NEW SUBSTITUTED PYRIDINES AS FUNGICIDE

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 ##STR00077## 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, OC.sub.1-C.sub.6-alkyl, 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, OC.sub.1-C.sub.6-alkyl, 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, phenyl, and benzyl, wherein the moieties 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 H, F, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl, C.sub.2-C.sub.6-alkenyl, phenyl, and benzyl, wherein the 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 ?O; 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, 2u or 3 heteroatoms from the group consisting of O and S; wherein the cycloalkyl or heterocycle can be unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-halogenalkyl; R.sup.7 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, phenyl, and benzyl, wherein the moieties are unsubstituted or substituted by one to three groups R.sup.7a, 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.8 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, phenyl, and benzyl, wherein the moieties are unsubstituted or substituted by one to three groups R.sup.8a, 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.7 and R.sup.8 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; 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, with the proviso that R.sup.5, R.sup.6, R.sup.7, R.sup.8 cannot be all H; and N-oxides and the agriculturally acceptable salts thereof as fungicides.

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

7. The compound of claim 1, wherein R.sup.6 is H or C.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 ?O or a C.sub.3-C.sub.6-cycloalkyl.

9. The compound of claim 1, wherein R.sup.7 is H or C.sub.1-C.sub.6-alkyl.

10. The compound of claim 1, wherein R.sup.8 is selected from the C.sub.1-C.sub.6-alkyl, phenyl, and benzyl, wherein the moieties are unsubstituted or substituted by one to three groups R.sup.5a, which independently of one another are ##STR00078##

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

12. 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.

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

14. A process for preparing a compound of formula I, comprising reacting a compound of formula Y: ##STR00079## wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and Xn are as defined in claim 1 and Hal is halogen.

15. A compound of the formula Y ##STR00080## wherein R.sup.5 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl, R.sup.6 is selected from the group consisting of H and C.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; R.sup.7 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl, R.sup.8 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl, or R.sup.7 and R.sup.8 form together with the C atoms to which they are bound a C.sub.3-C.sub.6-cycloalkyl; X is halogen or C.sub.1-C.sub.6-alkyl, N is 0, 1, or 2.

Description

I. Synthesis Examples

Step 1Preparation of 2,2,3-trimethylchroman-4-one oxime

[0439] Hydroxylamine hydrochloride (72.87 g, 3 eq) was added to a solution of 2,2,3-trimethylchroman-4-one (1 eq, 66.5 g) in pyridine (423 ml, 15 eq) and the reaction mixture was stirred for 18 h at 85? C. The reaction solution was poured into water (1000 ml), and the solution was extracted with heptane, washed successively with water and brine, and dried over anhydrous magnesium sulfate. Removal of solvent in vacuo afforded the titled compound (66.6) as a brown powder. The title compound was used directly without further purification. 1H NMR (400 MHZ, CDCl.sub.3): ? [ppm]: 9.15 (s, 1H), 7.75 (dd, J=7.9, 1.7 Hz, 1H), 7.26 (dd, J=7.1, 1.5 Hz, 1H), 6.91 (ddd, J=8.2, 7.2, 1.2 Hz, 1H), 6.86 (dd, J=8.3, 1.2 Hz, 1H), 3.39 (q, J=7.0 Hz, 1H), 1.45 (s, 3H), 1.27 (s, 3H), 1.13 (d, J=7.0 Hz, 3H).

Step 2Preparation of 2,2,3-trimethyl-3,4-dihydro-1,4-benzoxazepin-5-one

[0440] 2,2,3-trimethylchroman-4-one oxime (66 g, 1 eq) was added to thionyl chloride (80, 3.5 eq) at a temperature below 30? C., and the reaction mixture was stirred at 50? C. for 17 hours. After removal of thionyl chloride in vacuo the residue was poured into 1,4-dioxan (500 ml) and water (200 ml), and stirred for 1 h at 80? C. After removal of 1,4-dioxan in vacuo the resultant residue was extracted with ethyl acetate, washed successively with water and brine, and dried over anhydrous magnesium sulfate. Removal of solvent in vacuo the crude product was purified by flash chromatography on silica gel using heptane/MTBE as eluent to give the titled compound (25.4 g) as a with powder.

