HALOGEN-SUBSTITUTED PHENOXYPHENYLAMIDINES AND THE USE THEREOF AS FUNGICIDES

Abstract

The present invention relates to halogen-substituted phenoxyphenylamidines of the general formula (I), to a process for their preparation, to the use of the amidines according to the invention for controlling unwanted microorganisms and also to an agrochemical formulation for this purpose, comprising the halogen-substituted phenoxyphenylamidines according to the invention. Furthermore, the invention relates to a method for controlling unwanted microorganisms by applying the compounds according to the invention to the microorganisms and/or their habitat.

Claims

1. A phenoxyphenylamidine of formula (I) ##STR00030## in which R.sup.1 is selected from the group consisting of halogen and halomethyl; R.sup.2 is methyl; R.sup.3 is halogen; And/or a salt, N-oxide, metal complex and/or a stereoisomer thereof.

2. A compound according to claim 1 where R.sup.1 is selected from the group consisting of fluoro, chloro, bromo, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, and trifluoromethyl; R.sup.2 is methyl; R.sup.3 is selected from the group consisting of bromo, chloro and fluoro.

3. A compound according to claim 1 where R.sup.1 is selected from the group consisting of chloro, bromo, difluoromethyl, and trifluoromethyl; R.sup.2 is methyl; R.sup.3 is fluoro and chloro.

4. The phenoxyphenylamidines as claimed in claim 1 selected from the group consisting of N-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-(difluoromethyl)-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-bromo-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-bromo-4-(2-chlorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-chloro-4-(2-chlorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-chloro-4-(2-iodophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N-[2-bromo-4-(2-bromophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide.

5. A process for preparing a phenoxyphenylamidine as claimed in claim 1 which comprises at least one of the following: (a) reaction of nitrobenzene derivatives of the formula (III) with phenol derivatives of the formula (II) according to the reaction scheme below: ##STR00031## (b) reaction of nitrophenol derivatives of the formula (V) with phenyl derivatives of the formula (IV) according to the reaction scheme below: ##STR00032## (c) reaction of anilines of the formula (VII) with phenols (II) according to the reaction scheme below: ##STR00033## (d) reaction of aminophenols of the formula (XII) with phenyl derivatives of the formula (IV) according to the reaction scheme below: ##STR00034## (e) reduction of the nitrophenoxy ethers of the formula (VI) to aminophenyl ethers of the formula (VIII) according to the reaction scheme below: ##STR00035## (f) reaction of the aminophenyl ethers of the formula (VIII) with (i) aminoacetals of the formula (XIII) or (ii) with N-ethyl-N-methylformamide of the formula (XIV) or (iii) with N-methylethanamine of the formula (XV) in the presence of ortho esters of the formula (XVI) according to the reaction scheme below: ##STR00036## (g) reaction of the aminophenols of the formula (XII) with (i) aminoacetals of the formula (XIII) or (ii) with N-ethyl-N-methylformamide of the formula (XIV) or (iii) with N-methylethanamine of the formula (XV) in the presence of ortho esters of the formula (XVI) according to the reaction scheme below: ##STR00037## (h) reaction of the anilines of the formula (VII) with (i) aminoacetals of the formula (XIII) or (ii) with N-ethyl-N-methylformamide of the formula (XIV) or (iii) with N-methylethanamine of the formula (XV) in the presence of ortho esters of the formula (XVI) according to the reaction scheme below: ##STR00038## (i) reaction of amidines of the formula (XI) with phenol derivatives of the formula (II) according to the reaction scheme below: ##STR00039## (j) reaction of amidines of the formula (XI) with phenyl derivatives of the formula (IV) according to the reaction scheme below: ##STR00040## where in the above schemes Z is a leaving group; R.sup.6 and R.sup.7 independently of one another are selected from the group consisting of C.sub.1-12-alkyl, C.sub.2-12-alkenyl, C.sub.2-12-alkynyl or C.sub.5-18-aryl or C.sub.7-19-arylalkyl groups and together with the atoms to which they are attached may form a five-, six- or seven-membered ring; R.sup.8 to R.sup.10 independently of one another are selected from the group consisting of C.sub.1-12-alkyl, C.sub.2-12-alkenyl, C.sub.2-12-alkynyl or C.sub.5-18-aryl or C.sub.7-19-arylalkyl, C.sub.7-19-alkylaryl groups and in each case R.sup.8 with R.sup.9, R.sup.9 with R.sup.10 or R.sup.8 with R.sup.10 together with the atoms to which they are attached and if appropriate together with further carbon, nitrogen, oxygen or sulfur atoms may form a five-, six- or seven-membered ring.

