] 2.155 436.3 A 231 [00252] 2.16 422 A 232 [00253] 2.165 421 A 233 [00254] 2.21 469 A 234 [00255] 2.251 462 A 235 [00256] 2.251 465 A 236 [00257] 2.24 439 A 237 [00258] 2.325 463 A 238 [00259] 2.165 469 A 239 [00260] 2.315 437 A 240 [00261] 2.315 469 A 241 [00262] 2.208 468 A 242 [00263] 2.219 415 A 243 [00264] 2.112 414 A 244 [00265] 2.18 422 A 245 [00266] 2.176 456 A 246 [00267] 2.4 441 A 247 [00268] 2.283 440 A 248 [00269] 2.048 452 A 249 [00270] 2.133 441 A 250 [00271] 2.251 491 A 251 [00272] 2.197 457 A 252 [00273] 1.963 420 A 253 [00274] 208 421 A 254 [00275] 2.176 453 A 255 [00276] 2.229 490 A 256 [00277] 2.155 407 A 257 [00278] 2.251 503 A 258 [00279] 2.155 502 A 259 [00280] 2.251 453 A 260 [00281] 2.059 440 A 261 [00282] 2.165 452 A 262 [00283] 2.034 406 A 263 [00284] 2.144 441 A 264 [00285] 2.144 513 A 265 [00286] 2.229 514 A 266 [00287] 2.069 391 A 267 [00288] 390 2.005 A 268 [00289] 2.283 473 A 269 [00290] 2.229 457 A 270 [00291] 2.144 456 A 271 [00292] 2.176 472 A 272 [00293] 2.123 490 A 273 [00294] 2.123 436 A 274 [00295] 2.219 491 A 275 [00296] 2.165 491 A 276 [00297] 2.219 437 A 277 [00298] 1.952 398 A 278 [00299] 2.155 382 A 279 [00300] 2.347 411 A 280 [00301] 2.06 399 A 281 [00302] 2.176 431 A 282 [00303] 1.99 445.9 A 283 [00304] 2.12 407 A 284 [00305] 2.0 406 A 285 [00306] 2.16 387 A 286 [00307] 2.02 396 A 287 [00308] 2.14 397 A 288 [00309] 2.02 430 A 289 [00310] 2.20 457 A 290 [00311] 2.1 456 A 291 [00312] 1.95 394 A 292 [00313] 2.25 395 A 293 [00314] 2.02 386 A 294 [00315] 2.05 369 A 295 [00316] 1.94 384 A 296 [00317] 2.18 408 A 297 [00318] 2.20 395 A 298 [00319] 1.98 404 A 299 [00320] 2.14 394 A 300 [00321] 2.22 469 A 301 [00322] 2.1 468 A 302 [00323] 2.16 419 A 303 [00324] 2.04 418 A 304 [00325] 1.416 456.8 A 305 [00326] 1.95 447 B 306 [00327] 1.96 465 B 307 [00328] 1.99 427 B 308 [00329] 1.64 412 B 309 [00330] 1.9 413 B 310 [00331] 1.9 426 B 311 [00332] 1.74 413 B 312 [00333] 1.76 398 B 313 [00334] 1.88 411 B 314 [00335] 1.69 414 B 315 [00336] 1.82 412 B 316 [00337] 464 1.86 B 317 [00338] 1.86 399 B 318 [00339] 1.83 412 B 319 [00340] 1.93 413 B 320 [00341] 1.86 453 B 321 [00342] 1.87 446 B 322 [00343] 1.8 415 B 323 [00344] 1.386 456.7 A 324 [00345] 1.79 452 B 325 [00346] 1.64 456 B 326 [00347] 1.77 440 B 327 [00348] 1.83 436 B 328 [00349] 1.88 453 B 329 [00350] 1.78 410 B 330 [00351] 1.86 441 B 331 [00352] 1.77 452 B 332 [00353] 1.93 437 B 333 [00354] 2.25 503 A 334 [00355] 1.9 457 B 335 [00356] 1.53 549 A 336 [00357] 1.458 548.1 A 337 [00358] 1.67 468 B 338 [00359] 2 473 B 339 [00360] 1.85 426 B 340 [00361] 1.7 452 B 341 [00362] 1.65 437 B 342 [00363] 1.88 505 B 343 [00364] 1.95 506 B 344 [00365] 1.68 474 B 345 [00366] 1.6 440 B 346 [00367] 1.82 474 B 347 [00368] 1.92 355 B 348 [00369] 1.97 453 B 349 [00370] 3.04 522 C 350 [00371] 1.99 507 B 351 [00372] 1.92 457 B 352 [00373] 1.84 488 B 353 [00374] 1.86 419 B 354 [00375] 1.82 456 B 355 [00376] 2.97 535 C 356 [00377] 3.13 536 C 357 [00378] 1.62 458 B 358 [00379] 2.93 519 C 359 [00380] 1.95 459 B 360 [00381] 1.73 459 B 361 [00382] 1.76 475 B 362 [00383] 1.93 455 B 363 [00384] 1.89 506 B 364 [00385] 1.74 438 A 365 [00386] 1.7 441 B 366 [00387] 1.9 475 B 367 [00388] 1.84 354 B 368 [00389] 3.09 520 C 369 [00390] 1.87 458 B 370 [00391] 1.94 489 B 371 [00392] 3.79 523 C 372 [00393] 1.76 418 B 373 [00394] 374 [00395] 1.94 427 B 375 [00396] 1.91 472 B 376 [00397] 2.07 403 A 377 [00398] 1.95 402 A 378 [00399] 1.67 456 B 379 [00400] 2.2 457 A 380 [00401] 2.04 422 A 381 [00402] 2.13 423 A 382 [00403] 2.2 417 A 383 [00404] 2.07 416 A 384 [00405] 1.67 472 B 385 [00406] 1.78 473 B 386 [00407] 2.24 383 A 387 [00408] 2.25 383 A 388 [00409] 2.14 382 A 389 [00410] 2.11 382 A 390 [00411] 2.18 440 A 391 [00412] 2.15 437 A 392 [00413] 2.16 437 A 393 [00414] 2.03 436 A 394 [00415] 2.08 454 A 395 [00416] 2.19 421 A 396 [00417] 2.05 420 A 397 [00418] 2.23 381 A 398 [00419] 2.18 367 A 399 [00420] 2.03 380 A 400 [00421] 1.99 366 A 401 [00422] 2.03 396 A 402 [00423] 2.197 455 A 403 [00424] 1.25 436 A 404 [00425] 2.167 473 A 405 [00426] 2.22 472 A 406 [00427] 2.12 472 A 407 [00428] 2.26 512 A 408 [00429] 2.29 513 A 409 [00430] 2.21 459 A 410 [00431] 2.04 458 A 411 [00432] 2.24 489 A 412 [00433] 2.13 488 A 413 [00434] 2.25 498 A 414 [00435] 2.34 499 A 415 [00436] 2.18 509 A 416 [00437] 2.27 529 A 417 [00438] 2.24 494 A 418 [00439] 2.28 510 A 419 [00440] 2.106 528 A 420 [00441] 2.02 493 A 421 [00442] 2.18 457 A 422 [00443] 2.12 456 A 423 [00444] 2.03 448 A 424 [00445] 1.898 447 A 425 [00446] 2.26 517 A 426 [00447] 2.15 516 A 427 [00448] 1.86 507 B 428 [00449] 1.75 506 B 429 [00450] 2.27 491 A 430 [00451] 2.3 490 A 431 [00452] 2.17 490 A 432 [00453] 2.33 516 A 433 [00454] 2.4 514 A 434 [00455] 2.33 515 A 435 [00456] 2.15 514 A 436 [00457] 1.86 506 B 437 [00458] 1.71 436 B 438 [00459] 1.77 491 B 439 [00460] 1.82 507 B 440 [00461] 1.66 490 B 441 [00462] 1.71 506 B 442 [00463] 1.77 490 B 443 [00464] 1.72 489 B 444 [00465] 1.83 506 B 445 [00466] 2.23 500 A 446 [00467] 2.12 436 A 447 [00468] 1.87 475 B 448 [00469] 1.75 488 B 449 [00470] 1.8 490 B 450 [00471] 1.89 474 B 451 [00472] 1.78 474 B 452 [00473] 1.91 490 B 453 [00474] 1.85 488 B 454 [00475] 1.83 489 B 455 [00476] 1.9 491 B 456 [00477] 1.81 488 B 457 [00478] 1.72 488 B 458 [00479] 2.04 408 A 459 [00480] 2.16 409 A 460 [00481] 2.64 465 A 461 [00482] 2.00 438 A 462 [00483] 2.21 438 A 463 [00484] 2.31 472 A 464 [00485] 2.10 452 A

