Microbiocidal picolinamide derivatives

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as pesticides, and especially fungicides. ##STR00001##

Claims

1. A compound of formula (I): ##STR00093## wherein, R.sup.1 is C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.6haloalkyl; R.sup.2 is hydroxy, C.sub.2-C.sub.6acyloxy, C.sub.2-C.sub.6haloacyloxy, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxyC.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6haloalkoxy, C.sub.2-C.sub.6acyloxyC.sub.1-C.sub.6alkoxy, C.sub.2-C.sub.6haloacyloxyC.sub.1-C.sub.6alkoxy, or C.sub.2-C.sub.6acyloxyC.sub.1-C.sub.6haloalkoxy; R.sup.3 is hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy or C.sub.3-C.sub.8cycloalkyl; R.sup.4 and R.sup.5 are each independently C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.6haloalkyl or C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6alkyl; R.sup.6 is hydrogen, C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl, aryl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the aryl and heteroaryl moieties are each optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9; R.sup.7 is hydrogen, C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl, aryl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the aryl and heteroaryl moieties are each optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9; or R.sup.6 and R.sup.7 together with the carbon atom to which they are attached form a C.sub.3-C.sub.8cycloalkyl ring which is optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9; R.sup.8 is C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl, aryl, aryloxy, heteroaryl, or heteroaryloxy, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the aryl and heteroaryl moieties are each optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9; R.sup.9 is halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, or C.sub.1-C.sub.4haloalkoxy; or a salt or an N-oxide thereof.

2. The compound according to claim 1, wherein R.sup.1 is methyl or ethyl.

3. The compound according to claim 1, wherein R.sup.2 is hydroxy, acetoxy or 2-methyl-propanoyloxymethoxy.

4. The compound according to claim 1, wherein R.sup.3 is hydrogen.

5. The compound according to claim 1, wherein R.sup.4 and R.sup.5 are each independently C.sub.1-C.sub.4alkyl.

6. The compound according to claim 1, wherein R.sup.6 is hydrogen or C.sub.1-C.sub.4alkyl.

7. The compound according to claim 1, wherein R.sup.7 is hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, aryl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein the aryl and heteroaryl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.9.

8. The compound according to claim 1, wherein R.sup.6 is hydrogen and R.sup.7 is C.sub.3-C.sub.6cycloalkyl.

9. The compound according to claim 1, wherein R.sup.8 is C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, aryl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein the aryl and heteroaryl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.9.

10. The compound according to claim 1, wherein R.sup.8 is phenyl or naphthyl, wherein the phenyl and naphthyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.9.

11. The compound according to claim 1, wherein R.sup.9 is halogen, C.sub.1-C.sub.3alkyl, or C.sub.1-C.sub.3haloalkyl.

12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to claim 1.

13. The composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.

14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to claim 1, or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

Description

FORMULATION EXAMPLES

(1) 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% —

(2) 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.

(3) 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%

(4) 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.

(5) 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  4% oxide) Cyclohexanone 30% xylene mixture 50%

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

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

(8) 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.

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

(10) 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.

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

(12) 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.

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

(14) 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.

(15) 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% 0.5%   solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%   Water 45.3%  

(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) Slow Release Capsule Suspension

(18) 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 polyvinyl alcohol, 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.

(19) 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.

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

EXAMPLES

(21) The Examples which follow serve to illustrate the invention. The 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.

(22) Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

List of Abbreviations

(23) ° C.=degrees Celsius

(24) CDCl.sub.3=chloroform-d

(25) EDC=1-ethyl-3-(3-dimethylaminopropyl)carbodiimide

(26) H=hours

(27) M=molar

(28) m=multiplet

(29) MHz=mega hertz

(30) ppm=parts per million

(31) s=singlet

(32) t=triplet

Example 1

(33) This example illustrates the preparation of [benzhydryl(methyl)amino] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.13)

