NEW SUBSTITUTED PYRIDINES AS FUNGICIDES

Abstract

The present invention relates to the compounds of formula (I) wherein the variables are defined as given in the description and claims. The invention further relates to their use and composition.

##STR00001##

Claims

1. A compound of formula I ##STR00112## wherein R.sup.1 is H; R.sup.2 is selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-halogenalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-halogenalkynyl, OC.sub.1-C.sub.6-alkyl, OC.sub.2-C.sub.6-alkenyl, OC.sub.2-C.sub.6-alkynyl, and C.sub.3-C.sub.6-cycloalkyl; R.sup.3 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-halogenalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-halogenalkynyl, OC.sub.1-C.sub.6-alkyl, OC.sub.2-C.sub.6-alkenyl, OC.sub.2-C.sub.6-alkynyl, and C.sub.3-C.sub.6-cycloalkyl; R.sup.4 is H; R.sup.5 is selected from the group consisting of H, F, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-halogenalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-halogenalkynyl, phenyl, and benzyl, wherein the phenyl and benzyl moieties of R.sup.5 are unsubstituted or substituted by one to three groups R.sup.5a, which independently of one another are selected from the group consisting of: halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, and OC.sub.1-C.sub.6-alkyl; R.sup.6 is selected from the group consisting of F, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-halogenalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-halogenalkynyl, phenyl, and benzyl, wherein the phenyl and benzyl moieties of R.sup.6 are unsubstituted or substituted by one to three groups R.sup.6a, which independently of one another are selected from the group consisting of: halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, and OC.sub.1-C.sub.6-alkyl; or R.sup.5 and R.sup.6 form together with the C atoms to which they are bound a C.sub.3-C.sub.6-cycloalkyl or a 3- to 6-membered saturated heterocycle which contains 1, 2, or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubstituted or substituted by a halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl; X is in each case independently selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, OC.sub.1-C.sub.6-alkyl, OC.sub.1-C.sub.6-halogenalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, and C.sub.2-C.sub.6-alkynyl; n is 0, 1, 2, or 3 and N-oxides and agriculturally acceptable salts thereof as fungicides.

2. The compound of claim 1, wherein R.sup.2 is C.sub.1-C.sub.6-alkyl.

3. The compound of claim 1, wherein R.sup.2 is CH.sub.3.

4. The compound of claim 1, wherein R.sup.3 is selected from C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-halogenalkyl.

5. The compound of claim 1, wherein R.sup.3 is CH.sub.3 or CHF.sub.2.

6. The compound of claim 1, wherein R.sup.5 is C.sub.1-C.sub.6-alkyl.

7. The compound of claim 1, wherein R.sup.6 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, phenyl, and benzyl, wherein the phenyl and benzyl moieties of R.sup.5 are unsubstituted or substituted by one to three groups R.sup.5a, which independently of one another are selected from the group consisting of: halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, and OC.sub.1-C.sub.6-alkyl.

8. The compound of claim 1, wherein R.sup.5 and R.sup.6 form together with the C atoms to which they are bound a C.sub.3-C.sub.6-cycloalkyl.

9. The compound of claim 1, wherein X is selected from halogen, C.sub.1-C.sub.6-alkyl, OC.sub.1-C.sub.6-alkyl, and OC.sub.1-C.sub.6-halogenalkyl.

10. The compound of claim 1, wherein X is selected from the group consisting of F, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, OCHF.sub.2, and OCF.sub.3.

11. A composition, comprising a compound of formula I, as defined in claim 1, an N-oxide, or an agriculturally acceptable salt thereof.

12. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I, as defined in claim 1.

13. A seed, coated with at least one compound of the formula I, as defined in claim 1 or an agriculturally acceptable salt thereof, in an amount of from 0.1 to 10 kg per 100 kg of seed.