Biological Studies

Green House and Detached Leaf Tests

[0207] 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. Curative Control of Soybean Rust on Soybeans Caused by Phakopsora pachyrhizi (PHAKPA K4)

[0208] Leaves of potted soybean seedlings 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 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 hr. 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 the previously described spray solution, 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 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 P2)

[0209] 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 3. Protective Control of Soybean Rust on Soybeans Caused by Phakopsora pachyrhizi (PHAKPA P6)

[0210] 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%.

Use Example 4. Protective Control of Soybean Rust on Detached Soybean Leaves Caused by Phakopsora pachyrhizi (PHAKPA P1 DL)

[0211] 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 left for drying in a green house chamber at 20° C. and 14 hours lightning over night. The next day, leaves were harvested and placed on water agar plates. Subsequently, the leaves were inoculated with spores of Phakopsora pachyrhizi. Two different isolates were used: one being sensitive to Qo inhibitors (wt); and one which contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L). Inoculated leaves were incubated for 16 to 24 h at room temperature in a dark dust chamber, followed by incubation for 2 to 3 weeks in an incubator at 20° C. and 12 hours light/day. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Micro Titer Plate Tests

[0212] The active compounds were formulated separately as a stock solution having a concentration of 10,000 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.

[0213] After addition of the respective spore suspension as indicated in the different use examples below, 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 blank value to determine the relative growth in % of the pathogens in the respective active compounds.

Use Example 5. Activity Against Pyricularia Oryzae Causing Rice Blast (PYRIOR)

[0214] A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.

Use Example 6. Activity Against Septoria tritici Causing Leaf Blotch on Wheat (SEPTTR)

[0215] A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.

Use Example 7. Activity Against Colletotrichum orbiculare Causing Anthracnose (COLLLA)

[0216] A spore suspension of Colletotrichum orbiculare in an aqueous 2% malt solution was used.

Use Example 8. Activity Against Leptosphaeria nodorum Causing Wheat Leaf Spots (LEPTNO)

[0217] A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.

Use Example 9. Activity Against Alternaria solani Causing Early Blight (ALTESO, Wt and F129L)

[0218] Two different spore suspensions of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution were used: a sensitive wild-type isolate (wt) and a Qo inhibitor-resistant isolate containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L).

Use Example 10. Activity Against Pyrenophora teres Causing Net Blotch on Barley (PYRNTE, Wt and F129L)

[0219] Two different spore suspensions of Pyrenophora teres in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution were used: a sensitive wild-type isolate (wt) and a Qo inhibitor-resistant isolate containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L).

Use Example 11. Activity Against Cercospora sojina Causing Frogeye Leaf Spot of Soybeans (CERCSO)

[0220] A spore suspension of Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.

Use Example 12. Activity Against Microdochium nivale Causing Snow Mould (MONGNI)

[0221] A spore suspension of Microdochium nivale in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.

[0222] The results of the abovementioned use examples are given in the following Tables.