[0441] .sup.1H NMR (400 MHZ, CDCl.sub.3): ? [ppm]: 7.74 (dd, J=7.7, 1.8 Hz, 1H), 7.44 (td, J=7.7, 1.8 Hz, 1H), 7.20 (td, J=7.5, 1.1 Hz, 1H), 6.98 (dd, J=8.1, 1.1 Hz, 1H), 6.44 (s, 1H), 3.37 (qd, J=6.9, 5.2 Hz, 1H), 1.39 (s, 3H), 1.29 (s, 3H), 1.20 (d, J=6.9 Hz, 3H).

Step 3Preparation of 5-chloro-2,2,3-trimethyl-3H-1,4-benzoxazepine

[0442] A mixture of 2,2,3-trimethyl-3,4-dihydro-1,4-benzoxazepin-5-one (10 g, 1 eq) with phosphoryl chloride (100 ml) and 11.67 g phosphorus(V) chloride (1.15 eq) was stirred Heat for 2 h at 110? C. After cooling, the reaction solution concentrated in vacuo, diluted with dichloromethane, washed twice with saturated sodium carbonate solution, and dried over anhydrous magnesium sulfate. Removal of solvent in vacuo afforded the crude product (10.8 g). The title compound was used directly without further purification.

Step 4Preparation of 5-[6-(difluoromethoxy)-5-methyl-3-pyridyl]-2,2,3-trimethyl-3H-1,4-benzoxazepine

[0443] [6-(difluoromethyl)-5-methyl-3-pyridyl]boronic acid (3.11 g, 1.2 eq), potassium carbonate (3.83 g, 2 eq), silver oxide (1.61, 0.5 eq) and dichlorobis(triphenylphosphine)palladium(II) (490 mg, 0.05 eq) were added to a solution of 5-chloro-2,2,3-trimethyl-3H-1,4-benzoxazepine (3.1 g, 1 eq) in dry tetrahydrofuran (57 mL), and the mixture was stirred under argon atmosphere at 80 ?C for 18 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 RP-18 using acetonitrile/water as eluent to give the titled compound (1.5 g) as a white powder.

[0444] .sup.1H NMR (400 MHZ, CDCl.sub.3): ? [ppm]: 8.58 (d, J=1.9 Hz, 1H), 7.92 (s, 1H), 7.46 (t, J=7.7 Hz, 1H), 7.18 (td, J=7.5, 1.2 Hz, 1H), 7.09 (td, J=7.7, 1.4 Hz, 2H), 6.73 (t, J=54.5 Hz, 1H), 3.28 (d, J=6.8 Hz, 1H), 2.54 (d, J=2.2 Hz, 3H), 1.59 (s, 3H), 1.45 (s, 3H), 1.39 (s, 3H).

