PHENOXYHALOGENPHENYLAMIDINES AND THE USE THEREOF AS FUNGICIDES

Abstract

The present invention relates phenoxyhalogenphenylamidines 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 phenoxyhalogenphenylamidines 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 compound comprising a phenoxyphenylamidine of formula (I) ##STR00030## in which R.sup.1 is selected from the group consisting of halogen; R.sup.2 is methyl; R.sup.3 is hydrogen; And/or a salt, N-oxide, metal complex and/or a stereoisomer thereof.

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

3. Compound according to claim 1 where R.sup.1 is selected from the group consisting of chloro and bromo; R.sup.2 is methyl; R.sup.3 is hydrogen.

4. A compound as claimed in claim 1 selected from the group consisting of N-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, N-(2-bromo-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide and N-ethyl-N-(2-fluoro-5-methyl-4-phenoxyphenyl)-N-methylimidoformamide.

5. A process for preparing a compound as claimed in claim 1 which comprises at least one of the following (a) to (j): (a) reaction of a nitrobenzene derivative of formula (III) with a phenol derivative of formula (II) according to the reaction scheme below: ##STR00031## (b) reaction of a nitrophenol derivative of formula (V) with a phenyl derivative of formula (IV) according to the reaction scheme below: ##STR00032## (c) reaction of an aniline of formula (VII) with a phenol derivative of formula (II) according to the reaction scheme below: ##STR00033## (d) reaction of an aminophenol of formula (XII) with a phenyl derivative of formula (IV) according to the reaction scheme below: (e) reduction of a nitrophenyl ether of formula (VI) to an aminophenyl ether of the formula (VIII) according to the reaction scheme below: ##STR00034## (f) reaction of a aminophenyl ether of formula (VIII) with (i) aminoacetal of formula (XIII) or (ii) with N-ethyl-N-methylformamide of formula (XIV) or (iii) with N-methylethanamine of formula (XV) in the presence of ortho ester of formula (XVI) according to the reaction scheme below: ##STR00035## (g) reaction of an aminophenol of formula (XII) with (i) aminoacetal of formula (XIII) or (ii) with N-ethyl-N-methylformamide of formula (XIV) or (iii) with N-methylethanamine of formula (XV) in the presence of an ortho ester of formula (XVI) according to the reaction scheme below: ##STR00036## (h) reaction of an aniline of formula (VII) with (i) aminoacetal of formula (XIII) or (ii) with N-ethyl-N-methylformamide of formula (XIV) or (iii) with N-methylethanamine of formula (XV) in the presence of an ortho ester of formula (XVI) according to the reaction scheme below: ##STR00037## (i) reaction of an amidine of formula (XI) with a phenol derivative of the formula (II) according to the reaction scheme below: ##STR00038## (j) reaction of an amidine of formula (XI) with a phenyl derivative of formula (IV) according to the reaction scheme below: ##STR00039## 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. Nitrophenyl ether of the formula (VI) ##STR00040## in which R.sup.1 is selected from the group consisting of fluoro, chloro, and bromo; R.sup.2 is methyl; R.sup.3 is hydrogen.

7. Aminophenyl ether of the formula (VIII) ##STR00041## in which R.sup.1 is selected from the group consisting of fluoro, chloro, and bromo; R.sup.2 is methyl; R.sup.3 is hydrogen.

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

9. A product comprising a compound as claimed in claim 1 or of agrochemical formulation thereof for controlling unwanted microorganisms.

10. A method for controlling unwanted microorganisms, comprising applying a compound as claimed in claim 1 or agrochemical formulation thereof to the microorganisms and/or a habitat thereof.

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

12. A product comprising a compound as claimed in claim 1 for treating seed.

13. A product comprising a compound as claimed in claim 1 for treating transgenic plants.

14. A product comprising a compound 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 compound as claimed in claim 1.

Description

PREPARATION EXAMPLES

[0259] The preparation and the use of the inventive active ingredients of the formula (I) is illustrated by the examples which follow. However, the invention is not limited to these examples.

[0260] General Notes:

[0261] Unless stated otherwise, all chromatographic purification and separation steps are carried out on silica gel and using a solvent gradient from 0:100 ethyl acetate/cyclohexane to 100:0 ethyl acetate/cyclohexane.