[0223] The test results in Tables 1 and C1 to C4 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 (F129L) Disease level Treatment with compound P2 at P2 at P6 at P6 at No. Structure 4 ppm 16 ppm 4 ppm 16 ppm 1 [00486] 80 27 90 56 2 [00487] 5 0 26 1 3 [00488] 30 3 40 6 4 [00489] 2 0 13 1 5 [00490] 28 1 50 4 6 [00491] 1 0 19 1 8 [00492] 4 0 5 0 9 [00493] 35 23 41 4 10 [00494] 22 2 45 3 11 [00495] 23 1 20 0 12 [00496] 25 1 37 9 13 [00497] 28 0 25 0 14 [00498] 6 0 11 1 15 [00499] 4 0 24 1 17 [00500] 70 50 63 57 19 [00501] 87 0 87 1 20 [00502] 73 29 97 18 21 [00503] 100 77 97 88 22 [00504] 100 90 100 93 23 [00505] 12 1 20 1 24 [00506] 36 60 4 28 25 [00507] 16 3 50 2 26 [00508] 12 0 19 1 27 [00509] 5 0 32 0 28 [00510] 0 0 29 [00511] 0 0 30 [00512] 53 1 77 2 31 [00513] 0 0 4 0 32 [00514] 80 50 73 43 33 [00515] 50 33 60 75 34 [00516] 100 90 90 83 36 [00517] 100 42 100 43 37 [00518] 40 3 40 2 38 [00519] 37 4 47 1 39 [00520] 30 4 15 2 40 [00521] 40 18 63 22 41 [00522] 15 9 36 14 42 [00523] 60 23 60 20 43 [00524] 100 100 97 87 44 [00525] 77 17 77 21 46 [00526] 63 50 90 57 47 [00527] 13 0 12 0 48 [00528] 100 80 100 67 49 [00529] 60 18 60 7 50 [00530] 2 1 6 0 51 [00531] 28 2 15 0 52 [00532] 63 28 90 43 53 [00533] 63 17 100 47 54 [00534] 0 1 20 0 55 [00535] 3 1 13 5 56 [00536] 43 24 67 19 57 [00537] 25 8 43 15 58 [00538] 2 0 4 0 59 [00539] 67 20 63 11 60 [00540] 23 1 53 2 61 [00541] 70 15 90 18 62 [00542] 43 0 60 3 63 [00543] 90 77 93 77 64 [00544] 87 73 80 43 65 [00545] 93 77 100 87 66 [00546] 100 70 93 87 67 [00547] 67 2 80 30 69 [00548] 2 0 13 0 70 [00549] 30 0 10 1 71 [00550] 2 0 6 0 72 [00551] 100 87 93 80 73 [00552] 0 19 74 [00553] 27 6 16 3 75 [00554] 8 0 13 1 76 [00555] 30 3 9 0 77 [00556] 67 4 40 3 78 [00557] 40 1 30 1 79 [00558] 21 2 44 4 80 [00559] 50 10 30 3 81 [00560] 6 0 2 0 82 [00561] 87 57 83 [00562] 97 73 84 [00563] 0 0 0 0 85 [00564] 1 0 0 0 86 [00565] 12 3 23 3 87 [00566] 8 0 7 0 93 [00567] 83 32 43 37 94 [00568] 22 5 35 2 95 [00569] 11 0 33 4 96 [00570] 6 1 3 0 97 [00571] 4 1 1 0 98 [00572] 3 0 1 0 99 [00573] 43 12 87 33 100 [00574] 18 0 25 4 101 [00575] 70 37 60 17 102 [00576] 60 11 90 43 103 [00577] 40 3 35 4 104 [00578] 22 15 19 11 105 [00579] 18 1 39 13 106 [00580] 5 1 32 9 107 [00581] 1 0 15 1 108 [00582] 1 0 1 0 109 [00583] 8 1 12 0 110 [00584] 20 3 30 1 111 [00585] 28 8 46 10 112 [00586] 13 3 30 9 113 [00587] 25 26 41 25 114 [00588] 38 5 52 15 115 [00589] 83 63 92 75 116 [00590] 85 57 85 67 117 [00591] 85 10 88 12 118 [00592] 10 0 32 0 119 [00593] 93 63 92 63 120 [00594] 43 4 90 8 121 [00595] 100 98 98 92 122 [00596] 100 73 93 90 123 [00597] 100 82 90 78 124 [00598] 98 87 92 75 125 [00599] 72 9 90 44 126 [00600] 87 34 95 70 127 [00601] 90 44 93 62 128 [00602] 32 2 77 2 129 [00603] 28 1 24 2 130 [00604] 20 1 40 1 131 [00605] 0 0 2 0 132 [00606] 1 0 6 0 133 [00607] 1 0 2 0 134 [00608] 37 10 22 7 135 [00609] 15 1 16 2 136 [00610] 1 0 3 2 137 [00611] 19 2 50 5 138 [00612] 47 2 35 1 139 [00613] 47 2 72 24 140 [00614] 8 0 13 4 141 [00615] 2 0 2 0 142 [00616] 19 5 26 5 143 [00617] 4 0 15 0 144 [00618] 87 80 92 90 145 [00619] 28 8 37 16 146 [00620] 73 12 77 48 147 [00621] 73 18 95 18 148 [00622] 9 2 13 7 149 [00623] 83 45 87 31 150 [00624] 56 8 70 29 151 [00625] 37 3 53 6 152 [00626] 24 1 38 7 153 [00627] 12 3 22 1 154 [00628] 30 13 63 9 155 [00629] 97 30 93 20 156 [00630] 27 0 47 3 157 [00631] 1 0 1 0 158 [00632] 0 0 2 0 159 [00633] 28 2 28 1 160 [00634] 100 97 87 90 161 [00635] 100 100 100 90 162 [00636] 0 0 1 0 163 [00637] 20 1 47 9 164 [00638] 5 0 27 0 165 [00639] 0 0 17 0 166 [00640] 100 83 90 43 167 [00641] 2 0 9 0 168 [00642] 2 0 5 0 169 [00643] 77 0 77 0 170 [00644] 9 0 4 0 171 [00645] 100 100 80 50 172 [00646] 35 1 83 12 173 [00647] 100 53 97 17 174 [00648] 100 100 80 70 175 [00649] 100 97 100 93 176 [00650] 100 100 100 90 177 [00651] 100 21 87 47 178 [00652] 6 0 2 0 179 [00653] 100 47 90 28 180 [00654] 40 7 5 0 181 [00655] 22 11 33 5 182 [00656] 6 0 13 0 183 [00657] 16 0 38 2 184 [00658] 42 4 16 1 185 [00659] 100 67 90 77 186 [00660] 1 0 2 0 187 [00661] 100 100 90 90 188 [00662] 1 0 11 0 189 [00663] 82 28 97 37 190 [00664] 20 0 45 3 191 [00665] 77 2 83 22 193 [00666] 15 0 14 0 196 [00667] 1 0 11 5 197 [00668] 0 0 2 0 198 [00669] 4 1 0 0 199 [00670] 0 0 0 0 200 [00671] 93 73 100 77 202 [00672] 90 22 100 47 203 [00673] 87 32 93 32 204 [00674] 50 4 80 5 206 [00675] 100 67 100 90 207 [00676] 40 11 83 5 211 [00677] 100 43 100 77 213 [00678] 50 3 40 11 214 [00679] 14 0 28 4 215 [00680] 87 37 87 33 216 [00681] 77 13 80 29 217 [00682] 97 53 93 100 218 [00683] 100 87 100 100 219 [00684] 60 8 87 43 220 [00685] 90 30 100 77 221 [00686] 100 63 100 100 222 [00687] 100 57 100 93 223 [00688] 4 0 28 0 224 [00689] 97 100 100 100 225 [00690] 83 27 100 97 226 [00691] 28 3 57 7 227 [00692] 100 47 100 57 228 [00693] 5 0 22 2 229 [00694] 27 2 77 6 230 [00695] 22 1 73 4 231 [00696] 0 0 2 0 232 [00697] 100 73 100 83 233 [00698] 100 57 87 27 234 [00699] 53 18 53 15 235 [00700] 100 73 87 77 236 [00701] 97 77 97 100 238 [00702] 100 53 100 77 240 [00703] 70 8 73 3 241 [00704] 3 0 33 12 242 [00705] 87 10 87 20 243 [00706] 4 0 37 1 244 [00707] 14 0 15 2 245 [00708] 28 8 13 2 246 [00709] 40 15 77 7 247 [00710] 16 2 33 8 248 [00711] 33 2 30 2 249 [00712] 87 37 90 43 250 [00713] 90 90 90 80 251 [00714] 80 80 80 80 252 [00715] 50 3 87 32 253 [00716] 100 87 100 57 254 [00717] 100 77 100 100 255 [00718] 97 83 100 87 256 [00719] 50 18 70 20 257 [00720] 93 35 100 57 258 [00721] 32 7 73 8 259 [00722] 80 17 93 40 260 [00723] 22 0 22 0 261 [00724] 