TABLE-US-00007 TABLE I Compounds Ex-1 to Ex-101 of formula I, wherein the meaning of R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and Xn are as defined in each line. [00068] Ex-No R.sup.2 R.sup.3 R.sup.5 R.sup.6 R.sup.7 R.sup.8 Xn HPLC R.sub.t (min)* Ex-1 CH.sub.3 CH.sub.3 H C(CH.sub.3).sub.3 H H H 0.968 Ex-2 CH.sub.3 CH.sub.3 H H CH.sub.3 CH.sub.3 H 0.75 Ex-3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 0.789 Ex-4 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 0.887 Ex-5 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H H 0.684 Ex-6 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 H H H 0.794 Ex-7 CH.sub.3 CHF.sub.2 H H CH.sub.3 CH.sub.2OCH.sub.3 H 0.883 Ex-8 CH.sub.3 CHF.sub.2 H H CH.sub.3 CH.sub.3 H 0.86 Ex-9 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H 0.796 Ex-10 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H 0.893 Ex-11 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H 0.798 Ex-12 CH.sub.3 CHF.sub.2 H CH.sub.3 CH.sub.3 CH.sub.3 H 0.906 Ex-13 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H 0.797 Ex-14 CH.sub.3 CHF.sub.2 H CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H 0.927 Ex-15 CH.sub.3 CHF.sub.2 H C(CH.sub.3).sub.3 CH.sub.3 H H 1.132 Ex-16 CH.sub.3 CH.sub.3 C?O CH.sub.3 CH.sub.3 H 0.84 Ex-17 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 H 1.224 Ex-18 CH.sub.3 CHF.sub.2 H H (CH.sub.2).sub.4 H 0.962 Ex-19 CH.sub.3 CH.sub.3 H H (CH.sub.2).sub.4 H 0.841 Ex-20 CH.sub.3 CHF.sub.2 CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 H 0.932 Ex-21 CH.sub.3 CHF.sub.2 (CH.sub.2).sub.2 H H H 0.95 Ex-22 CH.sub.3 CHF.sub.2 H H (CH.sub.2).sub.3 H 0.939 Ex-23 CH.sub.3 CHF.sub.2 H C(CH.sub.3).sub.3 H H H 1.364 Ex-24 CH.sub.3 CH.sub.3 H C(CH.sub.3).sub.3 CH.sub.3 H H 0.954 Ex-25 CH.sub.3 CHF.sub.2 H H CH.sub.3 CH.sub.3 8-F 1.334 Ex-26 CH.sub.3 CHF.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 8-F 1.058 Ex-27 CH.sub.3 CH.sub.3 H H CH.sub.3 CH.sub.3 8-F 0.791 Ex-28 CH.sub.3 CHF.sub.2 (CH.sub.2).sub.3 H H H 0.917 Ex-29 CH.sub.3 CHF.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 8-Cl 1.116 Ex-30 CH.sub.3 CHF.sub.2 H H CH.sub.3 CH.sub.3 7-CH.sub.3 0.897 Ex-31 CH.sub.3 CHF.sub.2 H H H H 7-CH.sub.3 0.814 Ex-32 CH.sub.3 CHF.sub.2 H H (CH.sub.2).sub.2 H 0.855 Ex-33 CH.sub.3 CHF.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 8-CH.sub.3 0.945 Ex-34 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 8-F 0.823 Ex-35 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 8-CH.sub.3 0.837 Ex-36 CH.sub.3 CHF.sub.2 H c-propyl H H H 0.952 Ex-37 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 8-Br 1.33 Ex-38 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 2-F 1.226 Ex-39 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 8-CH.sub.3 1.273 Ex-40 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 8-F-7-OCH.sub.3 1.222 Ex-41 CH.sub.3 CHF.sub.2 C?O (CH.sub.2).sub.2 8-F 1.209 Ex-42 CH.sub.3 CHF.sub.2 C?O (CH.sub.2).sub.3 8-F 1.296 Ex-43 CH.sub.3 CHF.sub.2 C?O CH.sub.3 CH.sub.3 7,8-F.sub.2 1.287 Ex-44 CH.sub.3 CHF.sub.2 CH.sub.2CH.sub.3 CH.sub.3 H H H 0.850 Ex-45 CH.sub.3 CHF.sub.2 H CH.sub.3 H CH.sub.3 H 0.864 Ex-46 CH.sub.3 CHF.sub.2 C?O (CH.sub.2).sub.4 8-F 1.342 Ex-47 CH.sub.3 CHF.sub.2 (CH.sub.2).sub.2 H H 8-F 1.113 Ex-48 CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 H H 8-F 0.746 Ex-49 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 8-Cl 0.873 Ex-50 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 8-CF.sub.3 0.979 Ex-51 CH.sub.3 CHF.