(34) ##STR00049##
a) Preparation of N-methyl-1-phenyl-methanimine oxide

(35) ##STR00050##

(36) N-methylhydroxylamine hydrochloride (10.8 g, 127 mmol), sodium bicarbonate (21.8 g, 258 mmol) and magnesium sulfate (13.5 g, 113 mmol) were added at room temperature to a solution of benzaldehyde (5.0 g, 46.9 mmol) in dichloromethane (93.8 mL). The reaction was vigorously stirred at room temperature for 2 hours. Next the reaction mixture was filtered, the solid residue was washed with dichloromethane and the filtrate was concentrated under reduced pressure. Purification by chromatography on silica gel (eluent system: dichloromethane/methanol 20:1) afforded the desired N-methyl-1-phenyl-methanimine oxide (6.18 g, 45.7 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.90 (s, 3H), 7.38 (s, 1H), 7.41-7.47 (m, 3H), 8.20-8.26 (m, 2H).

(37) b) Preparation of N-benzhydryl-N-methyl-hydroxylamine

(38) ##STR00051##

(39) A 1M solution of phenylmagnesium bromide in tetrahydrofuran (2.4 mL, 2.4 mmol) was added dropwise at 0° C. to a solution of N-methyl-1-phenyl-methanimine oxide (270 mg, 2.0 mmol) in anhydrous tetrahydrofuran (6.65 mL) under inert atmosphere. The reaction mixture was allowed to reach room temperature and stirred for 17 additional hours. Next the mixture was diluted with dichloromethane and water. The aqueous layer was extracted twice with dichloromethane and the combined organic phases were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. Purification by chromatography on silica gel (eluent system: cyclohexane/ethyl acetate—gradient from 10:0 to 8:2) afforded the desired N-benzhydryl-N-methyl-hydroxylamine (346 mg, 1.62 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=2.62 (s, 3H), 4.61 (s, 1H), 4.89 (s, 1H), 7.22 (t, 2H), 7.31 (t, 4H), 7.47 (d, 4H).

(40) c) Preparation of [benzhydryl(methyl)amino] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.01)

(41) ##STR00052##

(42) N-benzhydryl-N-methyl-hydroxylamine (320 mg, 1.50 mmol), 4-pyrrolidinopyridine (230 mg, 1.5 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC, 390 mg, 2.5 mmol) were consecutively added at 0° C. to a suspension of (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoic acid (300 mg, 1.25 mmol) in dichloromethane (15 mL). The reaction mixture was stirred for 2 h at room temperature, then diluted with dichloromethane and water. The organic phase was separated, washed with a 1M HCl aqueous solution, then with brine, dried over sodium sulfate and concentrated under reduced pressure. Purification by chromatography on silica gel (eluent system: cyclohexane/ethyl acetate—gradient from 10:0 to 1:2) afforded the desired [benzhydryl(methyl)amino] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.01, 271 mg, 0.62 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=0.95 (bs, 3H), 2.78 (s, 3H, 3.95 (s, 3H), 4.47 (m, 1H), 4.88 (s, 1H), 6.88 (d, 1H), 7.15-7.22 (m, 2H), 7.25-7.32 (m, 4H), 7.45-7.50 (m, 4H), 7.99 (d, 1H), 8.25 (m, 1H), 12.04 (s, 1H).

(43) d) Preparation of [benzhydryl(methyl)amino] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.13)

(44) ##STR00053##

(45) Acetyl chloride (0.020 mL, 0.28 mmol) was added dropwise to a solution of [benzhydryl(methyl)amino] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.01, 82 mg, 0.19 mmol) and trimethylamine (0.053 mL, 0.46 mmol) in dichloromethane (4.6 mL). The reaction was stirred at room temperature for 1 hour. Next the reaction was diluted with dichloromethane and washed twice with an aqueous sodium bicarbonate saturated solution. The organic layer was washed with water, dried over sodium sulfate and concentrated under reduced pressure. Purification by chromatography on silica gel (eluent system: cyclohexane/ethyl acetate gradient from 10:0 to 4:6) afforded the desired [benzhydryl(methyl)amino] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound I.m.13, 72 mg, 0.15 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=0.87 (bs, 3H), 2.38 (s, 3H), 2.75 (s, 3H), 3.89 (s, 3H), 4.48 (m, 1H), 4.89 (s, 1H), 6.99 (d, 1H), 7.17-7.22 (m, 2H), 7.24-7.30 (m, 4H), 7.43-7.52 (m, 4H), 8.25-8.38 (m, 2H).

