Microbiocidal phenylamidine derivatives

Abstract

Compounds of the formula (I) wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and X are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi. ##STR00001##

Claims

1. A compound of formula (I): ##STR00214## wherein, R.sup.1 and R.sup.2 are each independently selected from C.sub.1-C.sub.4 alkyl and C.sub.3-C.sub.8 cycloalkyl; or R.sup.1 and R.sup.2 together with the nitrogen atom to which they are attached form a three to six-membered saturated cyclic group which may optionally contain one oxygen or one sulphur atom; R.sup.3 is hydrogen, halogen or C.sub.1-C.sub.4 alkyl; R.sup.4 is C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 haloalkyl; R.sup.5 and R.sup.6 are each independently selected from C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 haloalkenyl, C.sub.2-C.sub.6 alkynyl, aryl optionally substituted with one to three R.sup.7 groups, aryl(C.sub.1-C.sub.4)alkyl wherein the aryl is optionally substituted with one to three R.sup.7 groups, heteroaryl(C.sub.1-C.sub.4)alkyl wherein the heteroaryl is optionally substituted with one to three R.sup.7 groups and heteroaryl optionally substituted with one to three R.sup.7 groups; X is NR.sup.8, O or S; Each R.sup.7 is independently selected from halogen, cyano, hydroxyl, amino, nitro, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4haloalkylthio, C.sub.3-C.sub.6cycloalkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkenyloxy, C.sub.2-C.sub.6haloalkenyloxy, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkylC.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6alkynyloxy, aryl, aryl(C.sub.1-C.sub.4)alkyl, aryloxy, heteroaryl, heteroaryl(C.sub.1-C.sub.4)alkyl and heteroaryloxy; and R.sup.8 is selected from hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and C.sub.3-C.sub.8cycloalkyl; or a salt or an N-oxide thereof.

2. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are each independently C.sub.1-C.sub.4 alkyl.

3. A compound according to claim 1, wherein R.sup.3 is hydrogen, fluoro, chloro, or C.sub.1-C.sub.4 alkyl.

4. A compound according to claim 1, R.sup.4 is C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.3haloalkyl.

5. A compound according to claim 1, wherein R.sup.5 and R.sup.6 are each independently selected from C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.2-C.sub.6 alkenyl, phenyl optionally substituted with one to three R.sup.7 groups, phenyl(C.sub.1-C.sub.4)alkyl wherein the phenyl is optionally substituted with one to three R.sup.7 groups, pyrazolyl(C.sub.1-C.sub.4)alkyl wherein the pyrazole is optionally substituted with one to three R.sup.7 groups and pyridyl optionally substituted with one to three R.sup.7 groups, and wherein each R.sup.7 is independently selected from halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, phenyl, benzyl, phenoxy, pyridyl, pyridylmethyl and pyridyloxy.

6. A compound according to claim 1, wherein X is NR.sup.8 or O, where R.sup.8 is hydrogen, C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy.

7. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are each independently selected from methyl, ethyl, propyl and isopropyl.

8. A compound according to claim 1, wherein R.sup.3 is hydrogen or C.sub.1-C.sub.3 alkyl.

9. A compound according to claim 1, wherein R.sup.5 and R.sup.6 are each independently selected from C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.5 cycloalkyl, phenyl optionally substituted with one or two R.sup.7 groups and pyridyl optionally substituted with one or two R.sup.7 groups, and wherein each R.sup.7 is independently selected from halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkynyl, phenyl, phenoxy and pyridyl.

10. A compound according to claim 1, wherein X is O.

11. A compound according to claim 1, wherein R.sup.1 and R.sup.2 are each independently selected from methyl, ethyl and isopropyl; R.sup.3 is hydrogen or C.sub.1-C.sub.2 alkyl; R.sup.4 is methyl or ethyl; R.sup.5 and R.sup.6 are each independently selected from C.sub.1-C.sub.2 haloalkyl, phenyl optionally substituted with one or two R.sup.7 groups, ethyl, n-propyl, i-propyl, n-butyl, iso-butyl, neo-pentyl, cyclopropyl, cyclobutyl or cyclopentyl; X is N-methyl or O; and each R.sup.7 is independently selected from halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.2-C.sub.6alkynyl and phenyl; or a salt or N-oxide thereof.