Description

I. SYNTHESIS EXAMPLES

Example 254-[6-(difluoromethyl)-5-methyl-3-pyridyl]spiro[1,3-benzoxazine-2,1-cyclobutane]

Example 25.1Preparation of spiro[3H-1,3-benzoxazine-2,1-cyclobutane]-4-one

[0343] p-TsOH (98 mg, 0.2 eq) was added to a suspension of 3-fluoro-2-hydroxy-benzamide (400 mg, 1 eq) and cyclobutanone (542 mg, 3 eq) in toluene (30 ml), and the mixture was heated at reflux with azeotropic removal of water for 12 h. The reaction solution was cooled and concentrated in vacuo, and the resultant residue was diluted with ethyl acetate, washed successively with 2 N HCl, water and brine, and dried over anhydrous magnesium sulfate. Removal of solvent in vacuo afforded the titled compound (526 mg) as a brown powder.

[0344] .sup.1H NMR (400 MHz, CDCl3): ? [ppm]: 8.02-7.86 (m, 1H), 7.47 (ddd, J=8.3, 7.3, 1.7 Hz, 1H), 7.10 (td, J=7.5, 1.1 Hz, 1H), 7.01 (ddd, J=8.3, 1.1, 0.5 Hz, 1H), 6.62 (s, 1H), 2.65-2.50 (m, 2H), 2.34 (ddtt, J=12.5, 6.4, 3.1, 1.5 Hz, 2H), 2.07-1.91 (m, 1H), 1.84 (dtt, J=11.6, 9.3, 6.4 Hz, 1H).

Example 25.2Preparation of spiro[1,3-benzoxazine-2,1-cyclobutane]-4-yl trifluoromethanesulfonate

[0345] Trifluoromethanesulfonic anhydride (7.8 g, 2.5 eq) and 2,6-lutidine (2.38 g, 2 eq) were added dropwise to a suspension of spiro[3H-1,3-benzoxazine-2,1-cyclobutane]-4-one (2.1 g, 1 eq) in dichloromethane (120 mL) under cooling at ?78? C., and the mixture was stirred at the same temperature for 1.0 hour. The reaction mixture stirred for 20 min at 0? C., poured into ice water, and the solution was extracted with dichloromethane. The organic layer was washed successively with a saturated aqueous solution of sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give the titled compound (1.8 g) as a brown oil. The title compound was used directly without further purification.

Example 25.3Preparation of 4-[6-(difluoromethyl)-5-methyl-3-pyridyl]spiro[1,3-benzoxazine-2,1-cyclobutane]

[0346] [6-(difluoromethyl)-5-methyl-3-pyridyl]boronic acid (572 mg, 1.1 eq), potassium carbonate (1.54 g, 4 eq), water (2 ml) and dichlorobis(triphenylphosphine)palladium(II) (391 mg, 0.2 eq) were added to a solution of spiro[1,3-benzoxazine-2,1-cyclobutane]-4-yl trifluoromethanesulfonate (900 mg, 1 eq) in dimethoxyethane (10 mL), and the mixture was stirred under argon atmosphere at 80? C. for 2.5 hours. After cooling, the reaction solution was diluted with ethyl acetate, and the solution was washed successively with water and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The crude product was purified by High Performance Liquid Chromatography on silica gel (HPLC-column Kinetex XB C18 1.7? (50?2.1 mm); eluent: acetonitrile/water (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) to give the titled compound (97 mg) as a yellow-brown oil.

[0347] .sup.1H NMR (400 MHz, CDCl3): ? [ppm]: 8.67-8.60 (m, 1H), 7.90-7.84 (m, 1H), 7.42 (td, J=7.8, 1.6 Hz, 1H), 7.12 (dd, J=7.7, 1.6 Hz, 1H), 7.02 (d, J=8.2 Hz, 1H), 6.98-6.93 (m, 1H), 6.75 (t, J=54.5 Hz, 1H), 2.59 (s, 3H), 2.57-2.46 (m, 4H), 1.99 (dddd, J=25.7, 15.6, 7.8, 4.1 Hz, 2H).

[0348] The compounds listed in Table I were prepared in an analogous manner.