(46) Throughout this description, temperatures are given in degrees Celsius (° C.) and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method is: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 μm particle size, 110 Angström, 30×3 mm column, 1.7 mL/min., 60° C., H.sub.2O+0.05% HCOOH (95%)/CH.sub.3CN/MeOH 4:1+0.04% HCOOH (5%)—2 min. —CH.sub.3CN/MeOH 4:1+0.04% HCOOH (5%)—0.8 min., ACQUITY SQD Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700)).

(47) TABLE-US-00010 TABLE 2 Melting point and LC/MS data (Rt = Retention time) for selected compounds of Table 1 Compound Mp LC/MS No. Name Structure (° C.) (Method) I.a.01 [methyl(1- phenylethyl)amino] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 0.90 min; MS: m/z = 374 (M + 1) I.b.01 [methyl-[1-[4- (trifluoromethyl) phenyl]ethyl] amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.02 min; MS: m/z = 442 (M + 1) I.c.01 [methyl-[1-(2- naphthyl)ethyl] amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.02 min; MS: m/z = 424 (M + 1) I.d.01 [methyl-(2-methyl-1- phenyl-propyl)amino] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.05 min; MS: m/z = 402 (M + 1) I.e.01 [[cyclopropyl(phenyl) methyl]-methyl- amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 0.96- 0.98 min; MS: m/z = 400 (M + 1) I.f.01 [[cyclopropyl-[4- (trifluoromethyl) phenyl]methyl]- methyl-amino] (2S)-2-[(3- hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.08 min; MS: m/z = 468 (M + 1) I.g.01 [[cyclopropyl(2- naphthyl)methyl]- methyl-amino] (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate 0 (A) Rt = 1.07- 1.08 min; MS: m/z = 450 (M + 1) I.h.01 [[cyclopentyl(phenyl) methyl]-methyl- amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.11 min; MS: m/z = 428 (M + 1) I.j.01 [[cyclohexyl(phenyl) methyl]-methyl- amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.18 min; MS: m/z = 442 (M + 1) I.m.01 [benzhydryl(methyl) amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.04 min; MS: m/z = 436 (M + 1) I.m.02 [1,1-diphenylethyl (methyl)amino] (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.10 min; MS: m/z = 450 (M + 1) I.m.03 [1,1-diphenylpropyl (methyl)amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.16 min; MS: m/z = 464 (M + 1) I.m.13 [benzhydryl(methyl) amino] (2S)-2-[(3- acetoxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (B) Rt = 1.72 min; MS: m/z = 478 (M + 1) I.n.01 [[(4-fluorophenyl)- phenyl-methyl]-methyl- amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.72 min; MS: m/z = 436 (M + 1) I.o.01 [[(4-chlorophenyl)- phenyl-methyl]-methyl- amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.11 min; MS: m/z = 470 (M + 1) I.o.02 [[1-(4-chlorophenyl)-1- phenyl-ethyl]-methyl- amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.16 min; MS: m/z = 484 (M + 1) I.o.13 [[(4-chlorophenyl)- phenyl-methyl]-methyl- amino] (2S)-2-[(3- acetoxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate 0 (A) Rt = 1.12 min; MS: m/z = 512 (M + 1) I.q.01 [methyl-[phenyl-[4- (trifluoromethyl) phenyl]methyl] amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine- 