12. A compound according to claim 1, wherein R.sup.1 is methyl and R.sup.2 is ethyl or isopropyl; or, alternatively, R.sup.1 and R.sup.2 are both ethyl; R.sup.3 is hydrogen or methyl; R.sup.4 is methyl; R.sup.5 is CF.sub.3, CClF.sub.2 or CF.sub.2CF.sub.3; R.sup.6 is phenyl optionally substituted by one methyl group and/or one or two halogen atoms, preferably fluoro or chloro, n-propyl, i-propyl, n-butyl, iso-butyl or neo-pentyl; or, alternatively, R.sup.6 is cyclopropyl; and X is O; or a salt or N-oxide thereof.

13. A compound according to claim 12, wherein R.sup.3 is methyl.

14. A compound according to claim 12, wherein R.sup.5 is CF.sub.3.

15. A composition comprising a fungicidally effective amount of a compound of formula (I) as defined in claim 1.

16. A composition according to claim 15, wherein the composition further comprises at least one additional active ingredient and/or a diluent.

17. A method of combating or controlling phytopathogenic diseases which comprises applying to a phytopathogen, to the locus of a phytopathogen, or to a plant susceptible to attack by a phytopathogen, or to propagation material thereof, a fungicidally effective amount of a compound of formula (I) as defined in claim 1 or a composition comprising a fungicidally effective amount of a compound of formula (I) as defined in claim 1.

Description

EXAMPLES

(1) The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

(2) Throughout this description, temperatures are given in degrees Celsius and m.p. means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the methods are:

FORMULATION EXAMPLES

(3) TABLE-US-00002 Wettable powders a) b) c) active ingredient [compound of formula (I)] 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% 5% sodium diisobutylnaphthalenesulfonate 6% 10% phenol polyethylene glycol ether 2% (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27%

(4) The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

(5) TABLE-US-00003 Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% Kaolin 65% 40% Talcum 20

(6) The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

(7) TABLE-US-00004 Emulsifiable concentrate active ingredient [compound of formula (I)] 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50%

(8) Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

(9) TABLE-US-00005 Dusts a) b) c) Active ingredient [compound of formula (I)] 5% 6% 4% talcum 95% Kaolin 94% mineral filler 96%

(10) Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

(11) TABLE-US-00006 Extruder granules Active ingredient [compound of formula (I)] 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%

(12) The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

(13) TABLE-US-00007 Coated granules Active ingredient [compound of formula (I)] 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%

(14) The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

(15) TABLE-US-00008 Suspension concentrate active ingredient [compound of formula (I)] 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% Water 32%

(16) The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

(17) TABLE-US-00009 Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40% propylene glycol 5% copolymer butanol PO/EO 2% tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5% monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

(18) The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

(19) Slow Release Capsule Suspension

(20) 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

(21) The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

(22) The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

PREPARATION EXAMPLES

(23) Using techniques described above and below, and also in WO 08/101682 (pp. 22-33) and WO 12/146125 (pp. 370-378), together with further techniques generally known to the person skilled in the art, compounds of formula (I) may be prepared.

Example 1

This example illustrate the preparation N-ethyl-N-[4-(1-hydroxy-1-phenyl-ethyl)-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine

(24) ##STR00051##

a) Preparation of 4-bromo-5-methoxy-2-methyl-aniline

(25) N-bromosuccinimide (1.28 g, 7.29 mmol) was added portion wise to an ice-cold (0-5 C.) solution of 5-methoxy-2-methyl-aniline (1.0 g, 7.29 mmol) in CHC.sub.13 (15 mL). The resulting solution was stirred for 60 minutes at 0 C., warmed to room temperature and diluted with CH.sub.2Cl.sub.2. The mixture was washed with aqueous NaHCO.sub.3 (+2 mL Na.sub.2S.sub.2O.sub.3 solution), brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as off white solid.

(26) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.17 (s, 1H), 6.27 (s, 1H), 3.82 (s, 3H), 3.53-3.73 (br. s., 2H), 2.08 (s, 3H).

b) Preparation of N-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine

(27) To a suspension of 4-bromo-5-methoxy-2-methyl-aniline (1.4 g, 6.48 mmol) and p-toluene sulfonic acid (0.05 g, 0.32 mmol) in toluene (13 mL) was added N-(dimethoxymethyl)-N-methyl-ethanamine (1.3 g, 9.7 mmol) at room temperature. The resulting clear solution was warmed to 50 C. and stirred for 24 h at this temperature. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with aqueous NaHCO.sub.3, brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light yellow liquid.

