5-halogenopyrazole biphenylcarboxamides

Abstract

The present invention relates to novel 1-methyl-3-dihalogenomehtyl-5-halogenopyrazole(thio)biphenyl carboxamides, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials.

Claims

1. A compound of formula (I) ##STR00016## in which Hal.sup.1 represents a chlorine or fluorine; Hal.sup.2 represents a chlorine or fluorine; T represents an oxygen or sulfur atom; A represents ##STR00017## where the bond marked by * is attached to the amide while the bond marked # is attached to (O).sub.n; m represents 0, 1 or 2; B represents ##STR00018## where the bond marked by * is attached to (O).sub.n while the bond marked # is attached to the imidoyl substituent s represents 0, 1 or 2; n represents 0; R.sup.a represents halogen; nitro, cyano, C.sub.1-C.sub.16-alkyl; C.sub.1-C.sub.6-haloalkyl having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkoxy; C.sub.1-C.sub.6-haloalkoxy having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkylsulfanyl; C.sub.1-C.sub.6-haloalkylsulfanyl having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkylsulfonyl; C.sub.1-C.sub.6-haloalkylsulfonyl having 1 to 9 identical or different halogen atoms; C.sub.2-C.sub.12-alkenyl; C.sub.2-C.sub.12-alkynyl; C.sub.3-C.sub.7-cycloalkyl; tri(C.sub.1-C.sub.8)alkylsilyl; tri(C.sub.1-C.sub.8)alkylsilyl-C.sub.1-C.sub.8-alkyl; R.sup.b represents halogen; nitro, cyano, C.sub.1-C.sub.16-alkyl; C.sub.1-C.sub.6-haloalkyl having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkoxy; C.sub.1-C.sub.6-haloalkoxy having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkylsulfanyl; C.sub.1-C.sub.6-haloalkylsulfanyl having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.6-alkylsulfonyl; C.sub.1-C.sub.6-haloalkylsulfonyl having 1 to 9 identical or different halogen atoms; C.sub.2-C.sub.12-alkenyl; C.sub.2-C.sub.12-alkynyl; C.sub.3-C.sub.7-cycloalkyl; tri(C.sub.1-C.sub.8)alkylsilyl; tri(C.sub.1-C.sub.8)alkylsilyl-C.sub.1-C.sub.8-alkyl; R.sup.1 represents hydrogen; C.sub.1-C.sub.16-alkyl; C.sub.3-C.sub.8-cycloalkyl; C.sub.1-C.sub.6-haloalkyl having 1 to 9 identical or different halogen atoms; (C.sub.3-C.sub.8-cycloalkyl)-C.sub.1-C.sub.8-alkyl; (C.sub.3-C.sub.8-cycloalkyl)-C.sub.3-C.sub.8-cycloalkyl; C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-alkynyl; C.sub.2-C.sub.8-alkenyl-C.sub.1-C.sub.16-alkyl; C.sub.2-C.sub.8-alkynyl-C.sub.1-C.sub.16-alkyl; R.sup.2 represents hydrogen; C.sub.1-C.sub.16-alkyl; C.sub.3-C.sub.8-cycloalkyl; C.sub.1-C.sub.6-haloalkyl having 1 to 9 identical or different halogen atoms; (C.sub.3-C.sub.8-cycloalkyl)-C.sub.3-C.sub.8-cycloalkyl; R.sup.1 and R.sup.2 furthermore may be linked to form a 5 or 6-member heterocyclic ring; provided that R.sup.1 and R.sup.2 do not represent simultaneously a methyl group, further provided that R.sup.1 does not represent hydrogen when R.sup.2 represents isopropyl or tert-butyl.

2. The compound of formula (I) according to claim 1, wherein Hal.sup.1 represents a chlorine or fluorine; Hal.sup.2 represents a chlorine or fluorine; T represents an oxygen atom; R.sup.a represents fluorine, chlorine, methyl or trifluoromethyl; m represents 0, 1 or 2; R.sup.b represents halogen; nitro, cyano, C.sub.1-C.sub.12-alkyl; C.sub.1-C.sub.4-haloalkyl having 1 to 9 identical or different halogen atoms; C.sub.1-C.sub.4-alkoxy; C.sub.1-C.sub.4-haloalkoxy having 1 to 9 identical or different halogen atoms; C.sub.3-C.sub.6-cycloalkyl; tri(C.sub.1-C.sub.4)alkylsilyl; tri(C.sub.1-C.sub.4)alkylsilyl-C.sub.1-C.sub.6-alkyl; s represents 0, 1 or 2; n represents 0; R.sup.1 represents hydrogen; C.sub.1-C.sub.12-alkyl; C.sub.1-C.sub.4-haloalkyl having 1 to 9 identical or different halogen atoms; C.sub.3-C.sub.6-cycloalkyl; R.sup.2 represents hydrogen; C.sub.1-C.sub.12-alkyl; C.sub.3-C.sub.6-cycloalkyl; C.sub.1-C.sub.4-haloalkyl having 1 to 9 identical or different halogen atoms; (C.sub.3-C.sub.6-cycloalkyl)-C.sub.3-C.sub.6-cycloalkyl; provided that R.sup.1 and R.sup.2 do not represent simultaneously a methyl group, further provided that R.sup.1 does not represent hydrogen when R.sup.2 represents isopropyl or tert-butyl.

3. The compound of formula (I) according to claim 1, wherein Hal.sup.1 is fluorine.

4. The compound of formula (I) according to claim 1, wherein T is oxygen.

5. The compound of formula (I) according to claim 1, wherein m is 0.

6. The compound of formula (I) according to claim 1, wherein s is 0.

7. A composition for controlling phytopathogenic harmful fungi, comprising at least one compound of the formula (I) according to claim 1, and one or more extenders and/or surfactants.

8. The composition according to claim 7 comprising at least one further active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and semiochemicals.

9. A process for producing a composition for controlling phytopathogenic harmful fungi, comprising mixing the compound of formula (I) according to claim 1 with one or more extenders and/or surfactants.

10. A method for controlling phytopathogenic harmful fungi, wherein compounds of the formula (I) ##STR00019## according to claim 1 are applied to the phytopathogenic harmful fungi and/or their habitat.

11. The method according to claim 10, wherein seed is treated with the compound of the formula (I).

12. A method according to claim 10, wherein one or more transgenic plants is treated with the compound of the formula (I).

13. A seed or seed of one or more transgenic plants treated with the compound of formula (I) according to claim 1.

14. A compound of formula (I), ##STR00020## in which A represents ##STR00021## where the bond marked by * is attached to the amide while the bond marked # is attached to (O).sub.n; B represents ##STR00022## where the bond marked by * is attached to (O).sub.n while the bond marked # is attached to the imidoyl substituent, wherein Hal.sup.1 represents a fluorine; Hal.sup.2 represents a chlorine or fluorine; T represents an oxygen atom; R.sup.a represents fluorine, chlorine; m represents 0 or 1; R.sup.b represents methyl, fluorine, chlorine, trifluoromethyl; s represents 0, 1 or 2; n represents 0; R.sup.1 represents hydrogen; methyl, trifluoromethyl; R.sup.2 represents methyl, ethyl, propyl, i-propyl, propargyl, n-, iso-, sec-, tert-butynyl; provided that R.sup.1 and R.sup.2 do not represent simultaneously a methyl group, further provided that R.sup.1 does not represent hydrogen when R.sup.2 represents isopropyl or tert-butyl.

15. The compound of formula (I) according to claim 14, wherein R.sup.1 is hydrogen or methyl.

16. A method for controlling phytopathogenic harmful fungi, wherein compounds of the formula (I) according to claim 14 are applied to the phytopathogenic harmful fungi and/or their habitat.

Description

PREPARATION EXAMPLES

(1) In analogy to the examples above and according to the general description of the processes of preparing the compounds according to the invention the compounds in the following Table 1 may be obtained.

