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): ##STR00080## 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 independently C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6alkyl or C.sub.3-C.sub.8halocycloalkyl; R.sup.6 and R.sup.7 are independently C.sub.1-C.sub.4alkyl; 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, or is optionally substituted by a single substituent which is R.sup.10, or is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.9 and a single substituent which is R.sup.10; R.sup.8 is phenyl, phenoxy, naphthyl, naphthyloxy, 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, heterodiaryl or heterodiaryloxy, wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, wherein each phenyl, naphthyl, heteroaryl or heterodiaryl is 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, C.sub.1-C.sub.4haloalkoxy; and R.sup.10 is phenyl or cyclopropyl each optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from fluoro, chloro, bromo, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy; 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, propanoyloxy, acetoxymethoxy, propanoyloxymethoxy, 2-methyl-propanoyloxymethoxy.

4. The compound according to claim 1, wherein R.sup.2 is hydroxy.

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

6. The compound according to claim 1, wherein R.sup.4 is methyl or ethyl and R.sup.5 is methyl or ethyl.

7. The compound according to claim 1, wherein R.sup.6 and R.sup.7 together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring which is optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9, or is optionally substituted by a single substituent which is R.sup.10, or is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.9 and a single substituent which is R.sup.10.

8. The compound according to claim 1, wherein R.sup.8 is phenyl, naphthyl, furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, cinnolinyl, pyrimidinyl, quinazolinyl, pyrazinyl, phenoxy, naphthyloxy, pyridyloxy or quinolinyloxy, optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.9.

9. The compound according to claim 1, wherein R.sup.8 is phenyl, naphthyl, thienyl, indolyl, pyridyl, quinolinyl, pyridazinyl, pyrimidinyl, pyrazinyl, phenoxy, pyridyloxy or quinolinyloxy 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, thienyl, pyridyl, phenoxy or pyridyloxy optionally substituted by a single substituent selected from R.sup.9.

11. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to claim 1, and an agrochemically-acceptable carrier or diluent.

12. The composition according to claim 11, further comprising at least one additional active ingredient.

13. 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.

14. The compound according to claim 1, wherein R.sup.6 and R.sup.7 are methyl.

Description

FORMULATION EXAMPLES

(1) Wettable Powders a) b) c)

(2) TABLE-US-00002 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% —

(3) 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.

(4) Powders for Dry Seed Treatment a) b) c)

(5) TABLE-US-00003 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) Emulsifiable Concentrate

(8) TABLE-US-00004 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%
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Dusts a) b) c)

(9) TABLE-US-00005 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) Extruder Granules

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

(13) 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.

(14) Coated Granules

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

(16) 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.

(17) Suspension Concentrate

(18) TABLE-US-00008 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%

(19) 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.

(20) Flowable concentrate for seed treatment

(21) TABLE-US-00009 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 0.5%.sup.  (in the form of a 20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup.  Water 45.3%  

(22) 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.

(23) Slow Release Capsule Suspension

(24) 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.

(25) 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.

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

EXAMPLES

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

(28) 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.

(29) 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

(30) ° C.=degrees Celsius

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

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

(33) d=doublet

(34) m=multiplet

(35) MHz=mega hertz

(36) mp=melting point

(37) ppm=parts per million

(38) s=singlet

(39) t=triplet

EXAMPLES

Example 1: This example illustrates the preparation of 1-(1-phenylcyclopropyl)ethyl (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound 1.a.006)

(40) ##STR00053##

a) Preparation of N-methoxy-N-methyl-1-phenylcyclopropanecarboxamide

(41) 1,1′-Carbonyldiimidazole (2.5 g, 15 mmol) was added at room temperature to a solution of 1-phenylcyclopropancarboxylic acid (1.6 g, 10 mmol) in 20 ml of dichloroethane. The reaction mixture was heated to 60° C. for 4 h, then N-methoxy-N-methyl-hydroxylamine (1.7 g, 15 mmol) was added and the reaction mixture was stirred for 16 h at 60° C., then cooled to room temperature and diluted with water and dichloromethaner. The phases were separated and the aqueous phase was washed with dichloromethane. The combined organic layer was washed with water, dried over sodium sulfate and evaporated under reduced pressure, the remainder was purified by chromatography on silica gel, using ethyl acetate/cyclohexane as eluent system, to deliver N-methoxy-N-methyl-1-phenylcyclopropanecarboxamide (1.4 g, 6.7 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.13 (t, 2H), 1.44 (t, 2H), 3.12 (s, 3H), 3.20 (s, 3H), 7.20-7.36 (m, 5H).