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 8-CF.sub.3 1.22 Ex-52 CH.sub.3 CHF.sub.2 H H CH.sub.3 (S)CH.sub.2OCH.sub.3 H 6.33 Ex-53 CH.sub.3 CHF.sub.2 H H CH.sub.3 (R)CH.sub.2OCH.sub.3 H 6.49 Ex-54 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 (S)CH.sub.2OCH.sub.3 H 4.24 Ex-55 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 (R)CH.sub.2OCH.sub.3 H 4.07 Ex-56 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 (S)CH.sub.2OCH.sub.3 H Ex-57 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 (R)CH.sub.2OCH.sub.3 H Ex-58 CH.sub.3 CHF.sub.2 H (S)C(CH.sub.3).sub.3 H (S)CH.sub.3 H 10.70 Ex-59 CH.sub.3 CHF.sub.2 H (S)C(CH.sub.3).sub.3 H (R)CH.sub.3 H Ex-60 CH.sub.3 CHF.sub.2 H (R)C(CH.sub.3).sub.3 H (S)CH.sub.3 H Ex-61 CH.sub.3 CHF.sub.2 H (R)C(CH.sub.3).sub.3 H (R)CH.sub.3 H 9.59 Ex-62 CH.sub.3 CH.sub.3 H (S)C(CH.sub.3).sub.3 H (S)CH.sub.3 H 7.34 Ex-63 CH.sub.3 CH.sub.3 H (S)C(CH.sub.3).sub.3 H (R)CH.sub.3 H Ex-64 CH.sub.3 CH.sub.3 H (R)C(CH.sub.3).sub.3 H (S)CH.sub.3 H Ex-65 CH.sub.3 CH.sub.3 H (R)C(CH.sub.3).sub.3 H (R)CH.sub.3 H 7.12 Ex-66 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-F 7.34 Ex-67 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-F 7.12 Ex-68 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 H 4.02 Ex-69 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 H 4.291 Ex-70 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-Cl 9.22 Ex-71 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-Cl 9.09 Ex-72 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-CH.sub.3 Ex-73 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-CH.sub.3 Ex-74 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-F Ex-75 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-F Ex-76 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-CH.sub.3 Ex-77 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-CH.sub.3 Ex-78 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 H (R)CH.sub.3 H 5.998 Ex-79 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 H (S)CH.sub.3 H 7.793 Ex-80 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 H (S)CH.sub.3 H 8.259 Ex-81 CH.sub.3 CHF.sub.2 H (S)c-propyl H H H Ex-82 CH.sub.3 CHF.sub.2 H (R)c-propyl H H H Ex-83 CH.sub.3 CH.sub.3 H (S)CH.sub.3 H (S)CH.sub.3 H 4.64 Ex-84 CH.sub.3 CH.sub.3 H (S)CH.sub.3 H (R)CH.sub.3 H 4.107 Ex-85 CH.sub.3 CH.sub.3 H (R)CH.sub.3 H (S)CH.sub.3 H 4.82 Ex-86 CH.sub.3 CHF.sub.2 (S)CH.sub.3 (S)CH.sub.2CH.sub.3 H H H 5.42 Ex-87 CH.sub.3 CHF.sub.2 (R)CH.sub.3 (R)CH.sub.2CH.sub.3 H H H 5.37 Ex-88 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 H (S)CH.sub.3 H Ex-89 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 H (R)CH.sub.3 H Ex-90 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 H (S)CH.sub.3 H Ex-91 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 H (R)CH.sub.3 H Ex-92 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-F 5.521 Ex-93 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-F 6.011 Ex-94 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-Cl 5.68 Ex-95 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-Cl 5.54 Ex-96 CH.sub.3 CH.sub.3 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-CF.sub.3 Ex-97 CH.sub.3 CH.sub.3 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-CF.sub.3 Ex-98 CH.sub.3 CHF.sub.2 H (S)CH.sub.3 CH.sub.3 CH.sub.3 8-CF.sub.3 Ex-99 CH.sub.3 CHF.sub.2 H (R)CH.sub.3 CH.sub.3 CH.sub.3 8-CF.sub.3 Ex-100 CH.sub.3 CHF.sub.2 (CH.sub.2).sub.2 H (R)CH.sub.3 H Ex-101 CH.sub.3 CHF.sub.2 (CH.sub.2).sub.2 H (S)CH.sub.3 H *HPLC: High Performance Liquid Chromatography; HPLC-column Kinetex XB C18 1.7 ? (50 ? 2.1 mm); eluent: acetonitrile/water + 0.1% trifluoroacetate acid (gradient from 5:95 to 100:0 in 1.5 at 60 ?C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min). *Chiral HPLC: High Performance Liquid Chromatography on Shimadzu Nexera LC-30 LCMS-2020; flow: 0.6 ml/min; HPLC-column: LUX i-Amylose-3 5 ?m 150 ? 4.6 mm; Eluent A: water + 0.1% HCOOH; eluent B: acetonitrile; flow gradient from 50% B to 100% B in 10 min at 40 ?C.