Preparation of Compounds of the Formula (I-02)

Step 1

1-bromo-4-methyl-2-nitro-5-phenoxybenzene (VI-02)

[0262] 500 mg (2.14 mmol) 1-bromo-5-fluoro-4-methyl-2-nitrobenzene and 591 mg (4.27 mmol) potassium carbonate were suspended in 10 ml of dry DMF and heated to 90 C. To this solution was added drop wise over 1 h a solution of 200 mg (2.14 mmol) phenol in 10 ml of dry DMF. The reaction was finished after 2.5 h. The mixture was concentrated under reduced pressure, followed by addition of water and filtration of the product yielding 565 mg of 1-bromo-4-methyl-2-nitro-5-phenoxybenzene.

Step 2

2-bromo-5-methyl-4-phenoxyaniline (VIII-02)

[0263] 500 mg (1.62 mmol) 1-bromo-4-methyl-2-nitro-5-phenoxybenzene was dissolved in 5 ml EtOH followed by addition of 1.8 g (8.11 mmol) tin-dichloride dihydrat (SnCl2*2 H2O). The mixture was refluxed for 1 h, cooled to room temperature, followed by addition of ice and adjustment of the pH to 10 by slow addition of sodium carbonate. The water phase was extracted with ethyl acetate, the organic phase dried over MgSO4, then concentrated in vacuum and the crude product chromatographed via Combiflash (40 g silica gel, gradient cyclohexane/ethyl acetate). 350 mg 2-bromo-5-methyl-4-phenoxyaniline was obtained.

Step 3

N-(2-bromo-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide (I-02)

[0264] 350 mg (1.26 mmol) 2-bromo-5-methyl-4-phenoxyaniline and 218 mg (1.64 mmol) N-(dimethoxymethyl)-N-methylethanamine were dissolved in 10 ml of dry toluene and heated for 12 h at 80 C. The mixture was cooled to room temperature, concentrated under reduced pressure and purified by chromatography via Combiflash (40 g silica gel, solvent: gradient cyclohexane/ethyl acetate) to yield 280 mg N-(2-bromo-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide.

Examples

[0265]

TABLE-US-00003 (I) [00024] Ex N R.sup.1 R.sup.2 R.sup.3 LogP I-01 Cl Me H 1.60.sup.[a] I-02 Br Me H 1.61.sup.[a]; 4.67.sup.[b] I-03 F Me H 1.55.sup.[a]; 3.97.sup.[b] (VI) [00025] Ex N R.sup.1 R.sup.2 R.sup.3 LogP VI-01 Cl Me H 4.38.sup.[a]; 4.33.sup.[b] VI-02 Br Me H 4.51.sup.[a] (VIII) [00026] Ex N R.sup.1 R.sup.2 R.sup.3 LogP VIII-01 Cl Me H 3.51.sup.[a]; 3.51.sup.[b] VIII-02 Br Me H 3.66.sup.[a]; 3.65.sup.[b]

[0266] 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: [0267] .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). [0268] .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).

[0269] 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.

[0270] NMR-Peak Lists

[0271] 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.

[0272] The peak list of an example has therefore the form:

[0273] .sub.1(intensity.sub.1); .sub.2(intensity.sub.2); . . . ; (intensity.sub.i); . . . ; .sub.n (intensity.sub.n)

[0274] 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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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%).

[0280] 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.

[0281] 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.