(2) ##STR00014##

(3) TABLE-US-00001 TABLE 1 Ex. Hal.sup.1 Hal.sup.2 T A B n R.sup.a m R.sup.b s R.sup.1 R.sup.2 logP 1 F Cl O A-1 B-2 0 — 0 — 0 Me iPr 5.03[a] 2 F Cl O A-1 B-2 0 — 0 — 0 Me Et 4.58[a] 3 F Cl O A-1 B-2 0 — 0 — 0 Me propargyl 4.06[a] 4 F F O A-1 B-2 0 — 0 — 0 H propargyl 3.55[a] 5 F Cl O A-1 B-2 0 — 0 — 0 H propargyl 3.79[a] 6 F Cl O A-1 B-2 0 — 0 — 0 H Et 4.19[a] 7 F F O A-1 B-2 0 — 0 — 0 H Et 3.87[a] 8 F Cl O A-1 B-2 0 — 0 — 0 H Me 4.18[a] 9 F F O A-1 B-2 0 — 0 — 0 H Me 3.46[a] 10 F Cl O A-1 B-2 0 — 0 2-Cl 1 H Me 4.05[a] 11 F F O A-1 B-2 0 — 0 — 0 Me Et 4.24[a] 12 F F O A-1 B-2 0 — 0 — 0 Me propargyl  3.8[a] 13 F F O A-1 B-2 0 — 0 — 0 Me —CH.sub.2—C≡C—CH.sub.3 4.11[a] 14 F Cl O A-1 B-2 0 — 0 3,5-F 2 H Et 4.04[a] 15 F Cl O A-1 B-2 0 2-C1 1 — 0 H Et 3.73[a] 16 F F O A-1 B-2 0 — 0 — 0 Me Et 4.29[a] 17 F Cl O A-1 B-2 0 — 0 3-Cl 1 H Et 4.64[a] 18 F Cl O A-1 B-2 0 — 0 3-F 1 H Et 4.22[a] 19 F Cl O A-1 B-2 0 4-F 1 — 0 H Et 4.11[a] 20 F Cl O A-1 B-2 0 2-F 1 — 0 H Et 3.52[a] 21 F F O A-1 B-2 0 — 0 — 0 H —CH.sub.2—C≡C—CH.sub.3 3.87[a] 22 F Cl O A-1 B-2 0 — 0 — 0 H —CH.sub.2—C≡C—CH.sub.3 4.13[a] 23 F Cl O A-1 B-2 0 — 0 3,5-F 2 H Me 3.61[a] 24 F Cl O A-1 B-2 0 — 0 3-CF.sub.3 1 H Me 4.25[a] 25 F Cl O A-1 B-2 0 — 0 3-Me 1 H Me 4.04[a] 26 F Cl O A-1 B-2 0 — 0 3-CF.sub.3 1 H Et 4.65[a] 27 F Cl O A-1 B-2 0 — 0 — 0 Me —CH.sub.2—C≡C—CH.sub.3 4.41[a] 28 F Cl O A-1 B-2 0 3-F 1 — 0 H Me 3.76[a] 29 F F O A-1 B-2 0 — 0 — 0 CF.sub.3 Et 4.46[a] 30 F Cl O A-1 B-2 0 4-F 1 — 0 H Me 3.66[a] 31 F Cl O A-1 B-2 0 2-F 1 — 0 H Me 3.14[a] 32 F Cl O A-1 B-2 0 2-C1 1 — 0 H Me 3.33[a] 33 F Cl O A-1 B-2 0 — 0 3-F 1 H Me 3.75[a] 34 F Cl O A-1 B-2 0 — 0 — 0 Me Et 4.49[a] 35 F Cl O A-2 B-2 0 — 0 — 0 Me propargyl 4.01[a] 36 F Cl O A-1 B-2 0 — 0 2-Cl 1 H Et 4.49[a] 37 F Cl O A-1 B-2 0 — 0 2-F 1 H Et 3.65[a] 38 F Cl O A-1 B-2 0 — 0 3-Cl 1 H Me 4.19[a] 39 F Cl O A-1 B-2 0 — 0 3-Me 1 H Et 4.48[a] 40 F Cl O A-1 B-2 0 3-F 1 — 0 H Et 4.18[a] 41 F Cl O A-1 B-2 0 — 0 2-F 1 H Et 4.08[a] 42 F F O A-2 B-1 0 — 0 — 0 Me Me 3.85[a] 43 F Cl O A-2 B-1 0 — 0 — 0 Me Et 4.49[a] 44 F F O A-2 B-1 0 — 0 — 0 Me Et 4.29[a] 45 F Cl O A-2 B-1 0 — 0 — 0 Me Me 4.04[a] Me = methyl, Et = ethyl, iPr = isopropyl Measurement of logP values was performed according EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods: [a]Measurement of LC-MS was done at pH 2.7 with 0.1% formic acid in water and with acetonitrile (contains 0.1% formic acid) as eluent with a linear gradient from 10% acetonitrile to 95% acetonitrile. Calibration was done with not branched alkan2-ones (with 3 to 16 carbon atoms) with known logP-values (measurement of logP values using retention times with linear interpolation between successive alkanones). lambda-maX-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.

NMR Peak Lists Active Ingredient

Example 1

Solvent: DMSO, Spectrometer: 400.13 MHz

(4) 9.4761 (1.87); 7.7162 (3.12); 7.6952 (3.75); 7.6502 (1.15); 7.6305 (1.29); 7.4689 (3.72); 7.4641 (1.42); 7.4526 (1.64); 7.4480 (3.68); 7.4425 (1.06); 7.4400 (1.06); 7.4344 (0.57); 7.4282 (0.71); 7.4199 (0.84); 7.3873 (0.48); 7.3771 (3.68); 7.3690 (1.68); 7.3637 (1.21); 7.3611 (1.00); 7.1236 (0.51); 6.9892 (1.10); 6.8548 (0.54); 5.7651 (1.50); 4.4314 (0.41); 4.4158 (1.08); 4.4002 (1.49); 4.3846 (1.10); 4.3691 (0.42); 3.8580 (9.39); 3.3773 (0.54); 3.3272 (32.59); 3.2772 (0.37); 2.5644 (0.41); 2.5599 (0.57); 2.5553 (0.40); 2.5322 (0.58); 2.5187 (13.71); 2.5143 (28.43); 2.5098 (38.70); 2.5053 (27.49); 2.5008 (12.74); 2.4645 (0.33); 2.4598 (0.43); 2.1909 (14.96); 1.2809 (16.00); 1.2653 (15.86)

Example 2

Solvent: DMSO, Spectrometer: 400.13 MHz

(5) 9.4804 (1.91); 7.7155 (3.21); 7.7111 (1.15); 7.6989 (1.28); 7.6944 (3.94); 7.6473 (1.20); 7.6278 (1.33); 7.4731 (3.86); 7.4686 (1.30); 7.4630 (0.79); 7.4521 (3.55); 7.4406 (1.03); 7.4351 (0.59); 7.4289 (0.74); 7.4207 (0.85); 7.3878 (0.46); 7.3773 (3.77); 7.3695 (1.73); 7.3642 (1.26); 7.3615 (1.06); 7.1272 (0.53); 6.9928 (1.15); 6.8585 (0.57); 5.7649 (13.82); 4.2174 (1.28); 4.1999 (4.11); 4.1823 (4.16); 4.1647 (1.33); 3.8601 (9.70); 3.3273 (23.79); 3.2775 (0.36); 2.5597 (0.33); 2.5322 (0.41); 2.5188 (10.68); 2.5143 (22.39); 2.5098 (30.68); 2.5053 (21.82); 2.5008 (10.15); 2.4645 (0.36); 2.4600 (0.45); 2.2042 (16.00); 1.2951 (4.39); 1.2776 (9.35); 1.2600 (4.32)

Example 3

Solvent: DMSO, Spectrometer: 400.13 MHz

(6) 9.4937 (2.30); 7.7258 (3.49); 7.7049 (4.29); 7.6455 (1.35); 7.6259 (1.55); 7.4924 (4.17); 7.4713 (3.63); 7.4591 (0.92); 7.4541 (0.91); 7.4454 (1.17); 7.4399 (0.75); 7.4339 (0.87); 7.4255 (0.99); 7.3918 (0.57); 7.3814 (4.25); 7.3734 (2.08); 7.3683 (1.58); 7.3657 (1.33); 7.1364 (0.60); 7.0019 (1.32); 6.8678 (0.66); 4.8065 (5.30); 4.8006 (5.46); 3.8610 (10.65); 3.4995 (1.39); 3.4935 (3.09); 3.4877 (1.44); 3.3775 (0.58); 3.3274 (30.06); 3.3041 (0.50); 3.2776 (0.57); 2.5649 (0.49); 2.5603 (0.67); 2.5557 (0.48); 2.5324 (0.68); 2.5190 (15.28); 2.5146 (31.84); 2.5102 (43.88); 2.5057 (32.77); 2.5014 (16.96); 2.4698 (0.97); 2.4651 (1.06); 2.4605 (1.08); 2.4559 (0.79); 2.4514 (0.48); 2.2311 (16.00)

Example 4

Solvent: CDCl3, Spectrometer: 300.16 MHz

(7) 8.3813 (2.54); 8.3540 (2.76); 8.1911 (5.17); 8.0089 (0.35); 7.9846 (0.40); 7.7317 (4.72); 7.7072 (5.68); 7.6291 (3.06); 7.4162 (7.90); 7.3942 (6.36); 7.2515 (7.99); 7.2155 (3.46); 7.0328 (2.69); 6.9710 (0.45); 6.9185 (0.39); 6.8535 (1.36); 4.8451 (0.59); 4.8078 (9.93); 3.8447 (2.63); 3.7689 (16.00); 2.5336 (4.27); 1.2569 (0.48); −0.0002 (1.39)