70 9 87 32 262 [00725] 63 1 47 4 263 [00726] 80 15 73 22 266 [00727] 67 18 90 43 267 [00728] 2 0 10 4 268 [00729] 63 6 60 17 269 [00730] 5 0 18 0 270 [00731] 3 0 0 1 271 [00732] 5 1 272 [00733] 60 8 273 [00734] 60 3 277 [00735] 100 60 100 100 278 [00736] 90 60 90 93 282 [00737] 15 18 283 [00738] 83 30 87 22 284 [00739] 63 44 62 34 285 [00740] 87 50 90 35 286 [00741] 67 15 97 27 288 [00742] 87 30 97 20 290 [00743] 92 14 83 21 294 [00744] 1 1 2 0 295 [00745] 2 0 11 0 296 [00746] 100 40 100 83 297 [00747] 90 37 87 37 298 [00748] 63 7 97 37 299 [00749] 53 13 53 22 302 [00750] 47 4 47 3 303 [00751] 2 0 12 0 304 [00752] 53 28 100 37 312 [00753] 100 53 314 [00754] 100 40 315 [00755] 100 60 321 [00756] 100 40 324 [00757] 2 1 12 0 325 [00758] 24 4 22 1 326 [00759] 25 0 30 1 327 [00760] 23 3 48 4 328 [00761] 33 8 23 5 329 [00762] 100 53 100 73 330 [00763] 83 24 93 17 335 [00764] 77 53 80 25 336 [00765] 63 20 50 17 337 [00766] 9 0 13 1 340 [00767] 23 4 42 7 344 [00768] 6 0 16 0 345 [00769] 22 1 32 1 346 [00770] 4 0 5 0 349 [00771] 97 50 97 35 354 [00772] 17 2 21 4 355 [00773] 34 7 48 4 357 [00774] 13 1 18 0 358 [00775] 77 17 83 18 359 [00776] 100 37 100 43 360 [00777] 53 9 80 5 361 [00778] 80 18 88 31 363 [00779] 29 1 25 2 365 [00780] 77 15 97 43 366 [00781] 53 13 83 12 367 [00782] 63 9 93 30 368 [00783] 83 47 90 73 372 [00784] 85 26 85 16 373 [00785] 77 27 100 38 375 [00786] 47 8 40 6 378 [00787] 18 1 17 1 380 [00788] 53 5 60 12 387 [00789] 60 30 80 47 388 [00790] 1 0 3 0 389 [00791] 28 4 43 3 390 [00792] 22 0 18 2 393 [00793] 93 55 93 42 394 [00794] 9 3 12 2 395 [00795] 43 4 67 18 396 [00796] 3 0 4 0 399 [00797] 67 8 90 15 400 [00798] 2 0 8 0 401 [00799] 17 5 32 4 405 [00800] 97 27 70 27 406 [00801] 97 30 67 23 407 [00802] 12 6 17 4 408 [00803] 30 12 33 13 409 [00804] 77 40 83 73 410 [00805] 9 0 35 1 412 [00806] 47 6 40 6 413 [00807] 40 15 33 15 414 [00808] 53 9 53 15 415 [00809] 47 5 67 11 416 [00810] 57 27 67 25 417 [00811] 35 18 63 22 418 [00812] 70 33 73 57 419 [00813] 40 18 60 12 420 [00814] 8 0 12 1 421 [00815] 100 33 87 57 422 [00816] 30 0 32 2 423 [00817] 100 57 93 53 424 [00818] 100 27 97 50 425 [00819] 27 28 53 40 426 [00820] 7 1 27 10 427 [00821] 100 90 60 47 428 [00822] 70 11 83 20 429 [00823] 83 50 67 43 430 [00824] 22 6 37 17 431 [00825] 32 7 40 12 432 [00826] 12 0 13 3 433 [00827] 83 67 80 57 435 [00828] 93 57 87 60 436 [00829] 70 15 73 27 437 [00830] 2 0 8 0 440 [00831] 93 23 73 23 441 [00832] 100 43 97 50 442 [00833] 100 93 80 77 444 [00834] 100 47 83 53 445 [00835] 15 1 30 2 446 [00836] 2 0 6 0 447 [00837] 7 0 33 1 449 [00838] 33 10 57 9 450 [00839] 3 1 4 1 451 [00840] 1 0 2 0 452 [00841] 60 6 70 14 458 [00842] 93 57 83 50 461 [00843] 26 2 52 6 462 [00844] 37 6 55 10 463 [00845] 6 0 3 0 464 [00846] 1 0 8 0