##STR00057##

TABLE-US-00006 TABLE I Compounds Ex-1 to Ex-92 of the formula I Compounds Ex-1 to Ex-92 of formula I, wherein the meaning of R.sup.5, R.sup.6, R.sup.2, R.sup.3 and Xn are as defined in each line. *HPLC: High Performance Liquid Chromatography; HPLC-column Kinetex XB C18 1,7 ? (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). Rt: retention time in minutes. [00058] HPLC Rt Ex-No R.sup.2 R.sup.3 R.sup.5 R.sup.6 Xn (min)* Ex-1 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 H 1.22 Ex-2 CH.sub.3 CH.sub.3 CH.sub.3 C(CH.sub.3).sub.3 H 1.03 Ex-3 CH.sub.3 CHF.sub.2 CH.sub.3 C(CH.sub.3).sub.3 H 1.49 Ex-4 CH.sub.3 CH.sub.3 [00059] H Ex-5 CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H 0.921 Ex-6 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 0.783 Ex-7 CH.sub.3 CH.sub.3 CH.sub.2CH.sub.3 CH.sub.2CH.sub.3 H 0.906 Ex-8 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2CH(CH.sub.3).sub.2 H 0.976 Ex-9 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2C(CH.sub.3).sub.3 H 1.019 Ex-10 CH.sub.3 CH.sub.3 [00060] H Ex-11 CH.sub.3 CH.sub.3 [00061] H Ex-12 CH.sub.3 CH.sub.3 [00062] H Ex-13 CH.sub.3 CH.sub.3 [00063] H Ex-14 CH.sub.3 CH.sub.3 [00064] 8-tBu Ex-15 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 8-tBu 1.014 Ex-16 CH.sub.3 CH.sub.3 CH.sub.3 C(CH.sub.3).sub.3 8-tBu 1.216 Ex-17 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2CH.sub.3 H 0.852 Ex-18 CH.sub.3 CH.sub.3 H C(CH.sub.3).sub.3 H 0.982 Ex-19 CH.sub.3 CH.sub.3 [00065] H Ex-20 CH.sub.3 CH.sub.3 [00066] 8-CH.sub.3 Ex-21 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 8-CH.sub.3 0.859 Ex-22 CH.sub.3 CH.sub.3 [00067] 7,8-(CH.sub.3).sub.2 Ex-23 CH.sub.3 CH.sub.3 [00068] H Ex-24 CH.sub.3 CHF.sub.2 [00069] H Ex-25 CH.sub.3 CHF.sub.2 [00070] H Ex-26 CH.sub.3 CH.sub.3 [00071] H Ex-27 CH.sub.3 CH.sub.3 [00072] H Ex-28 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 8-F 0.81 Ex-29 CH.sub.3 CH.sub.3 [00073] 8-F Ex-30 CH.sub.3 CH.sub.3 CH.sub.3 C(CH.sub.3).sub.3 8-F 1.031 Ex-31 CH.sub.3 CH.sub.3 [00074] H Ex-32 CH.sub.3 CH.sub.3 [00075] H Ex-33 CH.sub.3 CH.sub.3 [00076] 8-Cl Ex-34 CH.sub.3 CH.sub.3 CH.sub.3 phenyl 8-F 1.379 Ex-35 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 7-OCH.sub.3 1.036 Ex-36 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 7-OCH.sub.3 0.795 Ex-37 CH.sub.3 CHF.sub.2 [00077] 7-OCH.sub.3 Ex-38 CH.sub.3 CH.sub.3 [00078] 7-OCH.sub.3 Ex-39 CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H 0.788 Ex-40 CH.sub.3 CH.sub.3 H c-propyl H 0.829 Ex-41 CH.sub.3 CH.sub.3 CH.sub.3 c-butyl H 0.968 Ex-42 CH.sub.3 CH.sub.3 CH.sub.3 c-butyl 8-Cl 1.039 Ex-43 CH.sub.3 CH.sub.3 CH.sub.3 c-butyl 8-F 0.987 Ex-44 