Example 5

Solvent: CDCl3, Spectrometer: 300.16 MHz

(8) 8.4286 (0.71); 8.4024 (0.75); 8.1794 (1.50); 7.9458 (0.90); 7.7200 (1.36); 7.6950 (1.62); 7.4247 (2.26); 7.3993 (1.76); 7.3187 (0.39); 7.2562 (4.94); 7.1389 (0.75); 6.9597 (0.38); 5.3017 (1.57); 4.8089 (2.82); 3.8510 (4.47); 2.5331 (1.19); 2.0481 (0.80); 1.5668 (4.70); 1.2627 (16.00); 0.8828 (8.60); −0.0002 (2.02)

Example 6

Solvent: CDCl3, Spectrometer: 300.16 MHz

(9) 8.4393 (2.57); 8.4127 (2.73); 8.1256 (5.35); 7.9682 (3.49); 7.6986 (4.84); 7.6743 (5.90); 7.4073 (7.66); 7.3829 (5.94); 7.3324 (1.41); 7.2421 (6.21); 7.2144 (2.51); 7.1528 (2.73); 6.9728 (1.37); 4.2753 (4.19); 4.2615 (3.66); 4.2521 (4.34); 4.2301 (1.64); 3.9118 (0.51); 3.8399 (16.00); 1.6276 (2.14); 1.3754 (4.33); 1.3673 (4.41); 1.3523 (8.57); 1.3291 (5.13); 1.2610 (10.68); 0.8815 (5.73); −0.0002 (0.85)

Example 7

Solvent: CDCl3, Spectrometer: 300.16 MHz

(10) 8.3981 (0.82); 8.3710 (0.87); 8.1412 (1.70); 7.7119 (1.56); 7.6880 (1.93); 7.6399 (0.96); 7.4079 (2.63); 7.3825 (2.07); 7.2617 (7.94); 7.2187 (1.24); 7.0414 (0.85); 6.8614 (0.43); 4.2785 (1.33); 4.2639 (1.26); 4.2546 (1.37); 3.8187 (0.51); 3.7655 (4.95); 1.5578 (5.48); 1.3552 (3.12); 1.3241 (2.57); 1.2618 (16.00); 0.8827 (8.77); −0.0002 (4.23)

Example 8

Solvent: CDCl3, Spectrometer: 300.16 MHz

(11) 8.4382 (2.44); 8.4109 (2.61); 8.1143 (5.21); 7.9602 (3.05); 7.6984 (4.56); 7.6727 (5.75); 7.4922 (0.32); 7.4441 (1.38); 7.4138 (7.26); 7.3882 (5.69); 7.3290 (1.39); 7.2520 (5.81); 7.2449 (5.87); 7.2174 (2.39); 7.1931 (0.79); 7.1490 (2.73); 6.9692 (1.33); 4.1325 (0.88); 4.1086 (0.92); 4.0825 (0.41); 4.0658 (0.33); 4.0110 (16.00); 3.9128 (1.16); 3.8440 (15.62); 2.0454 (3.55); 1.6083 (2.11); 1.2607 (13.55); 0.8814 (6.55); 0.8596 (3.23); −0.0002 (1.83)

Example 9

Solvent: CDCl3, Spectrometer: 300.16 MHz

(12) 8.3919 (1.82); 8.3643 (1.91); 8.1273 (3.82); 7.7104 (3.48); 7.6851 (4.25); 7.6373 (2.01); 7.4102 (5.88); 7.3848 (4.54); 7.2566 (4.63); 7.2152 (2.67); 7.0349 (1.92); 6.8556 (0.97); 4.1550 (0.32); 4.1317 (0.95); 4.1083 (0.97); 4.0843 (0.35); 4.0117 (11.81); 3.8165 (0.74); 3.7634 (11.08); 2.0448 (3.82); 1.6132 (1.56); 1.2624 (16.00); 0.8820 (7.79); −0.0002 (1.35)

Example 10

Solvent: DMSO, Spectrometer: 399.95 MHz

(13) 9.1335 (2.09); 8.2909 (4.85); 7.8062 (1.49); 7.7860 (1.72); 7.7694 (2.91); 7.7658 (2.95); 7.6426 (1.41); 7.6389 (1.33); 7.6227 (1.67); 7.6190 (1.57); 7.4975 (0.69); 7.4935 (0.74); 7.4753 (1.30); 7.4593 (0.81); 7.4551 (0.80); 7.4215 (2.68); 7.4017 (2.29); 7.3557 (0.69); 7.3346 (1.57); 7.3185 (1.07); 7.3161 (1.03); 7.2932 (1.92); 7.2892 (1.91); 7.2740 (1.04); 7.2703 (0.89); 7.1617 (0.83); 7.0275 (1.78); 6.8932 (0.89); 3.9244 (16.00); 3.9022 (3.10); 3.8273 (11.15); 3.3244 (170.59); 2.6751 (0.60); 2.6705 (0.76); 2.6658 (0.58); 2.5408 (0.83); 2.5100 (52.48); 2.5060 (97.88); 2.5016 (123.55); 2.4971 (89.79); 2.4628 (0.40); 2.3325 (0.56); 2.3283 (0.72); 2.3240 (0.53); −0.0002 (1.47)

Example 11

Solvent: DMSO, Spectrometer: 400.13 MHz

(14) 9.3298 (1.50); 7.7140 (3.26); 7.6929 (3.95); 7.6447 (1.12); 7.6252 (1.27); 7.4748 (3.67); 7.4536 (3.26); 7.4449 (0.74); 7.4360 (0.80); 7.4293 (1.06); 7.4257 (0.67); 7.4163 (0.65); 7.4096 (0.94); 7.3952 (0.66); 7.3820 (2.99); 7.3773 (2.84); 7.3648 (0.98); 7.3619 (0.94); 7.1578 (0.52); 7.0237 (1.12); 6.8896 (0.54); 4.2186 (1.30); 4.2010 (4.12); 4.1835 (4.16); 4.1659 (1.32); 3.7700 (7.06); 3.3782 (0.85); 3.3283 (83.24); 3.3047 (0.51); 3.2787 (0.78); 2.6789 (0.33); 2.5642 (0.47); 2.5597 (0.63); 2.5552 (0.46); 2.5320 (0.90); 2.5187 (20.22); 2.5143 (41.53); 2.5098 (56.44); 2.5053 (40.32); 2.5009 (18.91); 2.4693 (0.33); 2.4646 (0.48); 2.4601 (0.59); 2.4557 (0.41); 2.3367 (0.37); 2.2065 (16.00); 1.2953 (4.39); 1.2778 (9.36); 1.2602 (4.39)

Example 12

Solvent: DMSO, Spectrometer: 400.13 MHz

(15) 9.3374 (1.84); 7.7253 (3.41); 7.7043 (4.15); 7.6474 (1.19); 7.6280 (1.38); 7.4941 (3.89); 7.4731 (3.24); 7.4565 (0.60); 7.4496 (0.72); 7.4407 (0.85); 7.4341 (1.16); 7.4303 (0.72); 7.4209 (0.69); 7.4143 (1.03); 7.3985 (0.74); 7.3855 (3.11); 7.3807 (3.05); 7.3681 (1.06); 7.3651 (1.01); 7.1655 (0.59); 7.0314 (1.27); 6.8973 (0.62); 4.8078 (5.27); 4.8019 (5.23); 3.7702 (7.57); 3.4999 (1.43); 3.4940 (3.15); 3.4881 (1.36); 3.3782 (0.85); 3.3286 (60.59); 3.3048 (0.35); 3.2792 (0.47); 2.5637 (0.45); 2.5592 (0.62); 2.5547 (0.46); 2.5319 (0.96); 2.5186 (15.58); 2.5142 (31.37); 2.5097 (42.20); 2.5052 (29.83); 2.5008 (13.74); 2.4604 (0.34); 2.2336 (16.00); 1.9973 (0.81); 1.1834 (0.43); 0.8673 (0.35)

Example 13

Solvent: CDCl3, Spectrometer: 300.16 MHz

(16) 8.3787 (2.46); 8.3515 (2.61); 7.7964 (4.73); 7.7701 (5.46); 7.6533 (2.59); 7.4278 (1.25); 7.4039 (7.70); 7.3774 (6.16); 7.2570 (3.92); 7.2433 (5.33); 7.2173 (3.13); 7.1897 (0.72); 7.0444 (2.64); 6.8649 (1.32); 4.7982 (7.78); 4.1313 (0.56); 4.1068 (0.57); 3.7631 (14.95); 2.3135 (16.00); 2.0440 (2.29); 1.8991 (12.98); 1.6290 (3.62); 1.2614 (4.04); 0.8814 (1.64); 0.8595 (0.81); −0.0002 (1.46)