Comparative Trials

[0224]

TABLE-US-00008 TABLE C1 PHAKPA (F129L) Disease level (%) P2 at P2 at P6 at P6 at Compound Structure 4 ppm 16 ppm 4 ppm 16 ppm Trifloxystrobin as comparative example [00847] 71 17 79 33 Ex. 9 [00848] 35 23 41 4

TABLE-US-00009 TABLE C2 PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm P6 at 4 ppm Comparative example [00849] 6 30 Ex. 231 [00850] 0 2 Comparative example [00851] 27 70 Ex. 58 [00852] 0 4 Comparative example [00853] 100 100 Ex. 6 [00854] 0 23 Comparative example [00855] 40 80 Ex. 158 [00856] 1 4 Comparative example [00857] 43 80 Ex. 157 [00858] 0 2 Comparative example [00859] 100 97 Ex. 4 [00860] 2 17 Comparative example [00861] 87 100 Ex. 31 [00862] 0 12 Comparative example [00863] 12 38 Ex. 8 [00864] 1 13 Comparative example [00865] 43 77 Ex. 41 [00866] 4 35 Comparative example [00867] 35 83 Ex. 165 [00868] 0 27 Comparative example [00869] 87 97 Ex. 130 [00870] 33 67 Comparative example [00871] 60 70 Ex. 188 [00872] 2 30 Comparative example [00873] 43 90 Ex. 73 [00874] 1 37 Untreated 100 99

TABLE-US-00010 TABLE C3 PHAKPA (F129L) Disease level (%) Compound Structure P2 at 16 ppm P6 at 16 ppm Comparative example [00875] 23 28 Ex. 120 [00876] 6 15 Comparative example [00877] 87 80 Ex. 126 [00878] 32 60 Comparative example [00879] 37 28 Ex. 113 [00880] 17 6 Comparative example [00881] 37 63 Ex. 159 [00882] 0 0 Comparative example [00883] 11 4 Ex. 60 [00884] 0 0 Comparative example [00885] 16 35 Ex. 12 [00886] 3 9 Comparative example [00887] 15 15 Ex. 27 [00888] 0 0 Comparative example [00889] 70 53 Ex. 282 [00890] 15 18 Comparative example [00891] 23 32 Ex. 205 [00892] 1 1 Untreated 100 87