[0282] 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-00004 Example I-01: .sup.1H-NMR (600.1 MHz, d.sub.6-DMSO): = 7.755 (1.1); 7.642 (0.4); 7.357 (0.4); 7.353 (3.0); 7.350 (1.1); 7.345 (0.6); 7.341 (4.2); 7.339 (4.2); 7.335 (0.7); 7.330 (1.3); 7.326 (3.4); 7.322 (0.5); 7.068 (1.5); 7.066 (1.0); 7.055 (2.8); 7.045 (0.8); 7.043 (1.3); 7.042 (0.8); 6.954 (1.2); 6.931 (7.5); 6.869 (3.6); 6.867 (4.4); 6.854 (4.1); 6.853 (3.5); 3.454 (0.4); 3.443 (0.5); 3.368 (0.5); 3.357 (1.0); 3.346 (1.0); 3.335 (12.8); 3.001 (1.3); 2.935 (3.5); 2.512 (1.4); 2.509 (3.2); 2.506 (4.4); 2.503 (3.2); 2.500 (1.6); 2.075 (16.0); 1.158 (1.5); 1.146 (3.3); 1.136 (2.2) Example I-02: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): = 7.740 (1.1); 7.623 (0.5); 7.362 (2.6); 7.357 (1.0); 7.343 (4.0); 7.340 (4.0); 7.326 (1.3); 7.322 (3.2); 7.074 (1.8); 7.068 (6.8); 7.056 (2.7); 7.038 (1.2); 6.949 (1.4); 6.926 (0.7); 6.866 (4.3); 6.847 (3.9); 3.450 (0.5); 3.435 (0.6); 3.379 (0.5); 3.362 (1.1); 3.344 (1.1); 3.319 (44.1); 3.001 (1.6); 2.935 (3.7); 2.524 (0.8); 2.510 (17.3); 2.506 (34.2); 2.502 (44.6); 2.497 (33.1); 2.493 (16.6); 2.061 (16.0); 1.166 (4.0); 1.148 (8.4); 1.130 (3.9); 0.008 (0.9); 0.000 (24.7); 0.008 (1.1) Example I-03: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): = 7.794 (1.2); 7.704 (0.4); 7.359 (0.4); 7.354 (2.8); 7.335 (4.5); 7.333 (4.4); 7.314 (3.5); 7.065 (1.7); 7.047 (2.9); 7.028 (1.3); 6.952 (1.4); 6.927 (1.4); 6.860 (5.1); 6.841 (4.7); 6.756 (3.2); 6.727 (3.2); 3.429 (0.5); 3.348 (1.4); 3.318 (75.7); 2.984 (1.1); 2.910 (4.0); 2.675 (0.4); 2.671 (0.6); 2.666 (0.4); 2.524 (1.7); 2.510 (37.3); 2.506 (74.8); 2.502 (98.1); 2.497 (71.5); 2.333 (0.4); 2.328 (0.6); 2.324 (0.4); 2.044 (16.0); 1.234 (0.4); 1.150 (1.5); 1.133 (3.2); 1.116 (2.4); 0.000 (7.7) Example VI-02: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): = 8.129 (4.8); 7.506 (2.1); 7.485 (4.0); 7.466 (3.0); 7.298 (1.4); 7.280 (2.4); 7.261 (1.0); 7.154 (4.4); 7.134 (3.7); 7.023 (6.2); 3.323 (11.2); 2.892 (0.4); 2.733 (0.4); 2.508 (18.0); 2.503 (23.7); 2.499 (17.8); 2.299 (16.0); 2.278 (0.7); 2.273 (0.7); 0.000 (11.5); 0.008 (0.5) Example VIII-01: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): = 7.322 (2.4); 7.317 (1.0); 7.304 (3.6); 7.301 (3.8); 7.287 (1.1); 7.282 (3.0); 7.023 (1.4); 7.005 (2.4); 6.986 (1.1); 6.864 (5.6); 6.812 (3.2); 6.809 (4.2); 6.790 (3.7); 6.788 (3.3); 6.725 (4.8); 5.186 (4.5); 3.328 (27.7); 2.525 (0.9); 2.511 (17.8); 2.507 (35.8); 2.502 (47.6); 2.498 (36.7); 1.975 (16.0); 0.008 (1.8); 0.000 (46.7) Example VIII-02: .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): = 8.805 (0.3); 7.330 (0.6); 7.324 (2.7); 7.318 (1.1); 7.312 (0.9); 7.305 (3.8); 7.302 (3.9); 7.296 (1.0); 7.288 (1.9); 7.284 (3.5); 7.277 (0.9); 7.270 (1.0); 7.266 (1.0); 7.256 (0.5); 7.253 (0.4); 7.248 (0.8); 7.025 (1.7); 7.023 (1.1); 7.007 (2.6); 6.988 (7.3); 6.971 (0.4); 6.969 (0.4); 6.967 (0.4); 6.953 (0.7); 6.935 (0.4); 6.926 (0.4); 6.923 (0.5); 6.904 (0.4); 6.902 (0.4); 6.826 (0.3); 6.814 (3.4); 6.812 (4.4); 6.806 (1.5); 6.797 (1.5); 6.795 (2.2); 6.792 (3.9); 6.790 (3.4); 6.783 (0.7); 6.781 (0.7); 6.778 (0.5); 6.770 (0.9); 6.767 (1.1); 6.762 (0.4); 6.758 (0.4); 6.751 (0.8); 6.748 (1.2); 6.745 (1.2); 6.739 (4.9); 6.680 (0.7); 6.659 (0.9); 6.646 (0.4); 6.488 (0.5); 6.481 (0.7); 6.438 (0.9); 6.429 (0.4); 6.415 (0.4); 5.143 (4.5); 4.912 (1.0); 4.788 (0.6); 4.038 (0.8); 4.021 (0.8); 3.318 (27.1); 2.524 (0.8); 2.520 (1.1); 2.511 (17.0); 2.506 (35.3); 2.502 (47.2); 2.497 (34.8); 2.493 (17.1); 2.077 (0.8); 2.000 (1.9); 1.988 (3.9); 1.980 (0.4); 1.966 (16.0); 1.957 (4.3); 1.398 (0.6); 1.298 (0.6); 1.193 (1.0); 1.175 (1.9); 1.158 (1.0); 0.008 (1.3); 0.000 (43.1); 0.009 (1.6)