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2Ph H 1.005 Ex-45 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.2Ph H 1.363 Ex-46 CH.sub.3 CHF.sub.2 [00079] 8-F Ex-47 CH.sub.3 CHF.sub.2 CH.sub.3 OCH.sub.2CH.sub.3 8-F 1.191 Ex-48 CH.sub.3 CHF.sub.2 CH.sub.3 OCH.sub.2C(CH.sub.3).sub.3 8-F 1.453 Ex-49 CH.sub.3 CHF.sub.2 [00080] 8-CH.sub.3 Ex-50 CH.sub.3 CHF.sub.2 [00081] 8-Cl Ex-51 CH.sub.3 CHF.sub.2 CH.sub.3 4-ClPh H 1.434 Ex-52 CH.sub.3 CHF.sub.2 CH.sub.3 4-FPh H 1.36 Ex-53 CH.sub.3 CHF.sub.2 [00082] 8-Br Ex-54 CH.sub.3 CHF.sub.2 CH.sub.3 OCH.sub.2CH(CH.sub.3).sub.2 H 1.428 Ex-55 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 8-F 1.227 Ex-56 CH.sub.3 CHF.sub.2 CH.sub.3 c-butyl H 1.404 Ex-57 CH.sub.3 CHF.sub.2 CH.sub.3 c-butyl 8-F 1.418 Ex-58 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.24-FPh H 1.383 Ex-59 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.24-ClPh H 1.448 Ex-60 CH.sub.3 CHF.sub.2 CH.sub.3 OCH.sub.2CH.sub.3 H 1.153 Ex-61 CH.sub.3 CHF.sub.2 H c-propyl H 1.211 Ex-62 CH.sub.3 CHF.sub.2 CH.sub.3 c-propyl H 1.312 Ex-63 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 8-Cl 1.316 Ex-64 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 7-OCH.sub.38-F 1.167 Ex-65 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 7-Cl 0.888 Ex-66 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 7-Cl 1.339 Ex-67 CH.sub.3 CH.sub.3 [00083] 7-Cl Ex-68 CH.sub.3 CHF.sub.2 [00084] 7-Cl Ex-69 CH.sub.3 CHF.sub.2 CH.sub.3 4-Fph 8-F 1.38 Ex-70 CH.sub.3 CH.sub.3 [00085] 7-OCH.sub.38-F Ex-70* CH.sub.3 CHF.sub.2 [00086] 7,8-(CH.sub.3).sub.2 Ex-71 CH.sub.3 CHF.sub.2 [00087] H Ex-72 CH.sub.3 CHF.sub.2 [00088] H Ex-73 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 7,8-(CH.sub.3).sub.2 1.195 Ex-74 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 7,8-(CH.sub.3).sub.2 0.91 Ex-75 CH.sub.3 CH.sub.3 [00089] 7-CF.sub.3 Ex-76 CH.sub.3 CHF.sub.2 [00090] 7-CF.sub.3 Ex-77 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 8-CH.sub.3 1.249 Ex-78 Cl OCH.sub.3 [00091] 8-F 1.383 Ex-79 Br OCH.sub.3 [00092] 8-F 1.40 Ex-80 Cl CH.sub.3 [00093] 8-Cl 1.38 Ex-81 Cl CH.sub.2CH.sub.3 [00094] 8-Cl 1.48 Ex-82 CH.sub.3 OCH.sub.3 [00095] 8-Cl 1.373 Ex-83 CH.sub.3 SCH.sub.3 [00096] 8-Cl 1.437 Ex-84 H OCH.sub.3 [00097] 8-Cl 1.032 Ex-85 Cl OCH.sub.3 [00098] 7-Cl 1.496 Ex-86 CH.sub.3 CHF.sub.2 [00099] 7,8-F2 1.496 Ex-87 CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 8-F 1.299 Ex-88 OCH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.3 8-F 1.076 Ex-89 CH.sub.3 CF.sub.3 CH.sub.3 CH.sub.3 8-F 1.304 Ex-90 F CF.sub.3 CH.sub.3 CH.sub.3 8-F 1.304 Ex-91 CH.sub.3 F CH.sub.3 CH.sub.3 8-F 1.13 Ex-92 CH.sub.3 Cl CH.sub.3 CH.sub.3 8-F 1.13