(28) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40 (br. s., 1H), 7.26 (s, 1H), 6.33 (s, 1H), 3.85 (s, 3H), 3.34 (br. s., 2H), 3.00 (s, 3H), 2.16 (s, 3H), 1.22 (t, 3H).

c) Preparation of N-ethyl-N-[4-(1-hydroxy-1-phenyl-ethyl)-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine

(29) A solution of N-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (0.10 g, 0.35 mmol) in dry tetrahydrofuran (3.5 mL) under N.sub.2-atmosphere was cooled to 78 C. and tert-butyl lithium (1.5 M in pentanes, 0.49 mL, 0.74 mmol) was added slowly. The reaction was aged for 5 min at 78 C. and then 1-phenylethanone (0.044 g, 0.37 mmol) was added drop wise. The cooling bath was removed, the reaction was allowed to warm to room temperature and stirred for an additional 10 min. Aqueous NaHCO.sub.3 was added and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as white solid.

(30) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.41 (br. s., 1H), 7.28-7.34 (m, 2H), 7.12-7.25 (m, 4H), 6.32 (s, 1H), 4.64 (s, 1H), 3.51 (s, 3H), 3.20-3.47 (br. s, 2H), 3.00 (s, 3H), 2.24 (s, 3H), 1.80 (s, 3H), 1.21 (t, 3H).

Example 2

This example illustrate the preparation of N-ethyl-N-[4-[1-hydroxy-2-methyl-1-(trifluoromethyl)propyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine

(31) ##STR00052##

a) Preparation of N-ethyl-N-[5-methoxy-2-methyl-4-(2-methylpropanoyl)phenyl]-N-methyl-formamidine

(32) A solution of N-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (2.0 g, 7.01 mmol) in dry tetrahydrofuran (3.5 mL) under N.sub.2-atmosphere was added drop wise to a suspension of LiCl (0.33 g, 7.71 mmol) and Mg-turnings (0.26 g, 7.02 mmol) in dry tetrahydrofuran (3.5 mL) at a temperature between 20 C. to 40 C. (temperature controlled by addition rate). Upon completed addition, the reaction was aged for 1 h at 40 C. and then the mixture was then cooled to 0 C. N-methoxy-N,2-dimethyl-propanamide (1.01 g, 7.33 mmol) was added drop wise and the reaction was mixture was gradually warmed to RT over 1 h. Aqueous NH.sub.4Cl solution was added and the mixture was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light yellow oil.

(33) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.47 (br. s, 2H), 6.30 (s, 1H), 3.85 (s, 3H), 3.25-3.60 (m, 3H), 3.02 (s, 3H), 2.18 (s, 3H), 1.59 (s, 1H), 1.23 (t, 3H), 1.13 (d, 6H).

b) Preparation of N-ethyl-N-[4-[1-hydroxy-2-methyl-1-(trifluoromethyl)propyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine

(34) Trimethyl(trifluoromethyl)silane (0.26 g, 1.81 mmol) was added drop wise to a solution of N-ethyl-N-[5-methoxy-2-methyl-4-(2-methylpropanoyl)phenyl]-N-methyl-formamidine (0.50 g, 1.81 mmol) and CsF (0.03 g, 0.18 mmol) in toluene (9 mL) at 40 C. The resulting mixture was aged for 3 h at 40 C., a second portion of trimethyl(trifluoromethyl)silane (0.13 g, 0.91 mmol) was then added and the reaction was stirred for additional 30 min before being concentrated in vacuo to a brown oil.

(35) This residue was taken up in methanol (7 mL), treated with potassium carbonate (0.37 g, 2.71 mmol) and aq. sodium hydroxide (2 M, 3 drops), warmed to 40 C. and stirred for 24 h at this temperature. Aqueous NaHCO.sub.3 solution was then added and the emulsion was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light brown solid (m.p. 57-59 C.).

(36) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.47 (br s, 1H), 7.07 (s, 1H), 6.56 (br s, 1H), 6.40 (s, 1H), 3.90 (s, 3H), 3.22-3.66 (m, 2H), 3.03 (s, 3H), 2.46-2.66 (m, 1H), 2.22 (s, 3H), 1.25 (t, 3H), 1.16 (d, 3H), 0.87 (d, 3H).