6. An nitrophenyl ether of formula (VI) ##STR00041## in which R.sup.1 is selected from the group consisting of halogen and halomethyl; R.sup.2 is methyl; R.sup.3 is halogen.

7. An aminophenyl ether of formula (VIII) ##STR00042## in which R.sup.1 is selected from the group consisting of halogen and halomethyl; R.sup.2 is methyl; R.sup.3 is halogen.

8. Agrochemical formulation for controlling unwanted microorganisms, comprising at least one phenoxyphenylamidine as claimed in claim 1.

9. A phenoxyphenylamidine as claimed in claim 1 or agrochemical formulation thereof for controlling unwanted microorganisms.

10. A method for controlling unwanted microorganisms, wherein the substituted phenoxyphenylamidine as claimed in claim 1 or agrochemical formulation thereof is applied to the microorganisms and/or a habitat thereof.

11. Seed treated with at least one phenoxyphenylamidine as claimed in claim 1.

12. A phenoxyphenylamidine as claimed in claim 1 for treating seed.

13. A phenoxyphenylamidine as claimed in claim 1 for treating transgenic plants.

14. A phenoxyphenylamidine as claimed in claim 1 for treating seed of transgenic plants.

15. A method for protecting seed against unwanted microorganisms by using seed treated with at least one phenoxyphenylamidine as claimed in claim 1.

Description

EXAMPLES

[0248] ##STR00024##

TABLE-US-00005 Ex No R.sup.1 R.sup.2 R.sup.3 LogP I-01 Cl Me F 1.66.sup.[a] I-02 CHF.sub.2 Me F 1.76.sup.[a] I-03 Br Me F 1.66.sup.[a]; 4.53.sup.[b] I-04 Br Me Cl 1.84.sup.[a]; 4.97.sup.[b] I-05 Cl Me Cl 1.58.sup.[a] I-06 Cl Me I 1.78.sup.[a] I-07 Br Me Br 1.81.sup.[a]

##STR00025##

TABLE-US-00006 Ex No R.sup.1 R.sup.2 R.sup.3 LogP VI-01 Cl Me F 4.21[a]; 4.17[b] VI-02 CHF.sub.2 Me F 3.97[a] VI-03 Br Me F 4.26[a] VI-04 Br Me Cl 4.68[a] VI-05 Cl Me Cl 4.67[a] VI-06 Cl Me I 4.94[a] VI-07 Br Me Br 4.80[a]

##STR00026##

TABLE-US-00007 Ex No R.sup.1 R.sup.2 R.sup.3 LogP VIII-01 Cl Me F 3.45[a]; 3.40[b] VIII-02 CHF.sub.2 Me F VIII-03 Br Me F 3.55[a] VIII-04 Br Me Cl 3.53[b] VIII-05 Cl Me Cl 3.85[a] VIII-06 Cl Me I 4.23[a] VIII-07 Br Me Br 4.14[a]

[0249] Measurement of Log P values was performed according to EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods: [0250] [.sup.a] Log P value is determined by measurement of LC-UV, in an acidic range, with 0.1% formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile). [0251] [.sup.b] Log P value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).

[0252] Calibration was done with straight-chain alkan2-ones (with 3 to 16 carbon atoms) with known Log P values (measurement of Log P 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

[0253] 1H-NMR data of selected examples are written in form of 1H-NMR-peak lists. To each signal peak are listed the ?-value in ppm and the signal intensity in round brackets. Between the ?-valuesignal intensity pairs are semicolons as delimiters.

[0254] The peak list of an example has therefore the form:

?.sub.1 (intensity.sub.1); ?.sub.2 (intensity.sub.2); . . . ; ?.sub.i (intensity.sub.i); . . . ; ?.sub.n (intensity.sub.n)

[0255] 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.

[0256] 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.

[0257] The 1H-NMR peak lists are similar to classical 1H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.

[0258] 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.

[0259] 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.

[0260] 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%).

[0261] 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.

[0262] 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.

[0263] 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.