Example 14

Solvent: DMSO, Spectrometer: 399.95 MHz

(17) 9.8281 (3.92); 8.2317 (6.76); 7.5417 (1.39); 7.5237 (3.11); 7.5052 (1.43); 7.5014 (1.54); 7.4843 (2.16); 7.4628 (2.06); 7.4425 (3.21); 7.4128 (1.90); 7.4101 (1.89); 7.3933 (2.04); 7.3765 (0.74); 7.2567 (4.73); 7.2326 (4.68); 7.1392 (1.21); 7.0048 (2.62); 6.8704 (1.30); 4.2224 (1.99); 4.2048 (5.90); 4.1873 (5.94); 4.1697 (2.03); 3.9023 (3.46); 3.8794 (16.00); 3.3719 (0.36); 3.3242 (145.18); 2.6704 (0.81); 2.5403 (1.02); 2.5058 (111.07); 2.5016 (136.40); 2.4974 (103.06); 2.3284 (0.81); 1.2745 (6.12); 1.2569 (12.30); 1.2393 (6.06); −0.0002 (1.32)

Example 15

Solvent: DMSO, Spectrometer: 399.95 MHz

(18) 9.8418 (4.60); 8.2405 (7.37); 7.6308 (6.48); 7.6101 (7.45); 7.4899 (1.69); 7.4704 (3.59); 7.4472 (6.14); 7.4265 (4.61); 7.4011 (2.89); 7.3983 (2.90); 7.3818 (1.87); 6.9724 (1.23); 6.8381 (2.65); 6.7036 (1.34); 4.1833 (2.03); 4.1657 (6.24); 4.1481 (6.25); 4.1305 (2.05); 3.9022 (3.40); 3.8663 (16.00); 3.3624 (0.63); 3.3249 (241.20); 3.2960 (0.86); 2.6748 (0.90); 2.6705 (1.15); 2.5406 (1.07); 2.5058 (152.02); 2.5015 (187.89); 2.4971 (137.36); 2.3324 (0.92); 2.3279 (1.14); 1.2663 (6.68); 1.2487 (13.72); 1.2311 (6.55); −0.0002 (2.38)

Example 16

Solvent: CDCl3, Spectrometer: 300.16 MHz

(19) 7.8451 (4.61); 7.7973 (5.46); 7.6487 (2.20); 7.6237 (2.89); 7.5952 (3.65); 7.5701 (4.90); 7.4615 (2.76); 7.4365 (5.04); 7.4071 (5.97); 7.3790 (1.21); 7.2612 (11.80); 7.1935 (1.35); 7.0143 (2.57); 6.8345 (1.31); 4.3039 (1.37); 4.2808 (4.09); 4.2578 (4.23); 4.2336 (1.50); 3.8640 (14.70); 3.7250 (0.88); 2.2869 (16.00); 1.5661 (8.12); 1.3714 (4.24); 1.3482 (8.44); 1.3247 (4.57); 1.2616 (4.37); 0.8975 (1.23); 0.8815 (2.26); 0.8596 (1.14); −0.0002 (7.24)

Example 17

Solvent: DMSO, Spectrometer: 399.95 MHz

(20) 9.7334 (3.52); 8.4268 (7.02); 8.3149 (0.37); 7.8419 (3.58); 7.8215 (3.96); 7.5585 (5.49); 7.5542 (4.79); 7.5423 (2.72); 7.4860 (1.03); 7.4802 (1.14); 7.4697 (1.40); 7.4640 (1.71); 7.4496 (1.02); 7.4400 (2.31); 7.4366 (2.03); 7.4194 (2.37); 7.4161 (2.82); 7.4026 (3.79); 7.3973 (4.86); 7.3811 (1.64); 7.3784 (1.68); 7.3619 (0.49); 7.3590 (0.48); 7.1211 (0.97); 6.9869 (2.17); 6.8527 (1.06); 4.2372 (2.06); 4.2196 (6.29); 4.2020 (6.28); 4.1844 (1.98); 3.9021 (5.08); 3.8686 (16.00); 3.3721 (0.35); 3.3257 (237.08); 3.1686 (0.36); 2.6753 (0.73); 2.6707 (0.98); 2.6662 (0.71); 2.5618 (0.36); 2.5480 (0.75); 2.5410 (0.79); 2.5340 (0.90); 2.5104 (70.65); 2.5062 (134.60); 2.5017 (170.23); 2.4971 (122.01); 2.4928 (59.07); 2.3330 (0.77); 2.3283 (0.99); 2.3239 (0.72); 1.3020 (0.34); 1.2900 (6.81); 1.2723 (14.14); 1.2547 (6.60); −0.0002 (1.75)

Example 18

Solvent: DMSO, Spectrometer: 399.95 MHz

(21) 9.7021 (3.88); 8.3054 (6.40); 7.7761 (1.46); 7.7564 (2.82); 7.7372 (1.52); 7.5643 (1.90); 7.5444 (2.80); 7.4830 (1.06); 7.4785 (1.13); 7.4620 (1.92); 7.4465 (1.03); 7.4417 (1.19); 7.4216 (1.23); 7.4077 (3.61); 7.4027 (3.13); 7.3981 (2.94); 7.3791 (1.97); 7.3559 (2.26); 7.3238 (2.57); 7.3163 (2.72); 7.2956 (2.18); 7.1233 (1.09); 6.9886 (2.31); 6.8540 (1.15); 4.2201 (1.79); 4.2025 (5.35); 4.1848 (5.35); 4.1673 (1.77); 3.9022 (2.84); 3.8682 (16.00); 3.3247 (186.61); 3.2721 (0.39); 2.6703 (0.90); 2.5016 (146.35); 2.3283 (0.90); 1.2803 (5.61); 1.2627 (11.30); 1.2451 (5.52); −0.0002 (0.89)

Example 19

Solvent: DMSO, Spectrometer: 399.95 MHz

(22) 9.5956 (3.39); 8.3142 (0.37); 8.2526 (6.93); 7.6532 (4.67); 7.6326 (6.04); 7.5738 (1.20); 7.5600 (1.38); 7.5520 (1.46); 7.5382 (1.37); 7.4981 (5.99); 7.4775 (4.68); 7.3120 (0.85); 7.3045 (1.14); 7.2909 (1.44); 7.2833 (2.01); 7.2686 (2.68); 7.2618 (2.26); 7.2449 (2.17); 7.2376 (1.32); 7.1052 (0.84); 6.9709 (1.82); 6.8370 (0.91); 4.1885 (1.94); 4.1710 (5.91); 4.1534 (5.93); 4.1358 (1.94); 3.9018 (2.86); 3.8559 (16.00); 3.3572 (0.78); 3.3261 (293.52); 3.2833 (0.46); 2.6751 (0.73); 2.6707 (0.96); 2.6663 (0.70); 2.5408 (0.95); 2.5060 (126.79); 2.5016 (161.04); 2.4972 (118.39); 2.3324 (0.72); 2.3282 (0.97); 2.3238 (0.72); 1.2703 (6.35); 1.2527 (13.04); 1.2351 (6.31); −0.0002 (1.59)

Example 20

Solvent: DMSO, Spectrometer: 399.95 MHz

(23) 9.7157 (4.46); 8.2469 (6.73); 7.6437 (4.94); 7.6234 (6.03); 7.5012 (0.76); 7.4817 (1.99); 7.4677 (7.50); 7.4474 (5.65); 7.3758 (1.47); 7.3534 (2.16); 7.3313 (1.02); 7.2752 (2.65); 7.2561 (2.19); 7.0662 (0.75); 6.9310 (1.55); 6.7967 (0.81); 4.1854 (1.91); 4.1679 (5.54); 4.1504 (5.55); 4.1327 (1.85); 3.9019 (2.90); 3.8669 (16.00); 3.3256 (216.45); 2.6707 (0.97); 2.5015 (167.56); 2.3279 (1.03); 1.2674 (6.00); 1.2499 (11.81); 1.2323 (5.82); −0.0002 (1.53)

Example 21

Solvent: CDCl3, Spectrometer: 300.16 MHz

(24) 8.1785 (0.36); 7.7259 (0.33); 7.7000 (0.39); 7.4127 (0.54); 7.3875 (0.42); 7.2558 (0.58); 4.7797 (0.56); 4.1326 (0.43); 4.1089 (0.44); 3.7679 (1.04); 2.0437 (1.74); 1.8994 (0.93); 1.6008 (0.42); 1.2636 (16.00); 0.8824 (8.49); 0.8625 (4.13)

Example 22

Solvent: CDCl3, Spectrometer: 300.16 MHz

(25) 8.4305 (2.55); 8.4032 (2.67); 8.1655 (5.40); 7.9515 (3.21); 7.7130 (4.78); 7.6876 (5.76); 7.4459 (1.40); 7.4172 (7.62); 7.3915 (5.97); 7.3222 (1.39); 7.2574 (5.04); 7.2443 (6.52); 7.2184 (2.42); 7.1950 (0.69); 7.1429 (2.72); 6.9632 (1.36); 4.7786 (8.26); 4.1320 (0.84); 4.1085 (0.85); 4.0846 (0.39); 3.8987 (0.49); 3.8467 (16.00); 2.0452 (3.34); 1.9015 (13.83); 1.6138 (5.29); 1.2607 (7.59); 0.8817 (3.16); 0.8588 (1.61); −0.0002 (1.79)