(37) TABLE-US-00010 TABLE E Physical data of compounds of formula (I) The compounds of formula (I) in Table E were prepared using techniques analogous to those described above and/or common synthetic techniques generally known to the person skilled in the art, as well as those described in WO 12/146125 (pp.370-378) and WO 08/101682 (pp.22-33). RT [M + H] Entry STRUCTURE (min) (measured) Method MP C. E1.001 0.79 373 A 126-128 E1.002 0.80 395 A 148-151 E1.003 0.83 417 A 107-108 E1.004 0.81 399 A 102-104 E1.005 0.71 363 A E1.006 0.79 381 A 160-162 E1.007 0.74 327 A E1.008 0 0.80 393 A E1.009 0.81 395 A 110-111 E1.010 121-123 E1.011 0.90 411 A 67-71 E1.012 1.26 483 A E1.013 1.24 449 A E1.014 0.79 381 A E1.015 0.79 381 A E1.016 0.89 395 A 125-127 E1.017 0.92 449 A 119-121 E1.018 0 113-114 E1.019 0.94 449 A 124-126 E1.020 0.90 395 A 112-114 E1.021 0.90 415 A 134-135 E1.022 0.79 406 A 38-40 E1.023 0.91 459 A 98-100 E1.024 0.79 395 A 115-117 E1.025 0.91 459 A 127-129 E1.026 0.79 395 A 110.5-111.7 E1.027 0.79 395 A 110.5-111.7 E1.028 0 0.69 406 A 55-58 C. E1.029 0.81 399 A 130-132 E1.030 0.77 411 A E1.031 137-140 E1.032 0.77 427 A 104-106 E1.033 0.79 415 A 97-100 E1.034 0.78 399 A 96-98 E1.035 0.79 459 A 114-116 E1.036 0.74 459 A 177-180 E1.037 0.90 481 A 64-66 E1.038 0 0.84 463 A E1.039 0.82 453 A 118-120 E1.040 0.75 406 A 167-169 E1.041 0.81 427 A 89-91 E1.042 0.81 427 A E1.043 0.67 397 A 240-242 E1.044 0.81 447 A 119-121 E1.045 0.80 447 A 85-87 E1.046 1.24 387 A E1.047 1.15 347 A E1.048 00 0.67 333 A 69-73 E1.049 01 0.80 373 A E1.050 02 1.23 373 A E1.051 03 1.16 361 A E1.052 04 1.15 345 A 64-72 E1.053 05 0.82 375 A E1.054 06 1.13 347 A 57-59 E1.055 07 0.66 319 A 114-118 E1.056 08 0.78 361 A E1.057 09 128-132 E1.058 0 1.31 389 A E1.059 1.24 361 A 112-116 E1.060 0.87 387 A E1.061 0.95 416 A E1.062 0.92 401 A E1.063 73-76 E1.064 90-93 E1.065 0.85 375 A E1.066 0.78 375 A E1.067 0.82 361 A 78-79 E1.068 0 0.85 375 A E1.069 0.83 359 A E1.070 0.65 329 A E1.071 1.18 345 A 123-127 E1.072 1.20 369 A 76-78 E1.073 0.90 405 A 88-90 E1.074 0.73 345 A E1.075 0.75 359 A E1.076 0.74 359 A E1.077 0.63 331 A E1.078 0 0.73 345 A E1.079 0.81 371 A E1.080 0.84 385 A E1.081 110-113 E1.082 90-95 E1.083 0.82 343 A E1.084 45-50 E1.085 0.87 411 A 62-64 E1.086 0.82 395 A E1.087 0.86 409 A E1.088 0 0.84 331 A E1.089 1.32 437 A E1.090 0.84 429 A 63-65 E1.091 0.79 413 A E1.092 0.80 435 A E1.093 0.80 435 A E1.094 0.78 441 A 117-119 E1.095 0.89 427 A E1.096 0.80 447 A E1.097 0.63 435 A E1.098 0 0.61 386 A E1.099 0.70 411 A 82-85 E1.100 0.83 426 A 92-95 E1.101 0.71 414 A E1.102 0.77 414 A E1.103 0.85 437 A E1.104 0.74 401 A E1.105 0.83 387 A E1.106 0.76 416 A E1.107 0.73 412 A 100-102 E1.108 0 0.70 427 A E1.109 0.79 447 A E1.110 0.67 413 A E1.111 0.64 399 A E1.112 0.73 412 A E1.113 0.77 397 A 160-165 E1.114 E1.115 0.88 409 A 119-120 E1.116 0.81 401 A E1.117 0.82 381 A E1.118 0 0.64 321 A E1.119 0.80 363 A E1.120 0.79 361 A E1.121 0.75 361 A E1.122 0.78 397 A E1.123 0.71 313 A E1.124 0.89 355 A 82-84 E1.125 1.00 369 A 90-92 E1.126 0.82 341 A 87-89 E1.127 0.85 431 A 116-118 E1.128 0 0.80 417 A 108-110 E1.129 0.91 389 A E1.130 0.87 375 A E1.131 0.83 427 A 127-129 E1.132 0.83 413 A 107-109 E1.133 0.82 361 A 60-62 E1.134 0.80 373 A 103-105 E1.135 0.80 393 A 157-159 E1.135 0.83 359 A 102-104 E1.135 0.87 431 A 112-115 E1.136 0 0.77 347 A E1.137 0.73 367 A 133-135 E1.138 0.81 375 A 97-99 E1.139 0.80 395 A 102-104 E1.140 0.79 332 A 110-112 E1.141 0.76 373 A 77-79 E1.142 0.81 389 A E1.143 0.79 417 A 130-132 E1.144 0.82 431 A 97-99 E1.145 0.82 413 A 95-97 E1.146 00 0.85 427 A 116-118 E1.147 01 0.79 417 A 128-130 E1.148 02 0.82 431 A 119-121 E1.148 03 0.86 409 A 138-140 E1.149 04 0.83 431 A 110-112 E1.150 05 0.80 413 A 86-88 E1.151 06 0.86 429 A 67-69 E1.152 07 0.82 413 A 92-94 E1.153 08 0.77 385 A 144-146 E1.154 09 0.76 367 A E1.155 0 0.80 347 A E1.156 0.81 365 A E1.157 0.72 400 A 113-115 E1.158 0.75 414 A 120-122
HPLC Method Used