Stability Data Examples

[0283] Stability Towards Hydrolysis in Homogeneous Aqueous Solution

[0284] Hydrolysis stability test

[0285] 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:

[0286] 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 1004 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}$

[0287] In table III the results of the hydrolysis stability test are shown for the compounds (I-01), (I-02) and (I-03) 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-00005 TABLE III T.sub.1/2 T.sub.1/2 Ex No (pH 7) (pH 9) I-01 45 h 40 h Compound no. 1 24 h 16 h known from WO2008/110313 Compound no. 25 h 17 h 337 known from WO2008/110278

[0288] Stability Towards Photolysis

[0289] Photolysis stability test

[0290] 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 254 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.sub.1/2) 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}$

[0291] In table IV the results of the photolysis stability test are shown for the compounds (I-01), (I-02) and (I-03). 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 stability towards photolysis. This increased 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-00006 TABLE IV Ex No T.sub.1/2 I-01 >200 h Compound no. 1 10 h known from WO2008/110313

[0292] Plant Compatibility Test Using Soy Bean Plants

TABLE-US-00007 Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0293] 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. 0% means no damages are observed, while 100% means that the plants are totally damaged.

TABLE-US-00008 TABLE V Plant compatibility soy bean Rate of application of active compound Necrosis Active compound in ppm in % Known from WO2008/110313: Ex. 1 [00027] 500 90 According to the invention: Ex. I-01 [00028] 500 50 Ex. I-02 [00029] 500 10

USE EXAMPLES

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

[0294]

TABLE-US-00009 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 l of Tween 80 per mg of active ingredient

[0295] 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.

[0296] 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/Tween80.

[0297] 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.

[0298] 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.

[0299] 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-02

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

[0300]

TABLE-US-00010 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 l of Tween 80 per mg of active ingredient

[0301] 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.

[0302] 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/Tween80.

[0303] 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.

[0304] 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.

[0305] 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-02

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

[0306]

TABLE-US-00011 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 l of Tween 80 per mg of active ingredient

[0307] 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.

[0308] 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/Tween80.

[0309] 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.

[0310] 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.

[0311] 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-02

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

[0312]

TABLE-US-00012 Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0313] 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.

[0314] 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%.

[0315] 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.

[0316] 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.

[0317] 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: I-01; I-02

Example: In Vivo Preventive Leptosphaeria nodorum Test (Wheat)

[0318]

TABLE-US-00013 Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0319] 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.

[0320] 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.

[0321] 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%.

[0322] The plants are placed in the greenhouse at a temperature of approximately 25 C. and a relative atmospheric humidity of approximately 80%.

[0323] 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.

[0324] 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-02

Example: In Vivo Preventive Puccinia triticina Test (Wheat)

[0325]

TABLE-US-00014 Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0326] 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.

[0327] 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.

[0328] After the spray coating has been dried, the plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabinet at approximately 20 C. and a relative atmospheric humidity of approximately 100%.

[0329] The plants are placed in the greenhouse at a temperature of approximately 20 C. and a relative atmospheric humidity of approximately 80%.

[0330] 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.

[0331] 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-02

Example: In Vivo Preventive Pyrenophora Teres Test (Barley)

[0332]

TABLE-US-00015 Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0333] 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.

[0334] 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.

[0335] After the spray coating has been dried, the plants are sprayed with a spore suspension of Pyrenophora teres. The plants remain for 48 hours in an incubation cabinet at approximately 20 C. and a relative atmospheric humidity of approximately 100%.

[0336] The plants are placed in the greenhouse at a temperature of approximately 20 C. and a relative atmospheric humidity of approximately 80%.

[0337] 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.

[0338] 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-02