b) Preparation of 1-(1-phenylcyclopropyl)ethanone

(42) 16 ml of a 1 M solution of methylmagnesium brmide in tetrhydrofurane were added dropwise at 0° C. to a solution of N-methoxy-N-methyl-1-phenylcyclopropanecarboxamide (1.4 g, 6.7 mmol) in 16 ml of tetrahydrofuran. The reaction mixture was stirred for 16 h at 50° C., then cooled to 0° C. and quenched by addition of saturated aqueous ammoinium chloride solution. The mixture was diluted with ethyl acetate, the phases were separated and the aqueous phase was washed with ethyl acetate. The combined organic layer was washed with water, dried over sodium sulfate and evaporated under reduced pressure, the remainder was purified by chromatography on silica gel, using ethyl acetate/cyclohexane as eluent system, to deliver 1-(1-phenylcyclopropyl)ethanone (0.9 g, 4.6 mmol).sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.20 (t, 2H), 1.63 (t, 2H), 2.02 (s, 3H), 7.30-7.41 (m, 5H).

c) Preparation of 1-(1-phenylcyclopropyl)ethanol

(43) Sodium borohydride (0.1 g, 2.7 mmol) was slowly added at 0° C. to a solution of 1-(1-phenylcyclopropyl)ethanone (0.9 g, 4.6 mmol) in 30 ml of methanol. The reaction mixture was stirred for 16 h at room temperature, then again cooled to 0° C. and quenched by addition of saturated aqueous ammonium chloride solution. The mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by chromatography on silica gel, using ethyl acetate/heptane 1:3 as solvent system to deliver 1-(1-phenylcyclopropyl)ethanol (0.56 g, 3.5 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=0.77-0.90 (m, 4H), 1.15 (d, 3H), 3.41 (q, 1H), 7.25-7.41 (m, 5H).

d) Preparation of 1-(1-phenylcyclopropyl)ethyl (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound 1.a.006)

(44) 1-(1-phenylcyclopropyl)ethanol (0.28 g, 1.7 mmol), 4-pyrrolidinopyridine (0.26 g, 1.7 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC, 0.46 g, 2.9 mmol) were consecutively added at 0° C. to a suspension of (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoic acid (0.35 g, 1.5 mmol) in 18 ml of dichloromethane. The reaction mixture was stirred for 5 h at room temperature, then quenched by addition of diluted hydrochloric acid and diluted with dichloromethane. The phases were separated, the organic layer was washed with saturated aqueous sodium bicarbonate solution and brine, dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by chromatography on silica gel, using ethyl acetate/cyclohexane 1:3 as solvent system to deliver 1-(1-phenylcyclopropyl)ethyl (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate (Compound 1.a.006, 0.15 g, 0.4 mmol).sup.1H-NMR (400 MHz, CDCl.sub.3): δ=0.82-0.99 (m, 4H), 1.21 (t, 3H), 1.52-1.61 (m, 3H), 3.97 (s, 3H), 4.63-4.77 (m, 2H), 6.90 (d, 1H), 7.22-7.39 (m, 5H), 8.04 (d, 1H), 8.55 (bs, 1H), 12.21 (s, 1H).

(45) 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: (Method A: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 μm particle size, 30×2.1 mm column, 0.85 mL/min., 60° C., H.sub.2O/MeOH 95:5+0.05% HCOOH (90%)/CH.sub.3CN+0.05% HCOOH (10%)—1.2 min.—CH.sub.3CN+0.05% HCOOH (100%)—0.30 min., ACQUITY SQD Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650). Method B: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 μm particle size, 30×2.1 mm column, 0.85 mL/min., 60° C., H.sub.2O/MeOH 95:5+0.05% HCOOH (90%)/CH.sub.3CN+0.05% HCOOH (10%)—2.7 min.—CH.sub.3CN+0.05% HCOOH (100%)—0.30 min., ACQUITY SQD Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650)).