TABLE-US-00008 Example I-01: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.750 (1.4); 7.637 (0.6); 7.386 (0.9); 7.379 (0.6); 7.373 (0.8); 7.368 (0.7); 7.361 (1.2); 7.357 (1.1); 7.352 (0.8); 7.350 (0.7); 7.339 (1.0); 7.333 (1.1); 7.170 (0.5); 7.157 (2.2); 7.151 (1.9); 7.143 (2.5); 7.138 (2.3); 7.132 (2.4); 7.126 (1.2); 7.120 (0.9); 7.107 (0.3); 6.958 (1.6); 6.937 (0.7); 6.907 (0.9); 6.900 (0.6); 6.895 (0.8); 6.883 (1.3); 6.867 (0.7); 6.861 (0.8); 6.850 (5.7); 3.446 (0.5); 3.429 (0.6); 3.376 (0.6); 3.359 (1.2); 3.340 (1.4); 3.328 (27.2); 2.999 (1.7); 2.926 (4.4); 2.525 (0.7); 2.512 (14.1); 2.507 (28.3); 2.503 (37.5); 2.498 (28.2); 2.494 (14.5); 2.130 (16.0); 1.161 (1.6); 1.144 (3.5); 1.127 (2.4); 0.008 (1.7); 0.000 (43.5); ?0.009 (1.8) Example I-02: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.894 (1.3); 7.779 (0.8); 7.399 (1.4); 7.392 (1.1); 7.386 (1.6); 7.374 (2.0); 7.371 (1.9); 7.365 (1.5); 7.352 (1.5); 7.346 (1.7); 7.305 (0.8); 7.261 (0.4); 7.185 (1.0); 7.166 (5.0); 7.161 (5.0); 7.148 (4.2); 7.123 (1.1); 7.039 (1.7); 7.026 (1.8); 6.982 (0.5); 6.905 (1.8); 6.889 (1.1); 6.852 (7.9); 3.903 (2.8); 3.636 (1.4); 3.448 (1.1); 3.432 (1.3); 3.397 (1.3); 3.380 (2.4); 3.363 (2.5); 3.321 (201.6); 3.283 (0.4); 3.174 (0.3); 3.163 (0.4); 3.018 (3.0); 2.929 (6.7); 2.670 (1.5); 2.506 (182.9); 2.502 (228.4); 2.497 (170.7); 2.335 (2.0); 2.328 (1.4); 2.209 (16.0); 1.249 (0.4); 1.234 (0.8); 1.168 (2.7); 1.151 (5.3); 1.133 (3.9); 1.110 (2.5); 0.977 (0.6); 0.961 (0.6); 0.000 (9.6) Example I-03: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.737 (1.2); 7.620 (0.5); 7.384 (0.9); 7.378 (0.6); 7.372 (0.7); 7.367 (0.7); 7.360 (1.2); 7.356 (1.1); 7.351 (0.8); 7.337 (1.0); 7.331 (1.2); 7.172 (0.5); 7.159 (2.1); 7.154 (2.0); 7.145 (2.8); 7.142 (2.1); 7.139 (2.2); 7.135 (2.3); 7.127 (1.1); 7.122 (0.9); 6.987 (5.6); 6.956 (1.4); 6.932 (0.7); 6.912 (0.9); 6.905 (0.6); 6.900 (0.7); 6.888 (1.3); 6.872 (0.7); 6.867 (0.8); 3.445 (0.5); 3.429 (0.6); 3.375 (0.5); 3.359 (1.1); 3.342 (1.1); 3.316 (14.4); 2.999 (1.6); 2.931 (3.7); 2.524 (0.7); 2.511 (11.8); 2.506 (23.7); 2.502 (31.7); 2.498 (23.9); 2.493 (12.1); 2.121 (16.0); 1.398 (0.9); 1.163 (3.3); 1.145 (6.7); 1.128 (3.2); 0.008 (1.3); 0.000 (35.4); ?0.008 (1.4) Example I-04: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.744 (1.2); 7.627 (0.5); 7.574 (2.2); 7.570 (2.4); 7.554 (2.5); 7.550 (2.6); 7.320 (1.1); 7.316 (1.1); 7.299 (1.9); 7.297 (2.0); 7.281 (1.5); 7.277 (1.5); 7.146 (1.4); 7.142 (1.6); 7.126 (2.1); 7.123 (2.3); 7.107 (1.1); 7.104 (1.2); 6.996 (6.1); 6.968 (1.4); 6.944 (0.7); 6.814 (2.0); 6.811 (2.2); 6.793 (1.9); 6.790 (2.0); 5.753 (0.9); 3.449 (0.5); 3.433 (0.6); 3.379 (0.5); 3.363 (1.1); 3.345 (1.0); 3.315 (11.3); 3.002 (1.6); 2.935 (3.8); 2.524 (0.6); 2.520 (0.8); 2.511 (12.0); 2.506 (24.7); 2.502 (33.4); 2.497 (25.1); 2.493 (12.6); 2.082 (16.0); 1.989 (0.5); 1.398 (0.6); 1.176 (0.5); 1.165 (3.6); 1.147 (7.6); 1.130 (3.6); 0.008 (1.0); 0.000 (28.7); ?0.009 (1.1) Example I-05: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.757 (1.4); 7.644 (0.6); 7.573 (2.3); 7.569 (2.4); 7.553 (2.5); 7.549 (2.6); 7.316 (1.1); 7.312 (1.1); 7.295 (2.1); 7.294 (2.1); 7.277 (1.5); 7.273 (1.4); 7.143 (1.4); 7.140 (1.6); 7.124 (2.2); 7.121 (2.3); 7.105 (1.2); 7.101 (1.2); 6.969 (1.8); 6.945 (0.8); 6.861 (6.6); 6.811 (2.3); 6.808 (2.4); 6.791 (2.1); 6.788 (2.2); 3.453 (0.6); 3.437 (0.6); 3.379 (0.6); 3.362 (1.3); 3.345 (1.3); 3.325 (7.9); 3.002 (1.7); 2.933 (4.3); 2.509 (9.6); 2.504 (12.4); 2.500 (9.2); 2.093 (16.0); 2.071 (0.9); 1.397 (11.6); 1.324 (0.5); 1.162 (2.1); 1.146 (4.2); 1.129 (2.5); 0.000 (3.1) Example I-06: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.898 (1.9); 7.881 (1.9); 7.879 (1.9); 7.753 (1.2); 7.641 (0.5); 7.359 (0.9); 7.340 (1.8); 7.323 (1.0); 7.320 (1.0); 7.030 (0.3); 6.965 (1.8); 6.919 (1.2); 6.901 (2.3); 6.881 (1.0); 6.822 (5.0); 6.743 (0.6); 6.701 (2.0); 6.681 (1.9); 3.448 (0.5); 3.436 (0.6); 3.361 (1.1); 3.344 (1.2); 3.319 (11.6); 3.000 (1.5); 2.930 (3.7); 2.502 (31.0); 2.162 (0.4); 2.085 (12.9); 2.062 (1.2); 1.398 (16.0); 1.337 (0.3); 1.320 (0.6); 1.160 (1.8); 1.144 (3.7); 1.129 (2.3); 0.000 (24.3) Example I-07: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.744 (1.5); 7.716 (2.4); 7.696 (2.5); 7.628 (0.7); 7.354 (1.1); 7.336 (2.3); 7.315 (1.3); 7.074 (1.4); 7.056 (2.4); 7.037 (1.2); 6.992 (5.6); 6.969 (1.8); 6.944 (0.9); 6.783 (2.4); 6.762 (2.2); 3.448 (0.7); 3.434 (0.8); 3.363 (1.4); 3.345 (1.4); 3.320 (9.0); 3.002 (2.2); 2.935 (4.7); 2.502 (26.3); 2.078 (16.0); 1.165 (3.8); 1.147 (7.6); 1.130 (3.8); 0.000 (0.9) Example VI-01: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.181 (4.3); 7.504 (0.9); 7.501 (0.6); 7.484 (1.4); 7.479 (1.0); 7.477 (1.1); 7.473 (0.7); 7.455 (1.1); 7.391 (0.4); 7.386 (0.6); 7.380 (0.5); 7.374 (1.3); 7.369 (1.6); 7.363 (0.9); 7.356 (2.0); 7.351 (2.7); 7.337 (2.4); 7.329 (2.9); 7.325 (2.5); 7.312 (1.4); 7.309 (1.2); 7.304 (0.4); 7.291 (0.4); 7.288 (0.4); 6.861 (4.8); 3.330 (25.8); 2.513 (11.4); 2.509 (22.7); 2.504 (29.8); 2.499 (22.0); 2.495 (11.0); 2.364 (16.0); 0.008 (0.5); 0.000 (14.3); ?0.008 (0.5) Example VI-03: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.138 (4.6); 7.500 (0.8); 7.496 (0.6); 7.479 (1.3); 7.470 (1.0); 7.450 (1.1); 7.386 (0.4); 7.380 (0.5); 7.374 (0.5); 7.366 (1.4); 7.364 (1.4); 7.359 (1.5); 7.351 (1.1); 7.345 (2.6); 7.332 (1.4); 7.326 (3.8); 7.321 (2.9); 7.309 (1.4); 7.300 (0.4); 7.289 (0.4); 7.285 (0.4); 6.975 (5.0); 3.312 (10.0); 2.526 (0.3); 2.508 (16.3); 2.504 (21.5); 2.499 (16.1); 