II. BIOLOGICAL EXAMPLES

Microtest

[0349] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

Example 1Activity Against the Grey Mold Botrytis cinerea in the Microtiterplate Test

[0350] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18? C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

[0351] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-2, Ex-3, Ex-4, Ex-5 and Ex-6 respectively, showed 0% growth of the pathogen.

Example 2Activity Against Fusarium culmorum in the Microtiterplate Test

[0352] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18? C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

[0353] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4 and Ex-6 respectively, showed 1% growth of the pathogen.

Example 3Activity Against the Grey Mold Botrytis cinerea in the Microtiterplate Test

[0354] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.

[0355] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, 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-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70*, Ex-71, Ex-72, Ex-73, Ex-74, Ex-76, Ex-77, Ex-79, Ex-87, Ex-88, Ex-89 respectively, showed unto 11% growth of the pathogen.

Example 4Activity Against Fusarium culmorum in the Microtiterplate Test

[0356] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt yeast-bactopeptone-glycerine or DOB solution was then added.

[0357] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-6, Ex-8, Ex-9, Ex-13, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-26, Ex-27, Ex-28, Ex-29, Ex-32, Ex-33, Ex-35, Ex-36, Ex-38, Ex-39, Ex-42, Ex-44, Ex-51, Ex-63, Ex-64, Ex-65, Ex-67, Ex-73, Ex-74, Ex-76, Ex-77 respectively, showed unto 19% growth of the pathogen.

Example 5Activity Against the Leaf Blotch on Wheat Caused by Septoria tritici in the Microtiterplate Test

[0358] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septorion tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.

[0359] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-8, Ex-14, Ex-15, Ex-18, Ex-21, Ex-22, Ex-23, Ex-26, Ex-29, Ex-30, Ex-33, Ex-42, Ex-46, Ex-49, Ex-50, Ex-66, Ex-68, Ex-70*, Ex-72, Ex-73, Ex-74, Ex-76, Ex-77, Ex-79 respectively, showed unto 20% growth of the pathogen.

Example 6Activity Against Microdochium nivale in the Microtiterplate Test

[0360] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Microdochium nivale isolates in a DOB media (ph 7) was then added.

[0361] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-19, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70 respectively, showed unto 18% growth of the pathogen.

Example 7Activity Against Colletotrichum orbiculare in the Microtiterplate Test

[0362] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Colletotrichum orbiculare isolates in a DOB media (ph 7) was then added.

[0363] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-60, Ex-62, Ex-63, Ex-65, Ex-69 respectively, showed unto 17% growth of the pathogen.

Example 8Activity Against Leptosphaeria nodorum in the Microtiterplate Test

[0364] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Leptosphaeria nodorum isolates in a DOB media (ph 7) was then added.

[0365] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70 respectively, showed unto 19% growth of the pathogen.

Example 9Activity Against Fusarium Gramminearis in the Microtiterplate Test

[0366] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Fusarium gramminearis isolates in a DOB media (ph 7) was then added.

[0367] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-6, Ex-8, Ex-9, Ex-13, Ex-17, Ex-20, Ex-21, Ex-22, Ex-26, Ex-29, Ex-33, Ex-35, Ex-36, Ex-38, Ex-44, Ex-65, Ex-66, Ex-67 respectively, showed unto 17% growth of the pathogen.

Example 10Activity Against Monilinia laxa in the Microtiterplate Test

[0368] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Monilinia laxa isolates in a DOB media (ph 7) was then added.

[0369] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-5, Ex-6, Ex-7, Ex-11, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-44, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-62, Ex-63, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 16% growth of the pathogen.

Example 11Activity Against Ustilago maydis in the Microtiterplate Test

[0370] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Ustilago maydis isolates in a DOB media (ph 7) was then added.

[0371] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-5, Ex-7, Ex-8, Ex-11, Ex-12, Ex-13, Ex-15, Ex-18, Ex-20, Ex-21, Ex-33, Ex-36, Ex-40, Ex-42, Ex-44, Ex-67 respectively, showed unto 19% growth of the pathogen.