Microtest

[0445] 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

[0446] 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.

[0447] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-8, Ex-9, Ex-10 and Ex-11 respectively, showed 0% growth of the pathogen.

Example 2Activity Against Fusarium culmorum in the Microtiterplate Test

[0448] 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.

[0449] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-2 and Ex-3 respectively, showed 1% growth of the pathogen.

Example 3Activity Against Venturia inaequalis in the Microtiterplate Test

[0450] 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.

[0451] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-12 (at 50 ppm), Ex-18, Ex-21, Ex-22, Ex-24, Ex-28, Ex-29, Ex-31, Ex-36, Ex-44, Ex-45, Ex-47 respectively, showed unto 20% growth of the pathogen.

Example 4Activity Against the Grey Mold Botrytis cinerea in the Microtiterplate Test

[0452] 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.

[0453] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-3, Ex-4, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-15, Ex-16, Ex-17, Ex-19, Ex-20, Ex-21, Ex-22, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-38, Ex-39, Ex-43, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52+Ex-52 as racemat, Ex-68, Ex-69 respectively, showed unto 1% growth of the pathogen.

Example 5Activity Against Fusarium culmorum in the Microtiterplate Test

[0454] 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.

[0455] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-3, Ex-11, Ex-26, Ex-27, Ex-30, Ex-34, Ex-46, Ex-48, Ex-49, Ex-52 and Ex-53 as racemat, respectively, showed unto 9% growth of the pathogen.

Example 6Activity Against the Leaf Blotch on Wheat Caused by Septoria tritici in the Microtiterplate Test

[0456] 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.

[0457] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-21, Ex-28, Ex-33, Ex-47, Ex-48 respectively, showed unto 18% growth of the pathogen.

Example 7Activity Against Microdochium nivale in the Microtiterplate Test

[0458] 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.

[0459] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-7, Ex-9, Ex-11, Ex-12, Ex-13, Ex-15, Ex-16, 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-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-44, Ex-45, Ex-46, Ex-47, Ex-52 and Ex-53 as racemat, Ex-68, Ex-69 respectively, showed unto 19% growth of the pathogen.

Example 8Activity Against Colletotrichum orbiculare in the Microtiterplate Test

[0460] 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.

[0461] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-7, Ex-9, Ex-11, Ex-12, Ex-13, Ex-16, Ex-19, Ex-22, Ex-24, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-32, Ex-33, Ex-34, Ex-36, Ex-41, Ex-45, Ex-52 and Ex-53 as racemat, Ex-69 respectively, showed unto 15% growth of the pathogen.

Example 9Activity Against Leptosphaeria nodorum in the Microtiterplate Test

[0462] 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.

[0463] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-7, Ex-9, Ex-11, Ex-12, Ex-13, 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-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-42, Ex-43, Ex-44, Ex-45, Ex-46, Ex-47, Ex-52 and Ex-53 as racemat, Ex-68, Ex-69 respectively, showed unto 12% growth of the pathogen.

Example 10Activity Against Fusarium Gramminearis in the Microtiterplate Test

[0464] 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.

[0465] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-2, Ex-27, Ex-30, Ex-34 respectively, showed unto 16% growth of the pathogen.

Example 11Activity Against Monilinia laxa in the Microtiterplate Test

[0466] 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.

[0467] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-7, Ex-9, Ex-10, Ex-11, Ex-12, Ex-13, Ex-15, Ex-16, Ex-17, Ex-18, 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-36, Ex-40, Ex-44, Ex-45, Ex-47, Ex-52 and Ex-53 as racemat, Ex-68, Ex-69 respectively, showed unto 20% growth of the pathogen.

Example 12Activity Against Ustilago maydis in the Microtiterplate Test

[0468] 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.

[0469] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-24, Ex-41 respectively, showed 0% growth of the pathogen.