2.344 (16.0); 0.000 (1.6) Example VI-04: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.314 (4.7); 8.210 (0.5); 8.150 (4.5); 8.148 (4.5); 7.694 (2.0); 7.690 (2.1); 7.674 (2.3); 7.670 (2.3); 7.495 (0.9); 7.491 (0.9); 7.475 (1.9); 7.472 (2.0); 7.456 (1.6); 7.452 (1.5); 7.380 (1.3); 7.377 (1.7); 7.361 (2.0); 7.357 (2.5); 7.337 (3.7); 7.334 (2.3); 7.317 (2.1); 7.313 (1.8); 7.268 (0.4); 7.228 (0.4); 6.871 (6.4); 6.037 (0.8); 3.329 (16.3); 2.526 (0.5); 2.513 (12.0); 2.508 (24.1); 2.504 (31.6); 2.500 (23.5); 2.495 (11.8); 2.351 (2.2); 2.341 (16.0); 0.000 (3.4) Example VI-05: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.187 (4.8); 7.691 (2.2); 7.671 (2.4); 7.496 (0.8); 7.493 (0.9); 7.473 (2.2); 7.457 (1.5); 7.454 (1.6); 7.380 (1.7); 7.361 (2.5); 7.345 (3.3); 7.342 (3.5); 7.325 (1.9); 7.322 (1.9); 6.758 (5.9); 3.323 (6.0); 2.673 (0.5); 2.506 (16.8); 2.364 (16.0) Example VI-06: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.197 (4.9); 8.008 (2.1); 8.005 (2.2); 7.988 (2.2); 7.985 (2.3); 7.541 (1.0); 7.538 (1.0); 7.521 (2.0); 7.519 (2.0); 7.503 (1.3); 7.499 (1.3); 7.263 (2.4); 7.260 (2.6); 7.243 (2.1); 7.240 (2.1); 7.146 (1.3); 7.143 (1.3); 7.127 (2.2); 7.124 (2.2); 7.108 (1.1); 7.105 (1.1); 6.655 (6.2); 3.323 (7.8); 2.509 (11.5); 2.505 (15.1); 2.501 (11.6); 2.375 (16.0); 2.301 (0.4); 2.297 (0.4); 0.008 (0.3); 0.000 (8.1) Example VI-07: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 8.152 (4.7); 7.854 (0.3); 7.833 (2.1); 7.830 (2.1); 7.814 (2.2); 7.810 (2.2); 7.535 (1.0); 7.531 (1.0); 7.513 (2.0); 7.496 (1.4); 7.492 (1.3); 7.323 (2.1); 7.320 (2.8); 7.309 (1.9); 7.304 (2.3); 7.300 (2.3); 7.290 (2.4); 7.271 (1.2); 7.267 (1.0); 6.841 (6.5); 3.323 (10.0); 2.509 (14.0); 2.505 (17.6); 2.500 (12.7); 2.345 (16.0); 2.279 (1.0); 2.275 (1.0); 1.397 (3.1); 0.000 (4.3) Example VIII-01: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.346 (0.9); 7.341 (0.7); 7.339 (0.7); 7.328 (0.9); 7.322 (1.2); 7.317 (1.0); 7.313 (0.9); 7.298 (1.1); 7.293 (1.1); 7.116 (0.4); 7.112 (0.5); 7.097 (1.6); 7.092 (1.5); 7.084 (1.0); 7.079 (2.5); 7.073 (2.3); 7.068 (1.3); 7.065 (1.1); 7.059 (0.9); 7.053 (0.9); 7.049 (1.0); 7.034 (0.4); 6.844 (5.9); 6.778 (1.0); 6.772 (0.9); 6.757 (1.5); 6.754 (1.5); 6.752 (1.5); 6.732 (5.7); 5.205 (5.1); 3.337 (12.7); 2.513 (5.6); 2.509 (11.3); 2.505 (14.8); 2.500 (10.9); 2.077 (0.6); 2.022 (16.0); 0.000 (2.5) Example VIII-03: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.343 (0.9); 7.338 (0.8); 7.325 (1.0); 7.319 (1.3); 7.315 (1.2); 7.310 (1.0); 7.295 (1.2); 7.290 (1.3); 7.185 (0.5); 7.115 (0.6); 7.101 (1.8); 7.096 (1.7); 7.086 (1.5); 7.082 (2.6); 7.076 (2.5); 7.070 (1.7); 7.062 (1.2); 7.056 (1.2); 7.051 (1.2); 7.044 (0.4); 7.037 (0.5); 7.033 (0.5); 7.018 (0.8); 6.959 (5.8); 6.788 (1.0); 6.783 (1.0); 6.763 (1.7); 6.746 (6.1); 6.733 (0.4); 6.381 (0.6); 5.149 (5.1); 4.912 (0.5); 3.313 (10.3); 2.507 (17.2); 2.503 (22.7); 2.499 (17.2); 2.111 (1.9); 2.028 (1.8); 2.016 (16.0); 1.990 (0.4); 0.000 (2.8) Example VIII-04: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.534 (2.1); 7.530 (2.2); 7.525 (0.5); 7.521 (0.5); 7.515 (2.4); 7.511 (2.4); 7.505 (0.5); 7.501 (0.4); 7.488 (0.3); 7.472 (0.3); 7.468 (0.3); 7.267 (1.2); 7.263 (1.1); 7.248 (1.8); 7.246 (1.8); 7.244 (1.9); 7.227 (1.4); 7.223 (1.4); 7.087 (0.4); 7.080 (1.4); 7.076 (1.5); 7.060 (2.1); 7.057 (2.1); 7.041 (1.1); 7.038 (1.1); 7.008 (0.3); 6.978 (6.3); 6.885 (0.3); 6.882 (0.3); 6.771 (0.9); 6.752 (4.8); 6.700 (2.2); 6.696 (2.3); 6.679 (2.2); 6.676 (2.2); 6.652 (0.3); 6.648 (0.4); 6.371 (0.9); 5.754 (0.4); 5.185 (5.0); 4.888 (0.6); 3.321 (13.2); 2.525 (0.4); 2.512 (9.6); 2.508 (19.6); 2.503 (25.8); 2.499 (19.2); 2.494 (9.7); 2.058 (0.7); 1.989 (2.6); 1.970 (16.0); 1.323 (0.4); 0.008 (0.8); 0.000 (23.9); ?0.008 (1.0) Example VIII-05: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 9.442 (0.5); 7.533 (2.0); 7.530 (2.0); 7.513 (2.2); 7.510 (2.1); 7.262 (1.0); 7.259 (1.0); 7.242 (2.0); 7.240 (2.0); 7.223 (1.3); 7.219 (1.2); 7.095 (0.4); 7.077 (1.3); 7.073 (1.4); 7.057 (2.1); 7.055 (2.1); 7.038 (1.0); 7.035 (1.0); 6.976 (0.6); 6.945 (0.5); 6.860 (5.8); 6.815 (0.4); 6.796 (0.4); 6.744 (5.1); 6.696 (2.3); 6.693 (2.5); 6.676 (2.2); 6.673 (2.2); 5.224 (5.4); 4.002 (0.4); 3.984 (0.4); 3.328 (4.7); 2.509 (8.6); 2.505 (10.8); 2.501 (8.1); 2.071 (1.4); 1.982 (16.0); 1.396 (0.8); 1.341 (0.4); 1.324 (0.8); 1.307 (0.4); 0.000 (11.4) Example VIII-06: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 7.878 (0.4); 7.863 (2.6); 7.844 (2.6); 7.307 (1.2); 7.288 (2.4); 7.270 (1.6); 7.251 (0.6); 7.232 (1.0); 7.182 (0.5); 7.163 (0.5); 6.901 (0.3); 6.883 (1.1); 6.860 (1.7); 6.840 (3.2); 6.831 (6.2); 6.739 (5.2); 6.582 (2.7); 6.562 (2.6); 5.214 (6.6); 3.322 (8.5); 2.932 (0.6); 2.503 (32.7); 2.301 (1.7); 2.095 (0.9); 2.087 (1.9); 2.072 (2.2); 1.970 (16.0); 1.397 (5.0); 1.144 (0.6); 0.000 (21.3) Example VIII-07: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): ? = 9.498 (0.4); 7.679 (2.1); 7.675 (2.2); 7.659 (2.2); 7.656 (2.3); 7.305 (1.0); 7.301 (1.1); 7.284 (1.9); 7.282 (1.9); 7.266 (1.3); 7.262 (1.3); 7.189 (0.4); 7.166 (0.3); 7.108 (0.8); 7.013 (1.3); 7.010 (1.4); 6.993 (2.7); 6.991 (2.6); 6.975 (7.3); 6.936 (0.8); 6.929 (0.6); 6.922 (0.6); 6.813 (0.4); 6.791 (0.6); 6.750 (4.9); 6.671 (2.5); 6.667 (2.6); 6.650 (2.2); 6.647 (2.2); 5.186 (5.6); 5.047 (0.4); 4.006 (0.6); 3.988 (0.6); 3.320 (9.7); 2.507 (24.8); 2.503 (32.3); 2.498 (24.4); 2.086 (1.1); 2.082 (1.1); 2.056 (2.1); 1.964 (16.0); 1.340 (0.6); 1.323 (1.3); 1.306 (0.6); 0.008 (1.7); 0.000 (28.4); ?0.008 (1.6)