Example 23

Solvent: DMSO, Spectrometer: 399.95 MHz

(26) 9.8309 (2.16); 8.2419 (4.13); 7.5412 (0.70); 7.5233 (1.63); 7.5065 (0.77); 7.5024 (0.83); 7.4891 (0.98); 7.4851 (1.17); 7.4643 (1.12); 7.4595 (0.86); 7.4439 (1.80); 7.4403 (1.29); 7.4138 (1.02); 7.4103 (0.99); 7.3938 (1.04); 7.3774 (0.39); 7.3736 (0.38); 7.2623 (2.74); 7.2382 (2.70); 7.1396 (0.69); 7.0052 (1.53); 6.8708 (0.76); 3.9359 (16.00); 3.9020 (3.06); 3.8800 (9.13); 3.3245 (141.72); 2.6750 (0.42); 2.6706 (0.57); 2.6661 (0.41); 2.5408 (0.52); 2.5103 (37.91); 2.5060 (72.56); 2.5015 (92.58); 2.4970 (66.82); 2.4927 (32.70); 2.3327 (0.41); 2.3283 (0.55); 2.3239 (0.42); −0.0002 (1.27)

Example 24

Solvent: DMSO, Spectrometer: 399.95 MHz

(27) 9.7872 (2.03); 8.3642 (1.50); 8.3588 (1.51); 8.0224 (1.29); 8.0024 (1.50); 7.7672 (2.73); 7.7426 (0.99); 7.5410 (0.62); 7.5231 (1.63); 7.5201 (1.55); 7.5101 (0.85); 7.5050 (0.84); 7.4938 (0.96); 7.4888 (1.14); 7.4737 (0.42); 7.4689 (0.59); 7.4548 (0.44); 7.4501 (0.71); 7.4357 (1.86); 7.4311 (1.52); 7.4253 (1.36); 7.4217 (1.20); 7.4088 (0.86); 7.4054 (0.97); 7.0916 (0.61); 6.9571 (1.36); 6.8227 (0.66); 3.9709 (16.00); 3.9020 (2.71); 3.8581 (9.33); 3.3539 (0.38); 3.3243 (131.50); 2.6752 (0.41); 2.6707 (0.55); 2.6661 (0.41); 2.5407 (0.49); 2.5237 (1.67); 2.5105 (37.68); 2.5062 (73.10); 2.5016 (93.90); 2.4971 (67.24); 2.4926 (32.34); 2.3329 (0.43); 2.3283 (0.57); 2.3237 (0.41); −0.0002 (1.06)

Example 25

Solvent: DMSO, Spectrometer: 399.95 MHz

(28) 9.4729 (1.76); 8.4171 (4.18); 7.6689 (1.72); 7.6487 (2.57); 7.6262 (1.38); 7.4453 (0.50); 7.4370 (0.62); 7.4312 (0.67); 7.4231 (0.92); 7.4178 (0.56); 7.4109 (0.62); 7.4030 (0.71); 7.3640 (0.53); 7.3530 (3.74); 7.3455 (1.77); 7.3394 (1.19); 7.3008 (2.67); 7.2769 (1.08); 7.1425 (0.50); 7.0082 (1.05); 6.8739 (0.52); 3.9098 (16.00); 3.9020 (2.60); 3.8570 (9.51); 3.3242 (89.08); 2.6750 (0.37); 2.6706 (0.47); 2.6660 (0.34); 2.5405 (0.41); 2.5101 (33.32); 2.5059 (62.84); 2.5014 (79.30); 2.4969 (57.31); 2.4927 (28.22); 2.4028 (9.63); 2.3325 (0.37); 2.3283 (0.47); 2.3237 (0.34); −0.0002 (0.82)

Example 26

Solvent: DMSO, Spectrometer: 399.95 MHz

(29) 9.7821 (3.62); 8.3607 (2.55); 8.3551 (2.54); 8.3150 (0.40); 8.0334 (2.28); 8.0133 (2.65); 7.7634 (4.26); 7.7572 (2.57); 7.7362 (1.73); 7.5415 (1.17); 7.5238 (2.80); 7.5094 (1.35); 7.5041 (1.39); 7.4932 (1.58); 7.4881 (1.88); 7.4732 (0.73); 7.4682 (0.99); 7.4525 (0.73); 7.4478 (1.14); 7.4335 (3.35); 7.4285 (2.83); 7.4248 (2.58); 7.4211 (2.18); 7.4084 (1.48); 7.4049 (1.67); 7.3891 (0.52); 7.3855 (0.50); 7.0885 (1.04); 6.9540 (2.29); 6.8196 (1.12); 4.2598 (1.99); 4.2423 (6.29); 4.2247 (6.32); 4.2070 (2.05); 3.9021 (6.22); 3.8568 (16.00); 3.3446 (1.39); 3.3246 (249.07); 2.6751 (0.81); 2.6706 (1.09); 2.6660 (0.79); 2.5407 (0.77); 2.5236 (3.38); 2.5104 (73.74); 2.5061 (142.71); 2.5016 (183.09); 2.4971 (131.88); 2.4927 (64.21); 2.3329 (0.83); 2.3283 (1.11); 2.3240 (0.83); 1.2980 (6.88); 1.2803 (14.18); 1.2627 (6.68); 1.2358 (0.44); −0.0002 (2.93)

Example 27

Solvent: CDCl3, Spectrometer: 300.16 MHz

(30) 8.4360 (2.03); 8.4088 (2.16); 7.9683 (2.51); 7.7839 (3.94); 7.7574 (4.55); 7.4443 (0.99); 7.4048 (5.46); 7.3796 (4.17); 7.3280 (1.13); 7.2629 (5.15); 7.2424 (5.31); 7.2172 (1.97); 7.1931 (0.58); 7.1482 (2.21); 6.9684 (1.12); 4.7995 (6.59); 4.1338 (0.72); 4.1091 (0.73); 4.0866 (0.33); 3.8455 (12.99); 2.3071 (13.34); 2.0462 (2.94); 1.9016 (10.96); 1.6106 (5.29); 1.2641 (16.00); 0.8825 (8.01); 0.8610 (3.88); −0.0002 (2.73)

Example 28

Solvent: DMSO, Spectrometer: 399.95 MHz

(31) 9.2957 (2.33); 8.2773 (4.53); 7.6944 (3.28); 7.6738 (3.79); 7.6160 (1.34); 7.5957 (1.80); 7.5075 (0.64); 7.4916 (0.83); 7.4870 (1.17); 7.4712 (1.17); 7.4668 (0.67); 7.4509 (0.52); 7.4204 (3.16); 7.4004 (2.75); 7.2518 (0.85); 7.2303 (1.46); 7.2091 (0.72); 7.1251 (0.99); 6.9908 (2.30); 6.8566 (1.10); 3.9098 (16.00); 3.9023 (2.64); 3.8312 (10.91); 3.3230 (104.93); 2.6750 (0.44); 2.6705 (0.58); 2.6663 (0.42); 2.5409 (0.56); 2.5102 (40.77); 2.5060 (76.41); 2.5016 (96.49); 2.4971 (69.63); 2.4929 (34.40); 2.3327 (0.44); 2.3283 (0.58); 2.3238 (0.44); −0.0002 (1.25)

Example 29

Solvent: CDCl3, Spectrometer: 250.13 MHz

(32) 8.6080 (0.49); 8.4399 (0.54); 8.4082 (1.39); 8.3913 (1.07); 8.3758 (1.10); 8.3618 (0.71); 7.6764 (0.43); 7.6398 (1.70); 7.6079 (3.22); 7.5928 (3.33); 7.4762 (1.44); 7.4510 (3.48); 7.4333 (3.40); 7.4189 (3.15); 7.4024 (2.09); 7.2857 (1.67); 7.2616 (13.55); 7.2571 (11.23); 7.2427 (9.89); 7.0282 (1.24); 7.0115 (1.04); 6.8121 (0.61); 6.8025 (0.51); 4.4288 (0.62); 4.4047 (1.88); 4.3861 (1.47); 4.3766 (2.02); 4.3575 (1.51); 4.3417 (1.23); 4.3222 (0.88); 4.3126 (0.99); 4.2933 (0.62); 4.1364 (0.75); 4.1176 (0.62); 4.1076 (0.88); 4.0895 (0.53); 3.8122 (0.34); 3.7517 (5.71); 3.7359 (6.13); 2.0471 (3.23); 2.0427 (2.57); 2.0281 (2.17); 1.5625 (5.24); 1.5582 (4.18); 1.5436 (3.66); 1.4215 (2.09); 1.4171 (1.80); 1.4024 (1.85); 1.3932 (4.14); 1.3890 (3.41); 1.3743 (3.07); 1.3648 (3.43); 1.3457 (2.73); 1.3364 (3.05); 1.3172 (3.13); 1.3035 (3.44); 1.2606 (16.00); 0.8816 (9.72); 0.8627 (7.05); 0.8359 (2.65); 0.0002 (7.86); −0.0046 (6.25); −0.0192 (5.41)