Example 12Activity Against Pyrenophora teres Qoi (FL129) Resistant Isolate in the Microtiterplate Test

[0372] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Pyrenophora teres Qoi (FL129) resistant isolates in a DOB media (ph 7) was then added.

[0373] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-38, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-62, Ex-63, Ex-69 respectively, showed unto 16% growth of the pathogen.

Example 13Activity Against Leptosphaeria maculans in the Microtiterplate Test

[0374] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Leptosphaeria maculans isolates in a DOB media (ph 7) was then added.

[0375] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 10% growth of the pathogen.

Example 14Activity Against Corynespora cassiicola in the Microtiterplate Test

[0376] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Corynespora cassiicola isolates in a DOB media (ph 7) was then added.

[0377] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-17, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-27, Ex-29, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 19% growth of the pathogen.

Example 15Activity Against Corynespora cassiicola (CORYCA-G) G413A Mutant in the Microtiterplate Test

[0378] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Corynespora cassiicola (CORYCA-G) G413A mutant isolates in a DOB media (ph 7) was then added.

[0379] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 19% growth of the pathogen.

[0380] 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.

Green House

[0381] 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) solventemulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml.

[0382] This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.

Example 16Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper

[0383] Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 2411C and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0384] In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-13, Ex-14, Ex-17, Ex-20, Ex-30, Ex-31, Ex-34, Ex-36 and Ex-38 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 90% infected.

Example 17Preventative Fungicidal Control of White Mold on Oilseed Rape Caused by Sclerotinia sclerotiorum

[0385] Oilseed rapes were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to runoff with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the applicated rape petals were fixed with 25 ?l of 2.5% methylcellulose on leaf 1 and 2. 25 ?l of a spore suspension of Sclerotinia sclerotiorum was pipetted on each fixed rape petal. After 14 days at 20? C. and a relative humidity of 60% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0386] In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-1, Ex-25, Ex-33, Ex-42, Ex-46, Ex-47, Ex-49, Ex-50, Ex-54, Ex-55 and Ex-63 respectively, showed up to at most 10% growth of the pathogen whereas the untreated plants were 100% infected.

Example 18Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper

[0387] Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24? C. and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0388] In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-13, Ex-14, Ex-17, Ex-20, Ex-31, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-42, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-56, Ex-57, Ex-58, Ex-60, Ex-62, Ex-64, Ex-70* and Ex-73 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 100% infected.

Example 19Long Lasting Control of Botrytis cinerea on Leaves of Green Pepper

[0389] Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The plants were then cultivated in the greenhouse for 7 days and then inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24? C. and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0390] In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-1, Ex-2, Ex-35, Ex-37, Ex-49 and Ex-63 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 90% infected.

Comparative Examples

Example 1Activity Against Leaf Blotch on Wheat Caused by Septoria tritici

[0391] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18? C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00007 Growth (%) Compound Structure at 125 pm Ex-51 acc. to the pending application [00100] 46 D1 = WO 2010/125782 [00101] 69 Ex-58 acc. to the pending application [00102] 73 D1 = WO 2010/125782 [00103] 93

Example 2Activity Against Wheat Leaf Spots Caused by Leptosphaeria nodorum

[0392] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOE solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18? C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00008 Growth (%) at 125 Compound Structure pm Ex-51 acc. to the pending application [00104] 15 D1 = WO 2010/125782 [00105] 47 Ex-58 acc. to the pending application [00106] 8 D1 = WO 2010/125782 [00107] 43

Example 3Activity Against Anthracnose Caused by Colletotrichum orbiculare in the Microtiterplate Test

[0393] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Colletotrichum orbiculare in an aqueous bio malt solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18? C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00009 Growth (%) Compound Structure at 2 pm Ex-51 acc. to the pending application [00108] 22 D1 = WO 2010/125782 [00109] 88 Ex-58 acc. to the pending application [00110] 55 D1 = WO 2010/125782 [00111] 96

[0394] 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.