Stability Data Examples

Stability Towards Hydrolysis in Homogeneous Aqueous SolutionHydrolysis Stability Test

[0264] The chemical stability towards hydrolysis of the phenylamidines described in the prior art is good but an improved stability may be an advantage during the preparation and formulation processes in a large scale. The improved stability towards hydrolysis was proven by a hydrolysis stability test as described below:

[0265] To produce a suitable preparation of active compound for the hydrolysis stability test, a 1000 ppm stock solution (1 mg/mL) of active compound in acetonitrile is prepared. Three aliquots of 100 ?L are pipetted into HPLC vials and diluted with 750 ?L acetonitrile. In each vial 850 ?L of the appropriate buffer solution (pH4, pH7 and pH9, CertiPUR, Fa. Merck) is added. The buffer containing HPLC vials are incubated in a heated sample tray at 50? C. for 24 hours. The amount A of the active compound is analyzed by HPLC (UV-peak areas at 210 nm) at eight points in time t: 0 min, 140 min, 350 min, 560 min, 770 min, 980 min, 1190 min, 1400 min. The half-life time (T.sub.1/2) of each active compound is calculated via linear regression by using the following equations (first order degradation assumed):

[00001]$\ln ?\left[A?\left(t\right)\right]=-\mathrm{kt}+\ln ?\left[A?\left(0\right)\right]$$T_{1/2}=\frac{\ln .Math..Math.2}{k}$

[0266] In table III the results of the hydrolysis stability test are shown for the compounds (I-01), (I-02), (I-03) and (I-04) at various pH-values. To demonstrate the improved stability towards hydrolysis in view of phenylamidines known from the art, the results were compared with compound number 1 known from WO2008/110313 and compound no. 337 known from WO2008/110278. The data demonstrate that compounds according to the invention show indeed a higher stability towards hydrolysis. This increased stability will be of advantage during the preparation and formulation processes in a large scale compared to known amidines. The data are to be seen merely by way of example and are not limiting for the purposes of the invention.

TABLE-US-00009 TABLE III Ex No T.sub.1/2 (pH 7) T.sub.1/2 (pH 9) I-01 52 h 47 h I-02 160 h 140 h I-03 68 h 51 h I-04 64 h 58 h I-05 51 h 47 h I-07 63 h 57 h Compound no. 1 24 h 16 h known from WO2008/110313 Compound no.337 25 h 17 h known from WO2008/110278

Stability Towards PhotolysisPhotolysis Stability Test

[0267] The stability towards photolysis of the phenylamidines described in the prior art is good but an improved stability towards photolysis may be an advantage as it could offer a longer lasting efficacy when applied to plants by foliar application. The improved stability towards photolysis was proven by a hydrolysis stability test as described below: To produce a suitable preparation of active compound for the photolysis stability test, a 1000 ppm stock solution (1 mg/mL) of active compound in acetonitrile is prepared. Aliquots of 25 ?L of this stock solution are pipetted in three wells of a Bio-one microtiter plate (MTP) UVStar 96 (Fa. Greiner, Art. No. 655801). The MTP is dried overnight in the dark and then irradiated at 30? C. and 480 W/m.sup.2 with a UV irradiation device SUNTEST XLS+ or SUNTEST CPS (Fa. Atlas). The amount A of the active compound is analyzed by HPLC (UV-peak areas at 210 nm) at five points in time t: 0 h, 2 h, 4 h, 6 h, 24 h by using the following method: 200 ?L acetonitrile is added in the respective well of the MTP and the MTP is sealed with a Bio-one sealing foil, viewseal 80/140 mm (Fa. Greiner, Art. No. 676070). The MTPs are sonicated for 3 minutes and analysed by HPLC. The half-life time (T) of each active compound is calculated via linear regression by using the following equations (first order degradation assumed):

[00002]$\ln ?\left[A?\left(t\right)\right]=-\mathrm{kt}+\ln ?\left[A?\left(0\right)\right]$$T_{1/2}=\frac{\ln .Math..Math.2}{k}$

[0268] In table IV the results of the photolysis stability test are shown for the compounds (I-01), (I-02), (I-03) and (I-04). To demonstrate the improved stability towards photolysis in view of phenylamidines known from the art, the results were compared with compound number 1 known from WO2008/110313. The data demonstrate that compounds according to the invention show indeed a higher chemical stability towards photolysis. This increased chemical stability towards photolysis will be of advantage as it will offer a longer lasting efficacy when applied to plants by foliar application compared to known amidines. The data are to be seen merely by way of example and are not limiting for the purposes of the invention.