2-carbonyl)amino] propanoate (A) Rt = 1.13 min; MS: m/z = 504 (M + 1) I.r.01 [methyl-[2- naphthyl(phenyl) methyl]amino] (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.13 min; MS: m/z = 486 (M + 1) I.s.01 [bis(4- fluorophenyl)methyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.04 min; MS: m/z = 472 (M + 1) I.s.02 [1,1-bis(4- fluorophenyl)ethyl- methyl-amino] (2S)- 2-[(3-hydroxy-4- methoxy-pyridine- 2-carbonyl)amino] propanoate (A) Rt = 1.10 min; MS: m/z = 486 (M + 1) I.s.13 [bis(4- fluorophenyl)methyl- methyl-amino] (2S)-2- [(3-acetoxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.07 min; MS: m/z = 514 (M + 1) I.s.14 [1,1-bis(4- fluorophenyl)ethyl- methyl-amino] (2S)- 2-[(3-acetoxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.10 min; MS: m/z = 528 (M + 1) I.t.01 [[(4-chlorophenyl)-(4- fluorophenyl)methyl]- methyl-amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.11 min; MS: m/z = 488 (M + 1) I.t.02 [[1-(4-chlorophenyl)-1- (4-fluorophenyl)ethyl]- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.15 min; MS: m/z = 502 (M + 1) I.u.01 [bis(4- chlorophenyl)methyl- methyl-amino] (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.16 min; MS: m/z = 504 (M + 1) I.u.02 [1,1-bis(4- chlorophenyl)ethyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate 0 (A) Rt = 1.20 min; MS: m/z = 518 (M + 1) I.u.03 [1,1-bis(4- chlorophenyl)propyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.26 min; MS: m/z = 532 (M + 1) I.u.13 [bis(4- chlorophenyl)methyl- methyl-amino] (2S)-2- [(3-acetoxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.16 min; MS: m/z = 546 (M + 1) I.u.14 [1,1-bis(4- chlorophenyl)ethyl- methyl-amino] (2S)-2- [(3-acetoxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.20 min; MS: m/z = 560 (M + 1) I.u.26 [2-[[(1S)-2-[1,1-bis(4- chlorophenyl)ethyl- methyl-amino]oxy-1- methyl-2-oxo-ethyl] carbamoyl]-4-methoxy- 3-pyridyl] oxymethyl 2- methylpropanoate (A) Rt = 1.25 min; MS: m/z = 618 (M + 1) I.v.01 [bis-p-tolylmethyl (methyl)amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.16 min; MS: m/z = 464 (M + 1) I.w.01 [bis[4- (trifluoromethyl)phenyl] methyl-methyl-amino] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino] propanoate (A) Rt = 1.19 min; MS: m/z = 572 (M + 1) I.x.01 [bis(3,5- dimethylphenyl)methyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.22 min; MS: m/z = 492 (M + 1) I.y.01 [methyl-[2-naphthyl-[4- (trifluoromethyl)phenyl] methyl]amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.20 min; MS: m/z = 554 (M + 1) I.z.01 [bis(2-naphthyl)methyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.20 min; MS: m/z = 536 (M + 1) I.aa.01 [bis(4-tert- butylphenyl)methyl- methyl-amino] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate 0 (A) Rt = 1.37 min; MS: m/z = 548 (M + 1) I.ab.01 [bis(4-methoxy phenyl)methyl-methyl- amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.02 min; MS: m/z = 496 (M + 1) I.ac.01 [bis(4-ethoxy phenyl)methyl-methyl- amino] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate (A) Rt = 1.13 min; MS: m/z = 524 (M + 1)