Example 30

Solvent: DMSO, Spectrometer: 399.95 MHz

(33) 9.6017 (1.76); 8.2594 (4.05); 7.6549 (2.69); 7.6342 (3.52); 7.5721 (0.67); 7.5582 (0.77); 7.5504 (0.81); 7.5367 (0.77); 7.5023 (3.48); 7.4816 (2.65); 7.3133 (0.50); 7.3059 (0.64); 7.2923 (0.79); 7.2848 (1.15); 7.2717 (1.57); 7.2640 (1.26); 7.2483 (1.25); 7.2410 (0.73); 7.1090 (0.45); 6.9744 (0.97); 6.8402 (0.48); 3.9002 (16.00); 3.8572 (8.95); 3.3509 (0.42); 3.3255 (127.03); 2.6752 (0.40); 2.6706 (0.53); 2.6660 (0.39); 2.5408 (0.46); 2.5238 (1.57); 2.5105 (35.77); 2.5061 (69.90); 2.5016 (89.86); 2.4970 (64.42); 2.4926 (30.99); 2.3328 (0.41); 2.3282 (0.55); 2.3238 (0.40); −0.0002 (0.98)

Example 31

Solvent: DMSO, Spectrometer: 399.95 MHz

(34) 9.7205 (2.68); 8.2539 (4.52); 7.6455 (3.14); 7.6250 (3.96); 7.5026 (0.47); 7.4822 (1.20); 7.4713 (4.36); 7.4508 (3.47); 7.3772 (0.88); 7.3559 (1.34); 7.3348 (0.63); 7.2770 (1.60); 7.2580 (1.35); 7.0702 (0.47); 6.9352 (0.94); 6.8015 (0.47); 3.8971 (16.00); 3.8680 (10.23); 3.3240 (114.87); 3.1746 (0.91); 3.1617 (0.88); 2.6704 (0.61); 2.5403 (0.70); 2.5057 (83.13); 2.5013 (103.85); 2.4970 (76.31); 2.3323 (0.49); 2.3281 (0.62); 2.3238 (0.45); −0.0002 (1.25)

Example 32

Solvent: DMSO, Spectrometer: 399.95 MHz

(35) 9.8452 (2.63); 8.2469 (4.43); 7.6323 (4.00); 7.6115 (4.50); 7.4899 (1.02); 7.4704 (2.15); 7.4505 (4.53); 7.4298 (2.69); 7.4025 (1.67); 7.3992 (1.70); 7.3832 (1.08); 7.3800 (0.99); 6.9807 (0.71); 6.8462 (1.60); 6.7118 (0.79); 3.9021 (4.12); 3.8950 (16.00); 3.8673 (9.42); 3.3227 (126.86); 2.6748 (0.60); 2.6704 (0.81); 2.6659 (0.61); 2.5403 (0.65); 2.5099 (56.15); 2.5058 (105.55); 2.5013 (133.48); 2.4968 (96.91); 2.3324 (0.62); 2.3281 (0.81); 2.3235 (0.59); 1.2359 (0.37); −0.0002 (2.02)

Example 33

Solvent: DMSO, Spectrometer: 399.95 MHz

(36) 9.7072 (2.48); 8.3118 (4.63); 7.7702 (1.07); 7.7506 (2.05); 7.7311 (1.09); 7.5638 (1.34); 7.5441 (1.94); 7.4845 (0.76); 7.4795 (0.83); 7.4672 (1.17); 7.4628 (1.27); 7.4477 (0.71); 7.4426 (0.85); 7.4237 (0.98); 7.4097 (2.55); 7.4047 (1.96); 7.3984 (1.79); 7.3810 (1.33); 7.3606 (1.75); 7.3284 (1.86); 7.3218 (1.93); 7.3014 (1.49); 7.1254 (0.74); 6.9910 (1.55); 6.8565 (0.76); 3.9452 (1.60); 3.9309 (16.00); 3.9018 (1.96); 3.8695 (11.06); 3.3250 (124.29); 2.6748 (0.46); 2.6713 (0.56); 2.5480 (0.47); 2.5060 (79.72); 2.5018 (95.14); 2.4976 (67.07); 2.3284 (0.57); 2.3246 (0.42); −0.0002 (1.02)

Example 34

Solvent: CDCl3, Spectrometer: 300.16 MHz

(37) 8.0715 (2.64); 7.8479 (4.70); 7.8150 (4.60); 7.6499 (2.27); 7.6252 (4.72); 7.6003 (4.71); 7.5731 (3.02); 7.4643 (2.51); 7.4401 (4.44); 7.4283 (3.26); 7.4129 (5.65); 7.3856 (1.37); 7.2610 (17.47); 7.0654 (2.56); 6.8866 (1.31); 4.3039 (1.39); 4.2799 (4.07); 4.2570 (4.21); 4.2331 (1.54); 3.9599 (15.47); 2.2871 (16.00); 1.5566 (9.56); 1.3714 (4.16); 1.3477 (8.23); 1.3250 (4.25); 1.2590 (0.62); −0.0002 (11.43)

Example 35

Solvent: CDCl3, Spectrometer: 300.16 MHz

(38) 8.0812 (3.00); 7.8590 (4.92); 7.8327 (4.87); 7.6601 (2.24); 7.6133 (4.09); 7.5887 (5.35); 7.4682 (2.82); 7.4428 (5.18); 7.4090 (5.27); 7.3791 (1.42); 7.2606 (3.34); 7.2539 (3.05); 7.0624 (2.64); 6.8827 (1.32); 4.8186 (9.64); 3.9488 (15.45); 2.5000 (4.20); 2.3177 (16.00); 2.0445 (0.83); 1.6098 (4.90); 1.2618 (3.53); 0.8821 (1.65); −0.0002 (1.70)

Example 36

Solvent: DMSO, Spectrometer: 399.95 MHz

(39) 9.1291 (3.10); 8.3150 (0.33); 8.2833 (6.69); 7.8082 (2.18); 7.7881 (2.52); 7.7669 (4.19); 7.7635 (4.10); 7.6429 (2.01); 7.6395 (1.82); 7.6230 (2.34); 7.6194 (2.18); 7.4969 (1.00); 7.4928 (1.02); 7.4773 (1.86); 7.4585 (1.19); 7.4542 (1.12); 7.4181 (3.70); 7.3982 (3.16); 7.3551 (1.02); 7.3360 (2.32); 7.3178 (1.52); 7.2915 (2.76); 7.2879 (2.64); 7.2725 (1.49); 7.2686 (1.20); 7.1600 (1.15); 7.0258 (2.50); 6.8915 (1.23); 4.2124 (1.75); 4.1948 (5.41); 4.1772 (5.45); 4.1597 (1.73); 3.9022 (4.87); 3.8261 (16.00); 3.3238 (210.82); 2.6752 (0.87); 2.6705 (1.11); 2.5405 (0.92); 2.5059 (152.82); 2.5015 (189.48); 2.4971 (137.54); 2.3282 (1.14); 1.2812 (5.83); 1.2636 (12.13); 1.2460 (5.79); −0.0002 (1.75)

Example 37

Solvent: DMSO, Spectrometer: 399.95 MHz

(40) 9.4640 (2.23); 8.2762 (4.12); 7.6699 (1.51); 7.6499 (1.83); 7.5002 (0.81); 7.4888 (2.20); 7.4827 (1.95); 7.4753 (2.54); 7.4716 (2.35); 7.4583 (2.12); 7.4342 (1.39); 7.4144 (1.85); 7.3953 (0.86); 7.3623 (3.97); 7.3517 (2.94); 7.1254 (0.78); 6.9910 (1.67); 6.8566 (0.84); 3.9642 (0.51); 3.9156 (16.00); 3.9022 (3.80); 3.8440 (11.03); 3.3628 (0.32); 3.3237 (129.12); 2.6749 (0.54); 2.6705 (0.69); 2.6659 (0.52); 2.5406 (0.67); 2.5058 (92.08); 2.5014 (116.19); 2.4970 (84.44); 2.3322 (0.54); 2.3282 (0.68); 2.3237 (0.49); −0.0002 (1.12)