(38) Method A:

(39) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters 10 (SQD, SQDII or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. 15 Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 mm, 302.1 mm, Temp: 60 C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2 min; Flow (ml/min) 0.85

BIOLOGICAL EXAMPLES

(40) Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)

(41) Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20 C. and 60% rh under a light regime of 24 h darkness followed by 12 h light/12 h darkness in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6-8 days after application).

(42) The following compounds gave at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development

(43) E1.001, E1.003, E1.004, E1.005, E1.006, E1.007, E1.010, E1.011, E1.013, E1.014, E1.015, E1.016, E1.017, E1.018, E1.019, E1.020, E1.021, E1.022, E1.023, E1.024, E1.025, E1.026, E1.027, E1.029, E1.030, E1.031, E1.032, E1.033, E1.034, E1.035, E1.037, E1.038, E1.039, E1.040, E1.041, E1.042, E1.043, E1.044, E1.045, E1.046, E1.047, E1.048, E1.049, E1.050, E1.051, E1.052, E1.053, E1.054, E1.055, E1.056, E1.057, E1.058, E1.059, E1.060, E1.061, E1.062, E1.063, E1.064, E1.065, E1.066, E1.067, E1.068, E1.069, E1.070, E1.071, E1.072, E1.074, E1.075, E1.076, E1.077, E1.078, E1.079, E1.080, E1.081, E1.082, E1.083, E1.084, E1.086, E1.087, E1.088, E1.089, E1.090, E1.091, E1.092, E1.093, E1.094, E1.095, E1.098, E1.099, E1.100, E1.101, E1.102, E1.103, E1.104, E1.105, E1.106, E1.107, E1.108, E1.109, E1.112, E1.113, E1.114, E1.117, E1.118, E1.119, E1.120, E1.121, E1.122, E1.123, E1.126.

(44) Phakopsora pachyrhizi/Soybean/Leaf Disk Preventative (Soybean Rust)

(45) Four-week old soybean plants are sprayed in a spray chamber with the formulated test compound diluted in water. Leaf disks are cut from treated plants and placed on agar into 24-well plates one day after application. Leaf disks are inoculated by spraying them with a spore suspension on their lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20 C. and 75% rh, the leaf disks are then kept at 20 C. with 12 h light/day and 75% rh. The percentage leaf disk area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (12-14 days after application).