TABLE-US-00011 TABLE C4 PHAKPA (F129L) Disease level (%) Compound Structure P2 at 16 ppm P6 at 16 ppm Comparative example [00893] 27 17 Ex. 3 [00894] 2 1 Comparative example [00895] 80 87 Ex. 56 [00896] 32 15 Comparative example [00897] 87 90 Ex. 36 [00898] 47 57 Comparative example [00899] 25 10 Ex. 5 [00900] 1 4 Comparative example [00901] 67 33 Ex. 216 [00902] 20 15 Comparative example [00903] 83 77 Ex. 1 [00904] 28 47 Comparative example [00905] 43 13 Ex. 37 [00906] 0 0 Comparative example [00907] 87 43 Ex. 30 [00908] 2 1 Comparative example [00909] 57 60 Ex. 181 [00910] 12 5 Comparative example [00911] 87 53 Ex. 155 [00912] 23 18 Comparative example [00913] 100 90 Ex. 28 [00914] 30 18 Comparative example [00915] 63 43 Ex. 154 [00916] 25 17 Comparative example [00917] 93 83 Ex. 76 [00918] 1 0 Comparative example [00919] 90 80 Ex. 86 [00920] 6 7 Comparative example [00921] 73 70 Ex. 153 [00922] 5 1 Comparative example [00923] 80 43 Ex. 104 [00924] 37 28 Comparative example [00925] 11 9 Ex. 244 [00926] 0 2 Comparative example [00927] 1 22 Ex. 131 [00928] 0 0 Untreated >90 >85

[0225] The results in Tables C1 to C4 show that the specific substituent at position R.sup.3 improves the fungicidal activity against phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors compared to compounds where the position R.sup.3 is unsubstituted.

TABLE-US-00012 TABLE C5 Fungal growth (%) 0.016 0.016 Concentration applied (ppm) 0.016 ALTESO ALTESO 0.016 Compound Structure PYRIOR wt F129L MONGNI Comparative example from WO 2017/157923 [00929] 87 98 100 97 Ex. 158 [00930] 38 66 79 71

TABLE-US-00013 TABLE C6a PHAKPA P1 DL Disease level (%) Qo I-sensitive wt isolate (0% F129L) Test concentration (ppm) Compound Structure 0 0.3 1 3 10 30 100 300 Comparative example from WO 17/157923 [00931] 93 78 80 77 48 30 18 5 Ex. 158 [00932] 38 7 2 1 4 5 4

TABLE-US-00014 TABLE C6b PHAKPA P1 DL Disease level (%) Qo I-resistant F129L isolate (100% F129L) Test concentration (ppm) Compound Structure 0 0.3 1 3 10 30 100 300 Comparative example from WO 17/157923 [00933] 93 88 90 95 92 90 65 52 Ex. 158 [00934] 87 57 8 2 4 4 5

[0226] The results in Tables 05 to C6b show that the compounds to the present invention significantly improve the fungicidal activity against phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors compared to the use of a compound disclosed in WO 2017/157923.

TABLE-US-00015 TABLE C7a Fungal growth (%) 0.016 0.025 Concentration applied (ppm) 0.016 ALTESO PYRNTE 4 Compound Structure PYRIOR wt wt CERCSO Comparative example from WO 98/23156 [00935] 100 94 84 33 Ex. 9 [00936] 38 73 44 11

TABLE-US-00016 TABLE C7b PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm Comparative example from WO 98/23156 [00937] 17 Ex. 9 [00938] 6 Untreated 92

TABLE-US-00017 TABLE C8a Fungal growth (%) 0.016 4 Concentration applied (ppm) 0.016 0.063 ALTESO ALTESO Compound Structure PYRIOR COLLLA wt F129L Comparative example from WO 98/23156 [00939] 100 77 94 87 Ex. 84 [00940] 48 33 43 39

TABLE-US-00018 TABLE C8b Fungal growth (%) 0.25 0.25 Concentration applied (ppm) PYRNTE PYRNTE 0.063 0.016 Compound Structure wt F129L LEPTNO MONGNI Comparative example from WO 98/23156 [00941] 87 84 79 86 Ex. 84 [00942] 39 49 60 32

[0227] The results in Table C7a to C8b show that the specific substituent R.sup.a of the terminal phenyl improves the fungicidal activity against phytopathogenic fungi compared to compounds from the prior art.

TABLE-US-00019 TABLE C9 Fungal growth (%) Concentration applied (ppm) 0.016 0.063 4 Compound Structure PYRIOR LEPTNO CERCSO Comparative example from WO 98/23156 [00943] 58 100 56 Ex. 9 [00944] 38 67 11

TABLE-US-00020 TABLE C10 Fungal growth (%) 0.016 Concentration applied (ppm) 0.016 0.063 ALTESO 4 0.016 Compound Structure PYRIOR LEPTNO F129L CERCSO MONGNI Comparative example from WO 98/23156 [00945] 49 93 85 66 84 Ex. 8 [00946] 13 70 55 27 54