TABLE-US-00010 TABLE IV Ex No T.sub.1/2 I-01 >200 h I-02 185 h I-03 178 h I-04 >200 h Compound no. 1 10 h known from WO2008/110313

Plant Compatibility Test Using Soy Bean Plants

[0269] Solvent: 24.5 parts by weight of acetone [0270] 24.5 parts by weight of dimethylacetamide [0271] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0272] 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. Young plants are sprayed with the preparation of active compound at the stated application rate. The plants are then placed in a greenhouse at approximately 21? C. and a relative atmospheric humidity of approximately 80%. The test is evaluated 6 days after application and comprises plant damages like leaf deformation, chlorosis, necrosis, shoot damage or stunting. The results are summarized in table V. 0% means no damages are observed, while 100% means that the plants are totally damaged.

TABLE-US-00011 TABLE V Plant compatibility soy bean Rate of application of active compound Active compound in ppm Necrosis in % Known from WO2008/110313: Ex. 1 [00027] 1000 90 Known from WO2008/110278: Ex. 337 [00028] 1000 90 According to the invention: Ex. I-01 [00029] 1000 20

Use Examples

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

[0273] Solvent: 5% by volume of Dimethyl sulfoxide [0274] 10% by volume of Acetone [0275] Emulsifier: 1 ?l of Tween? 80 per mg of active ingredient

[0276] The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/Tween? 80 and then diluted in water to the desired concentration.

[0277] The young plants of wheat are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween? 80.

[0278] After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores. 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.

[0279] The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

[0280] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01; 1-02; 1-03; 1-04

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

[0281] Solvent: 5% by volume of Dimethyl sulfoxide [0282] 10% by volume of Acetone [0283] Emulsifier: 1 ?l of Tween? 80 per mg of active ingredient

[0284] The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/Tween? 80 and then diluted in water to the desired concentration.

[0285] The young plants of barley are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween? 80.

[0286] After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. 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. and at 70-80% relative humidity.

[0287] The test is evaluated 14 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

[0288] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: I-01; I-03; I-04

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

[0289] Solvent: 5% by volume of Dimethyl sulfoxide [0290] 10% by volume of Acetone [0291] Emulsifier: 1 ?l of Tween? 80 per mg of active ingredient

[0292] The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/Tween? 80 and then diluted in water to the desired concentration.

[0293] The young plants of wheat are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween? 80.

[0294] After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores. The contaminated wheat plants are incubated for 72 hours at 18? C. and at 100% relative humidity and then for 21 days at 20? C. and at 90% relative humidity.

[0295] The test is evaluated 24 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

[0296] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01; 1-02; 1-04

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

[0297] Solvent: 5% by volume of Dimethyl sulfoxide [0298] 10% by volume of Acetone [0299] Emulsifier: 1 ?l of Tween? 80 per mg of active ingredient

[0300] The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/Tween? 80 and then diluted in water to the desired concentration.

[0301] The young plants of gherkin are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween? 80.

[0302] After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores. The contaminated gherkin plants are incubated for 72 hours at 18? C. and at 100% relative humidity and then for 12 days at 20? C. and at 70-80% relative humidity.

[0303] The test is evaluated 15 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

[0304] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01; 1-02; 1-03; 1-04

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

[0305] Solvent: 5% by volume of Dimethyl sulfoxide [0306] 10% by volume of Acetone [0307] Emulsifier: 1 ?l of Tween? 80 per mg of active ingredient

[0308] The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/Tween? 80 and then diluted in water to the desired concentration.

[0309] The young plants of bean are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween? 80.

[0310] After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores. 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.

[0311] The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

[0312] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01; 1-02; 1-03; 1-04

Example: In Vivo Preventive Test on Phakopsora Test (Soybeans)

[0313] Solvent: 24.5 parts by weight of acetone [0314] 24.5 parts by weight of dimethylacetamide [0315] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0316] 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.

[0317] 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 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%.

[0318] 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.

[0319] 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.

[0320] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 10 ppm of active ingredient: 1-02; 1-03; 1-04

[0321] In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 100 ppm of active ingredient: 1-01