Example 38

Solvent: DMSO, Spectrometer: 399.95 MHz

(41) 9.7375 (2.24); 8.4313 (4.30); 7.8340 (2.24); 7.8136 (2.49); 7.5619 (3.75); 7.5582 (3.75); 7.5411 (1.70); 7.4866 (0.64); 7.4811 (0.74); 7.4701 (0.94); 7.4649 (1.15); 7.4450 (2.13); 7.4246 (1.57); 7.4211 (1.53); 7.4043 (2.41); 7.3984 (2.98); 7.3789 (1.14); 7.3618 (0.33); 7.1237 (0.63); 6.9895 (1.39); 6.8549 (0.69); 3.9484 (16.00); 3.9021 (2.95); 3.8695 (10.23); 3.3225 (102.36); 3.1748 (0.34); 3.1617 (0.33); 2.6748 (0.57); 2.6705 (0.73); 2.6662 (0.56); 2.5409 (0.81); 2.5099 (49.81); 2.5059 (92.27); 2.5015 (116.09); 2.4970 (84.29); 2.3324 (0.48); 2.3281 (0.66); 2.3235 (0.49); −0.0002 (1.62)

Example 39

Solvent: DMSO, Spectrometer: 399.95 MHz

(42) 9.4678 (3.35); 8.4118 (6.50); 7.6712 (2.91); 7.6509 (4.32); 7.6280 (2.43); 7.4447 (0.85); 7.4359 (1.13); 7.4304 (1.22); 7.4226 (1.60); 7.4103 (1.08); 7.4024 (1.14); 7.3519 (6.60); 7.3444 (3.18); 7.3382 (2.24); 7.3169 (0.46); 7.2983 (4.62); 7.2729 (1.94); 7.1411 (0.89); 7.0063 (1.84); 6.8717 (0.92); 4.1978 (1.82); 4.1803 (5.45); 4.1627 (5.56); 4.1451 (1.81); 3.9021 (3.07); 3.8560 (15.95); 3.3239 (219.46); 2.6705 (1.14); 2.5692 (0.35); 2.5055 (150.65); 2.5015 (182.00); 2.4977 (136.13); 2.4047 (16.00); 2.3284 (1.08); 1.2831 (5.79); 1.2655 (11.65); 1.2480 (5.72); −0.0002 (1.33)

Example 40

Solvent: DMSO, Spectrometer: 399.95 MHz

(43) 9.2888 (3.34); 8.3152 (0.34); 8.2710 (6.47); 7.6939 (4.78); 7.6733 (5.47); 7.6192 (2.02); 7.5987 (2.68); 7.5066 (0.92); 7.4903 (1.24); 7.4862 (1.68); 7.4703 (1.72); 7.4499 (0.79); 7.4168 (4.68); 7.3966 (4.05); 7.2513 (1.27); 7.2290 (2.16); 7.2074 (1.05); 7.1224 (1.43); 6.9882 (3.27); 6.8540 (1.57); 4.1981 (1.91); 4.1805 (5.64); 4.1629 (5.65); 4.1453 (1.80); 3.9022 (3.49); 3.8296 (16.00); 3.3231 (172.25); 2.6751 (0.82); 2.6704 (1.06); 2.6662 (0.80); 2.5405 (1.15); 2.5059 (140.74); 2.5015 (176.80); 2.4971 (129.39); 2.3324 (0.82); 2.3283 (1.04); 2.3237 (0.80); 1.2779 (5.96); 1.2603 (12.41); 1.2427 (5.88); −0.0002 (2.05)

Example 41

Solvent: DMSO, Spectrometer: 399.95 MHz

(44) 9.4595 (3.22); 8.7752 (0.58); 8.3151 (0.47); 8.2688 (5.94); 7.6717 (2.24); 7.6519 (2.73); 7.6354 (0.60); 7.6156 (0.69); 7.5598 (0.34); 7.4991 (1.23); 7.4884 (3.48); 7.4817 (2.95); 7.4741 (3.87); 7.4705 (3.88); 7.4576 (4.02); 7.4387 (1.25); 7.4306 (2.30); 7.4109 (3.17); 7.3916 (1.82); 7.3614 (5.74); 7.3510 (4.42); 7.2792 (0.84); 7.2590 (0.76); 7.2393 (0.73); 7.2187 (0.68); 7.1996 (0.36); 7.1232 (1.13); 7.0025 (0.49); 6.9886 (2.67); 6.9201 (0.63); 6.9010 (0.54); 6.8543 (1.23); 4.2032 (1.80); 4.1856 (5.65); 4.1680 (5.68); 4.1504 (1.82); 3.9022 (7.13); 3.8430 (16.00); 3.6396 (2.19); 3.6329 (2.08); 3.3904 (0.34); 3.3668 (0.72); 3.3253 (333.53); 3.3035 (2.09); 3.2927 (0.75); 3.2749 (0.39); 2.6749 (1.14); 2.6708 (1.48); 2.6661 (1.08); 2.5408 (1.26); 2.5061 (201.32); 2.5017 (252.19); 2.4972 (181.97); 2.3328 (1.15); 2.3285 (1.50); 2.3240 (1.08); 2.1438 (2.30); 2.1246 (1.26); 1.9578 (2.69); 1.9525 (2.59); 1.4144 (2.50); 1.4077 (2.15); 1.2880 (0.54); 1.2757 (6.16); 1.2581 (12.77); 1.2405 (6.08); −0.0002 (1.77)

(45) NMR Peak Lists

(46) 1H-NMR data of selected examples are written in form of 1H-NMR-peak lists. To each signal peak are listed the δ-value in ppm and the signal intensity in round brackets. Between the δ-value-signal intensity pairs are semicolons as delimiters.

(47) The peak list of an example has therefore the form:

(48) δ.sub.1 (intensity.sub.1); δ.sub.2 (intensity.sub.2); . . . ; δ.sub.i (intensity); . . . ; δ.sub.n (intensity.sub.n)

(49) Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.

(50) For calibrating chemical shift for 1H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.

(51) The 1H-NMR peak lists are similar to classical 1H-NMR prints and contain therefore usually all peaks, which are listed at classical NMR-interpretation.

(52) Additionally they can show like classical 1H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.

(53) To show compound signals in the delta-range of solvents and/or water the usual peaks of solvents, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water are shown in our 1H-NMR peak lists and have usually on average a high intensity.

(54) The peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).

(55) Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via “side-products-fingerprints”.

(56) An expert, who calculates the peaks of the target compounds with known methods (MestreC, ACD-simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1H-NMR interpretation.

(57) Further details of NMR-data description with peak lists you find in the publication “Citation of NMR Peaklist Data within Patent Applications” of the Research Disclosure Database Number 564025.

Example: In Vivo Preventive Test on Alternaria brassicae (Leaf Spot on Radish)

(58) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(59) Radish plants (“Pernod Clair” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 17° C., are treated at the cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(60) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of Alternaria brassicae spores (50 000 spores per ml). The spores are collected from a 15-day-old culture. The contaminated radish plants are incubated at 20° C. and at 100% relative humidity.

(61) Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.

(62) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(63) TABLE-US-00002 Ex_no. Eff. % 5 88 6 97 11 97 12 97 14 100 16 100 17 98 18 94 19 88 20 90 22 75 23 97 24 92 25 94 28 92 30 97 31 96 33 88 36 81 37 88 38 94 39 94 40 94 41 88 44 100

Example: In Vivo Preventive Test on Botrytis cinerea (Grey Mould)

(64) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.

(65) Gherkin plants (“Vert petit de Paris” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 24° C., are treated at the Z11 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(66) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of cryopreserved Botrytis cinerea spores (50 000 spores per ml). The spores are suspended in a nutrient solution composed of 10 g/L of PDB, 50 g/L of D-Fructose, 2 g/L of NH.sub.4NO.sub.3 and 1 g/L of KH.sub.2PO.sub.4. The contaminated gherkin plants are incubated at 17° C. and at 90% relative humidity.

(67) Grading (% of efficacy) is carried out 4 to 5 days after the contamination, in comparison with the control plants.

(68) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(69) TABLE-US-00003 Ex_no. Eff. % 5 100 6 93 7 85 8 73 12 85 13 80 14 70 16 80 18 70 19 70 20 96 21 98 22 98 25 98 33 95 36 95 37 100 39 99 44 80

Example: In Vivo Preventive Test on Phytophthora infestans (Tomato Late Blight)

(70) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.

(71) Tomato plants (“Rentita” variety), sown in started cups on a 50/50 peat soil-pozzolana substrate and grown at 26° C., are treated at the Z12 leaf stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(72) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Phytophthora infestans spores (20 000 spores per ml). The spores are collected from infected plants. The contaminated tomato plants are incubated at 16-18° C. and at 100% relative humidity.

(73) Grading (% of efficacy) is carried out 5 days after the contamination, in comparison with the control plants.

(74) Under these conditions, good protection (at least 70%) is observed at a dose of 500 ppm with the following compounds:

(75) TABLE-US-00004 Ex_no. Eff. % 3 99 4 100

Example: In Vivo Preventive Test on Pyrenophora teres (Net Blotch on Barley)

(76) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(77) Barley plants (“Plaisant” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 22° C., are treated at the 1-leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(78) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores (12 000 spores per ml). The spores are collected from a 12-day-old culture. The contaminated barley plants are incubated for 48 hours at 20° C. and at 100% relative humidity, and then for 12 days at 20° C. at 70-80% relative humidity.