TABLE-US-00021 TABLE C11a Fungal growth (%) 0.016 0.016 Concentration applied (ppm) 0.016 0.25 0.063 ALTESO ALTESO Compound Structure PYRIOR SEPTTR LEPTNO wt F129L Comparative example from WO 98/23156 [00947] 39 77 95 100 87 Ex. 8 [00948] 13 57 70 56 52

TABLE-US-00022 TABLE C11b Fungal growth (%) Concentration applied (ppm) 4 0.016 Compound Structure CERCSO MONGNI Comparative example from WO 98/23156 [00949] 60 80 Ex. 8 [00950] 27 54

TABLE-US-00023 TABLE C12 Fungal growth (%) 0.25 Concentration applied (ppm) 0.016 0.25 0.063 0.016 PYRTNE Compound Structure PYRIOR SEPTTR COLLLA MONGNI F129L Comparative example from WO 98/23156 [00951] 87 61 81 69 Comparative example from WO 98/23156 [00952] 82 89 93 84 87 Ex. 76 [00953] 43 0 39 35 66

TABLE-US-00024 TABLE C13 Fungal growth (%) 0.016 0.016 0.25 Concentration applied (ppm) 0.063 ALTESO ALTESO PYRNTE 4 Compound Structure LEPTNO wt F129L wt CERCSO Comparative example from WO 98/23156 [00954] 85 67 66 59 71 Comparative example from WO 98/23156 [00955] 65 93 81 53 67 Comparative example from WO 98/23156 [00956] 100 100 87 78 87 Ex. 76 [00957] 39 55 37 39 28

TABLE-US-00025 TABLE C14 Fungal growth (%) 0.016 0.016 Concentration applied (ppm) 0.016 0.25 0.063 ALTESO ALTESO Compound Structure PYRIOR SEPTTR COLLLA wt F129L Comparative example from WO 98/23156 [00958] 80 100 81 93 95 Comparative example from WO 98/23156 [00959] 81 87 93 89 93 Ex. 77 [00960] 20 49 39 73 69

TABLE-US-00026 TABLE C15a Fungal growth (%) 0.016 0.016 Concentration applied (ppm) 0.016 0.25 0.063 ALTESO ALTESO Compound Structure PYRIOR SEPTTR COLLLA wt F129L Comparative example from WO 98/23156 [00961] 88 39 82 94 100 Comparative example from WO 98/23156 [00962] 83 39 89 81 89 Ex. 153 [00963] 50 0 55 71 68

TABLE-US-00027 TABLE C15b Fungal growth (%) 0.25 Concentration applied (ppm) 0.063 PYRNTE 4 0.016 Compound Structure LEPTNO wt CERCSO MONGNI Comparative example from WO 98/23156 [00964] 88 57 62 95 Comparative example from WO 98/23156 [00965] 69 61 Ex. 153 [00966] 55 31 26 75

TABLE-US-00028 TABLE C16a Fungal growth (%) 0.25 0.016 Concentration applied (ppm) 0.016 0.25 0.063 ALTESO ALTESO Compound Structure PYRIOR SEPTTR COLLLA wt F129L Comparative example from WO 98/23156 [00967] 100 59 82 43 90 Ex. 157 [00968] 15 20 63 27 57

TABLE-US-00029 TABLE C16b Fungal growth (%) 0.25 0.25 Concentration applied (ppm) PYRNTE PYRNTE 4 0.016 Compound Structure wt F129L CERCSO MONGNI Comparative example from WO 98/23156 [00969] 76 80 78 100 Ex. 157 [00970] 54 58 36 56

TABLE-US-00030 TABLE C17 PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm P6 at 16 ppm Comparative example from WO 98/23156 [00971] 83 57 Comparative example from WO 98/23156 [00972] 80 37 Comparative example from WO 98/23156 [00973] 60 30 Ex. 76 [00974] 35 4 Comparative example from WO 98/23156 [00975] 45 Comparative example from WO 98/23156 [00976] 67 67 Ex. 77 [00977] 37 20 Comparative example from WO 98/23156 [00978] 23 Ex. 9 [00979] 1 Comparative example from WO 98/23156 [00980] 20 9 Ex. 157 [00981] 1 1 Comparative example from WO 98/23156 [00982] 83 87 Comparative example from WO 98/23156 [00983] 47 18 Ex. 153 [00984] 19 5 Untreated 92 75

TABLE-US-00031 TABLE C18 PHAKPA (F129L) Disease level (%) Compound Structure P2 at 1 ppm P6 at 4 ppm Comparative example from WO 98/23156 [00985] 32 43 Ex. 8 [00986] 6 1 Untreated 92 75

[0228] The result in Tables C9 to C18 show that the specific substituent R.sup.4 improves the fungicidal activity against phytopathogenic fungi compared to compounds from the prior art.