BIOLOGICAL EXAMPLES

(48) Alternaria solani/Tomato/Leaf Disc (Early Blight)

(49) Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23° C./21° C. (day/night) and 80% rh under a light regime of 12 h light/12 h dark in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5-7 days after application).

(50) The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: I.o.02.

(51) Blumeria graminis f. Sp. Tritici (Erysiphe Graminis f. Sp. Tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)

(52) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the test compound formulated with DMSO and Tween20 and diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are 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 is 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).

(53) Compound I.m.13 at 200 ppm in the formulation 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.

(54) Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

(55) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.

(56) Compounds I.m.01, I.m.03, I.u.26, I.v.01, I.ac.01, I.u.14, I.s.02, I.ab.01, I.u.02 and I.t.01 at 200 ppm in the formulation give at least 80% disease control in this test when compared to untreated checks under the same conditions, which show extensive mycelial growth.

(57) Glomerella Lagenarium (Colletotrichum lagenarium)/Liquid Culture (Anthracnose)

(58) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is measured photometrically 3 to 4 days after application.

(59) Compounds I.h.01, I.v.01, I.ac.01, I.u.14, I.t.02, I.s.02, I.ab.01, I.x.01, I.u.02, I.m.01, I.n.01, I.o.01, I.s.01, I.t.01 and I.u.01 at 200 ppm in the formulation give at least 80% disease control in this test when compared to untreated checks under the same conditions, which show extensive mycelial growth.

(60) Magnaporthe grisea (Pyricularia oryzae)/Rice/Leaf Disc Preventative (Rice Blast)

(61) Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the test compound formulated with DMSO and Tween20 and diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22° C. and 80% rh under a light regime of 24 h darkness followed by 12 h light/12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application).

(62) Compounds I.h.01, I.m.01, I.m.13, I.n.01, I.s.01, I.u.14, I.s.02, I.s.14, I.m.02, I.o.02 and I.u.01 at 200 ppm in the formulation 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

(63) Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot Rot Cereals)

(64) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 4-5 days after application.

(65) Compounds I.m.01, I.n.01, I.u.26, I.m.03, I.v.01, I.ac.01, I.u.03, I.u.14, I.t.02, I.aa.01, I.x.01, I.u.02 and I.s.01 at 200 ppm in the formulation give at least 80% disease control in this test when compared to untreated checks under the same conditions, which show extensive mycelial growth.

(66) Mycosphaerella arachidis (Cercospora arachidicola)/Liquid Culture (Early Leaf Spot)

(67) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 4-5 days after application.

(68) Compounds I.d.01, I.h.01, I.m.01, I.m.13, I.n.01, I.o.01, I.s.01, I.t.01, I.u.26, I.m.03, I.v.01, I.ac.01, I.u.03, I.u.14, I.t.02, I.s.02, I.s.14, I.ab.01, I.m.02, I.o.02, I.u.02, I.s.13 and I.u.01 at 200 ppm in the formulation give at least 80% disease control in this test when compared to untreated checks under the same conditions, which show extensive mycelial growth.

(69) Mycosphaerella Graminicola (Septoria tritici)/Liquid Culture (Septoria Blotch)

(70) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 4 to 5 days after application.

(71) Compounds I.d.01, I.e.01, I.h.01, I.m.01, I.m.13, I.n.01, I.o.01, I.s.01, I.u.26, I.m.03, I.v.01, I.ac.01, I.u.03, I.u.14, I.t.02, I.s.02, I.s.14, I.ab.01, I.aa.01, I.x.01, I.m.02, I.o.02, I.u.02, I.s.13 and I.u.01 at 200 ppm in the formulation give at least 80% disease control in this test when compared to untreated checks under the same conditions, which show extensive mycelial growth.

(72) Phaeosphaeria nodorum (Septoria nodorum)/Wheat/Leaf Disc Preventative (Glume Blotch)

(73) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20° 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 is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5-7 days after application).

(74) Compound I.e.01, I.h.01, I.j.01, I.m.01, I. m. 03, I.m.13, I.n.01, I.o.01, I.g.01, I.r.01, I.s.01, I.t.01, I. ac.01, I.u.14, I.s.02, I.s.14, I.ab.01, I.m.02, I.o.02, I.u.02, I.s.13 and I.u.01 at 200 ppm in the formulation 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.

(75) Puccinia Recondite f. Sp. Tritici/Wheat/Leaf Disc Preventative (Brown Rust)

(76) Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are 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 is 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).

(77) Compounds I.d.01, I.h.01, I.m.01, I.m.13, I.n.01, I.o.01, I.s.01, I.t.01, I.u.26, I.v.01, I.ac.01, I.u.14, I.t.02, I.ab.01, I.m.02, I.o.02, I.s.13 and I.u.01 at 200 ppm in the formulation 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.

(78) Pyrenophora teres/Barley/Leaf Disc Preventative (Net Blotch)

(79) Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20° C. and 65% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5-7 days after application).

(80) The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: I.m.03, I.u.14, I.t.02, I.s.02, I.m.02, I.o.02.