(79) Grading (% of efficacy) is carried out 14 days after the contamination, in comparison with the control plants.

(80) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(81) TABLE-US-00005 Ex_no. Eff. % 4 100 5 86 6 100 7 100 8 97 9 79 11 96 12 80 13 88 14 100 16 79 17 96 18 100 19 80 20 80 21 88 23 97 24 97 25 100 26 90 28 93 29 97 30 93 33 96 34 80 36 90 37 100 38 96 39 100 40 90 41 88 42 70 43 80 44 79 45 80

Example: In Vivo Preventive Test on Pyricularia oryzae (Rice Blast)

(82) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(83) Rice plants (“Koshihikari” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 26° C., are treated at the 2-leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(84) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyricularia oryzae spores (40 000 spores per ml). The spores are collected from a 15-day-old culture and are suspended in water containing 2.5 g/l of gelatin. The contaminated rice plants are incubated at 25° C. and at 80% relative humidity.

(85) Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.

(86) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(87) TABLE-US-00006 Ex_no. Eff. % 4 80 5 90 6 100 7 90 8 80 9 80 29 83

Example: In Vivo Preventive Test on Puccinia recondita (Brown Rust on Wheat)

(88) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(89) Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 22° C., are treated at the 1-leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(90) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia condita spores (100 000 spores per ml). The spores are collected from an infected plant and are suspended in water containing 2.5 ml/l of Tween 80 at 10%. The contaminated wheat plants are incubated for 24 hours at 20° C. and at 100% relative humidity, and then for 10 days at 20° C. and at 70-80% relative humidity.

(91) Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.

(92) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(93) TABLE-US-00007 Ex_no. Eff. % 1 98 2 98 3 98 4 100 5 100 6 100 7 94 8 100 9 100 10 97 11 94 12 98 13 100 14 100 15 89 16 94 17 97 18 97 19 97 20 94 21 94 22 98 23 98 24 100 25 100 26 97 27 98 28 89 29 97 30 100 31 94 32 83 33 100 34 89 36 97 37 97 38 97 39 97 40 97 41 97 42 89 43 89 44 94 45 94

Example: In Vivo Preventive Test on Septoria tritici (Leaf Spot on Wheat)

(94) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(95) Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 22° C., are treated at the 1-leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(96) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of cryopreserved Septoria tritici spores (500 000 spores per ml). The contaminated wheat plants are incubated for 72 hours at 18° C. and at 100% relative humidity, and then for 21 days at 90% relative humidity.

(97) Grading (% of efficacy) is carried out 24 days after the contamination, in comparison with the control plants.

(98) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(99) TABLE-US-00008 Ex_no. Eff. % 1 75 4 95 8 100 9 80 12 75 13 80 18 75 21 96 22 96 23 97 24 92 25 75 27 70 28 92 30 97 35 75 39 92 40 75 41 81

Example: In Vivo Preventive Test on Sphaerotheca fuliginea (Powdery Mildew on Cucurbits)

(100) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.

(101) Gherkin plants (“Vert petit de Paris” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 24° C., are treated at the Z11 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(102) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of Sphaerotheca fuliginea spores (100 000 spores per ml). The spores are collected from infected plants. The contaminated to gherkin plants are incubated at about 20° C. and at 70-80% relative humidity.

(103) Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.

(104) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(105) TABLE-US-00009 Ex_no. Eff. % 1 100 2 100 3 70 4 100 5 100 6 100 7 100 8 100 9 100 10 100 11 100 12 96 13 100 14 100 17 100 18 100 19 100 21 100 22 100 23 100 24 100 25 100 26 100 27 100 28 100 29 100 30 100 33 100 36 100 37 100 38 100 39 100 40 100 41 100

Example: In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

(106) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(107) Bean plants (“Saxa” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 24° C., are treated at the 2-leaf stage (9 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(108) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores (150 000 spores per ml). The spores are collected from infected plants and are suspended in water containing 2.5 ml/l of Tween 80 at 10%. The contaminated bean plants are incubated for 24 hours at 20° C. and at 100% relative humidity, and then for 10 days at 20° C. and at 70-80% relative humidity.

(109) Grading (% of efficacy) is carried out 11 days after the contamination, in comparison with the control plants.

(110) Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds:

(111) TABLE-US-00010 Ex_no. Eff. % 1 100 2 100 3 100 4 100 5 100 6 100 7 100 8 100 9 100 10 100 11 100 12 100 13 100 14 100 15 89 16 100 17 100 18 100 19 100 20 100 21 100 22 100 23 100 24 100 25 94 26 100 27 100 28 100 29 100 30 100 31 100 32 97 33 99 34 100 35 98 36 94 37 97 38 100 39 100 40 100 41 100 42 97 43 100 44 100 45 100

Example: In Vivo Phakopsora Test (Soybeans)/Preventive

(112) Solvent: 24.5 parts by weight of acetone

(113) 24.5 parts by weight of dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(114) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(115) To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous to spore suspension of the causal agent of soybean rust (Phakopsora pachyrhizi) and stay for 24 h without light in an incubation cabinet at approximately 24° C. and a relative atmospheric humidity of 95%.

(116) The plants remain in the incubation cabinet at approximately 24° C. and a relative atmospheric humidity of approximately 80% and a day/night interval of 12 h.

(117) The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(118) In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of 100 ppm of active ingredient.

(119) TABLE-US-00011 Ex_no. Eff. % 13 100 27 100 29 91

(120) Under the same conditions, excellent (at least 90%) protection is observed at a dose of 10 ppm of active ingredient with compound of example 7, whereas no protection is observed with the example 87 from disclosed in patent application WO2002008197:

(121) TABLE-US-00012 Example dose (ppm) Efficacy 7 from this patent 10 90 Example 87 form WO2002008197 10 0

Example: In Vivo Blumeria Test (Barley)/Preventive

(122) Solvent: 49 parts by weight of N,N-dimethylacetamide

(123) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(124) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(125) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(126) After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis fsp. hordei.

(127) The plants are placed in the greenhouse at a temperature of approximately 18° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

(128) The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(129) In this test the following compounds according to the invention showed an efficacy of 70% or even higher at a concentration of 500 ppm of active ingredient.

(130) TABLE-US-00013 Ex_no. Eff. % 7 100 8 100

Example: In Vivo Leptosphaeria nodorum Test (Wheat)/Preventive

(131) Solvent: 49 parts by weight of N,N-dimethylacetamide

(132) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(133) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(134) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(135) After the spray coating has been dried, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

(136) The plants are placed in the greenhouse at a temperature of approximately 22° C. and a relative atmospheric humidity of approximately 80%.

(137) The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(138) In this test the following compounds according to the invention showed an efficacy of 70% or even higher at a concentration of 500 ppm of active ingredient.

(139) TABLE-US-00014 Ex_no. Eff. % 7 90

(140) Under the same conditions, excellent (at least 90%) protection is observed at a dose of 500 ppm of active ingredient with compound of example 7, whereas no protection is observed with the example 87 from disclosed in patent application WO2002008197:

(141) TABLE-US-00015 Example dose (ppm) Efficacy 7 from this patent 500 90 Example 87 form WO2002008197 500 0

Example: In Vivo Fusarium nivale (Var. Majus)-Test (Wheat)/Preventive

(142) Solvent: 49 parts by weight of N,N-dimethylacetamide

(143) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(144) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(145) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(146) After the spray coating has been dried, the plants are slightly injured by using a sandblast and afterwards to they are sprayed with a conidia suspension of Fusarium nivale (var. majus).

(147) The plants are placed in the greenhouse under a translucent incubation cabinet at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100%.

(148) The test is evaluated 5 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(149) In this test the following compounds according to the invention showed an efficacy of 70% or even higher at a concentration of 500 ppm of active ingredient.

(150) TABLE-US-00016 Ex_no. Eff. % 4 80 29 86

EXPERIMENTAL EXAMPLES

(151) Process (a)

(152) ##STR00015##

5-fluoro-3-(difluoromethyl)-N-{4′-[(methoxyimino)methyl]biphenyl-2-yl}-1-methyl-1H-pyrazole-4-carboxamide

Example 9

(153) In a 25 ml round bottom flask, a solution of 4′-[(methoxyimino)methyl]biphenyl-2-amine (200 mg, 0.799 mmol, 1 eq.) in 5 ml of DCM is cooled to 0° C. and triethylamine (0.245 ml, 1.758 mmol, 2.2 eq) is added followed by DMAP (9 mg, 0.08 mmol, 0.1 eq). A solution of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride (186 mg, 0.879 mmol, 1.1 eq) in 1 ml of DCM is added dropwise. Stirring is allowed for 4h at r.t. The reaction is quenched with 1N aq. HCl, and diluted with EtOAc. The aqueous layer was separated and extracted with EtOAc. The organics were combined, washed with NaOH 1N, dried over MgSO.sub.4 and concentrated. The crude material was purified by chromatography on silica gel to give pure material (88%)