Example 13Activity Against Pyrenophora teres Qoi (FL129) Resistant Isolate in the Microtiterplate Test

[0470] 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.

[0471] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-7, Ex-9, Ex-10, Ex-11, Ex-12, Ex-13, Ex-15, Ex-16, 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-32, Ex-33, Ex-34, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-43, Ex-44, Ex-45, Ex-47, Ex-52 and Ex-53 as racemat, Ex-68, Ex-69 respectively, showed unto 19% growth of the pathogen.

Example 14Activity Against Leptosphaeria maculans in the Microtiterplate Test

[0472] 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.

[0473] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-11, Ex-12, 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-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-43, Ex-44, Ex-45, Ex-46, Ex-68, Ex-69 respectively, showed unto 19% growth of the pathogen.

Example 15Activity Against Phytophthora infestans in the Microtiterplate Test

[0474] 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 infestans in a DOB media (ph 7) was then added.

[0475] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-8, Ex-9, Ex-10, Ex-11, Ex-12, Ex-13, Ex-15, Ex-20, Ex-23, Ex-24, Ex-31 respectively, showed unto 19% growth of the pathogen.

Example 16Activity Against Mycosphaerella fijiensis in the Microtiterplate Test

[0476] 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 Mycosphaerella fijiensis isolates in a DOB media (ph 7) was then added.

[0477] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-6, Ex-15, 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-36, Ex-37, Ex-38, Ex-39, Ex-44, Ex-45 respectively, showed unto 20% growth of the pathogen.

Example 17Activity Against Corynespora cassiicola in the Microtiterplate Test

[0478] 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.

[0479] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-24, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-44, Ex-45, Ex-47, Ex-69 respectively, showed unto 16% growth of the pathogen.

Example 18Activity Against Corynespora cassiicola (CORYCA-G) G413A Mutant in the Microtiterplate Test

[0480] 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.

[0481] In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-24, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-38, Ex-44, Ex-45, Ex-47, Ex-69 respectively, showed unto 18% growth of the pathogen.

[0482] 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

[0483] 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.

[0484] This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.

Example 19Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper

[0485] 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.

[0486] In this test, the samples which had been treated with 250 ppm of the active substance from examples from examples Ex-1, Ex-2, Ex-3, Ex-4, Ex-8, Ex-9, Ex-12, Ex-13, Ex-16 and Ex-18 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 90% infected.

Example 20Preventative Fungicidal Control of White Mold on Oilseed Rape Caused by Sclerotinia sclerotiorum

[0487] Oilseed rapes were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to run-off 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.

[0488] In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-1, Ex-2, Ex-3, Ex-4, Ex-7, Ex-8, Ex-11, Ex-12, Ex-15, Ex-17, Ex-20, Ex-21, Ex-22, Ex-25, Ex-26, Ex-27, Ex-28, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-40, Ex-45, Ex-47 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 100% infected.

Example 21Preventative Fungicidal Control of Botrytis cinerea on Leaves of Green Pepper

[0489] 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.

[0490] In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-8, Ex-12, Ex-25, Ex-26, Ex-27 respectively, showed up to at most 18% growth of the pathogen whereas the untreated plants were 100% infected.

Example 22Long Lasting Control of Botrytis cinerea on Leaves of Green Pepper

[0491] 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.

[0492] In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-21, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-45, Ex-47, Ex-69 respectively, showed up to at most 14% growth of the pathogen whereas the untreated plants were 90% infected.

Comparative Examples

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

[0493] 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-00008 Growth (%) at 125 pm Compound Structure SEPTTR D1 = WO 2010/125782 [00069] 98 Ex-2 acc. to the pending application [00070] 51 Ex-11 acc. to the pending application [00071] 52 Ex-3 acc. to the pending application [00072] 64

Example 2Activity Against Wheat Leaf Spots Caused by Leptosphaeria nodorum

[0494] 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 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-00009 Growth (%) at 8 pm Compound Structure LEPTNO D1 = WO 2010/125782 [00073] 45 Ex-2 acc. to the pending application [00074] 4 Ex-11 acc. to the pending application [00075] 6 Ex-3 acc. to the pending application [00076] 30