(46) The following compounds gave at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development

(47) E1.001, E1.002, E1.003, E1.004, E1.005, E1.006, E1.007, E1.010, E1.011, E1.014, E1.015, E1.016, E1.017, E1.018, E1.020, E1.022, E1.023, E1.024, E1.026, E1.027, E1.029, E1.030, E1.031, E1.033, E1.034, E1.035, E1.037, E1.044, E1.045, E1.046, E1.047, E1.048, E1.049, E1.050, E1.051, E1.052, E1.053, E1.054, E1.055, E1.056, E1.057, E1.058, E1.059, E1.061, E1.062, E1.063, E1.064, E1.065, E1.066, E1.067, E1.068, E1.069, E1.070, E1.071, E1.072, E1.074, E1.075, E1.076, E1.077, E1.078, E1.081, E1.082, E1.083, E1.084, E1.086, E1.087, E1.088, E1.089, E1.090, E1.091, E1.093, E1.095, E1.096, E1.099, E1.100, E1.101, E1.102, E1.103, E1.104, E1.105, E1.106, E1.111, E1.112, E1.114, E1.117, E1.118, E1.119, E1.120, E1.121, E1.122, E1.123, E1.124, E1.125, E1.126

(48) Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Preventative (Brown Rust)

(49) Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 C. and 75% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7-9 days after application).

(50) The following compounds gave at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:

(51) E1.001, E1.002, E1.003, E1.004, E1.005, E1.006, E1.007, E1.008, E1.009, E1.010, E1.011, E1.013, E1.014, E1.015, E1.016, E1.017, E1.018, E1.019, E1.020, E1.021, E1.022, E1.023, E1.024, E1.025, E1.026, E1.027, E1.028, E1.029, E1.030, E1.031, E1.032, E1.033, E1.034, E1.035, E1.036, E1.046, E1.047, E1.048, E1.049, E1.050, E1.051, E1.052, E1.053, E1.054, E1.055, E1.056, E1.057, E1.058, E1.059, E1.060, E1.061, E1.062, E1.063, E1.064, E1.065, E1.066, E1.067, E1.068, E1.069, E1.070, E1.071, E1.072, E1.073, E1.074, E1.075, E1.076, E1.077, E1.078, E1.079, E1.080, E1.081, E1.082, E1.083, E1.084, E1.086, E1.087, E1.088, E1.089, E1.092, E1.093, E1.094, E1.095, E1.098, E1.099, E1.100, E1.101, E1.103, E1.104, E1.105, E1.106, E1.107, E1.108, E1.109, E1.110, E1.111, E1.112, E1.116, E1.117, E1.118, E1.119, E1.120, E1.121, E1.122, E1.123, E1.124, E1.125, E1.126

(52) Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Curative (Brown Rust)

(53) Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19 C. and 75% rh. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19 C. and 75% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6-8 days after application).

(54) The following compounds gave at 200 ppm gaive at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:

(55) E1.001, E1.002, E1.003, E1.004, E1.005, E1.006, E1.007, E1.008, E1.009, E1.010, E1.011, E1.013, E1.014, E1.015, E1.016, E1.017, E1.018, E1.019, E1.020, E1.021, E1.022, E1.023, E1.024, E1.025, E1.026, E1.027, E1.028, E1.029, E1.030, E1.031, E1.032, E1.033, E1.034, E1.035, E1.036, E1.037, E1.038, E1.039, E1.040, E1.041, E1.042, E1.043, E1.044, E1.045, E1.046, E1.047, E1.048, E1.049, E1.050, E1.051, E1.052, E1.053, E1.054, E1.055, E1.056, E1.057, E1.058, E1.059, E1.060, E1.061, E1.062, E1.063, E1.064, E1.065, E1.066, E1.067, E1.068, E1.069, E1.070, E1.071, E1.072, E1.074, E1.075, E1.076, E1.077, E1.078, E1.079, E1.080, E1.081, E1.082, E1.083, E1.084, E1.085, E1.086, E1.087, E1.088, E1.089, E1.090, E1.091, E1.092, E1.093, E1.094, E1.095, E1.098, E1.099, E1.100, E1.101, E1.102, E1.103, E1.104, E1.105, E1.106, E1.107, E1.108, E1.109, E1.110, E1.111, E1.112, E1.113, E1.114, E1.116, E1.117, E1.118, E1.119, E1.120, E1.121, E1.122, E1.123, E1.124, E1.125, E1.126