(46) TABLE-US-00010 TABLE 2 LC/MS data (Rt = Retention time) for selected compounds of Table 1. Compound No. Compound name Structure LC/MS I.a.001 (1,2-dimethyl-2-phenyl- propyl) (2S)-2-[(3-hydroxy- 4-methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.09 min; MS: m/z = 387 (M + 1) I.a.006 1-(1-phenylcyclopropyl)- ethyl (2S)-2-[(3-hydroxy- 4-methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.07 min; MS: m/z = 385 (M + 1) I.a.010 1-(1,2-diphenylcyclo- propyl)ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.92 min, 1.95 min, 1.97 min; MS: m/z = 461 [M + 1] I.a.015 1-(1-phenylcyclohexyl)- ethyl (2S)-2-[(3-hydroxy- 4-methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.21 min; MS: m/z = 427 (M + 1) I.d.006 1-[1-(3-bromophenyl)- cyclopropyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.15 min; MS: m/z = 463 (M + 1) I.j.001 [2-(4-fluorophenyl)-1,2- dimethyl-propyl] (2S)-2- [(3-hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.75 min; MS: m/z = 405 (M + 1) I.j.010 1-[1-(4-fluorophenyl)- 2-phenyl-cyclopropyl]- ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate 0 (B) Rt = 1.93 min, 1.97 min; MS: m/z = 479 (M + 1) I.j.011 1-[1,2-bis(4-fluoro- phenyl)cyclopropyl]- ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.95 min, 1.97 min; MS: m/z = 496 (M + 1) I.k.001 [2-(4-chlorophenyl)- 1,2-dimethyl-propyl] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (B) Rt = 1.89 min; MS: m/z = 421 (M + 1) I.k.006 1-[1-(4-chlorophenyl)- cyclopropyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.12 min; MS: m/z = 419 (M + 1) I.k.012 1-[1-(4-chlorophenyl)- cyclobutyl]ethyl (2S)-2- ((3-hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (A) Rt = 1.17 min; MS: m/z = 433 (M + 1) I.k.014 1-[1-(4-chlorophenyl)- cyclopentyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.22 min; MS: m/z = 447 (M + 1) I.k.015 1-[1-(4-chlorophenyl)- cyclohexyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.25 min; MS: m/z = 462 (M + 1) I.k.075 1-[1-(4-chlorophenyl)- cyclohexyl]ethyl (2S)-2- [(3-acetoxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 2.13 min; MS: m/z = 503 (M + 1) I.m.001 [2-(4-bromophenyl)- 1,2-dimethyl-propyl] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (A) Rt = 1.17 min; MS: m/z = 465 (M + 1) I.m.006 1-[1-(4-bromophenyl)- cyclopropyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (B) Rt = 1.88 min; MS: m/z = 463 (M + 1), 465 (M + 3) I.m.012 1-[1-(4-bromophenyl)- cyclobutyl]ethyl (2S)- 2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate 0 (A) Rt = 1.20 min; MS: m/z = 477 (M + 1) I.o.014 1-[1-[4-(trifluoromethyl)- phenyl]cyclopentyl]ethyl (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]prapanoate (B) Rt = 2.08 min; MS: m/z = 481 (M + 1) I.q.006 1-[1-[4-(trifluoro- methoxy)phenyl]cyclo- propyl]ethyl (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]propanoate (B) Rt = 1.95 min; MS: m/z = 470 (M +1) I.t.006 1-[1-(3,4-dichloro- phenyl)cyclopropyl]- ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.96 min; MS: m/z = 453 (M + 1) I.u.007 1-[1-(4-ethoxyphenyl)- 2,2-difluorocyclopropyl]- ethyl (2S)-2-[(3-hydroxy- 4-methoxy-pyridine-2- carbonyl)amino]propanoate (B) Rt = 1.69 min; MS: m/z = 466 (M + 1) I.v.006 1-[1-(1-naphthyl)cyclo- propyl]ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.90 min; MS: m/z = 435 (M + 1) I.v.010 1-[1-(1-naphthyl)-2- phenyl-cyclopropyl]- ethyl (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 2.06 min, 2.09 min, 2.11 min; MS: m/z = 511 (M + 1) I.v.011 1-[2-(4-fluorophenyl)- 1-(1-naphthyl)cyclo- propyl]ethyl (2S)-2- [(3-hydroxy-4- methoxy-pyridine-2- carbonyl)amino]- propanoate (B) Rt = 2.08 min, 2.10 min, 2.11 min; MS: m/z = 529 (M + 1) I.v.066 1-[1-(1-naphthyl)cyclo- propyl]ethyl (2S)-2-[(3- acetoxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.92 min; MS: m/z = 477 (M + 1) I.ah.001 [2-(2,5-difluoro- phenyl)-1,2-dimethyl- propyl] (2S)-2-[(3- hydroxy-4-methoxy- pyridine-2-carbonyl)- amino]propanoate (B) Rt = 1.76 min; MS: m/z = 424 (M + 1)

BIOLOGICAL EXAMPLES

(47) Blumeria graminis f. sp. tritici (Erysiphe raminis f. sp. tritici)/wheat/leaf disc preventative (Powdery Mildew on Wheat)

(48) 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).

(49) Compounds I.k.012, I.k.015 and I.m.012 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.

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

(51) 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.

(52) Compounds I.a.001, I.a.006, I.a.010, I.a.015, I.d.006, I.j.001, I.k.006, I.k.012 I.k.014, I.k.015, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, and I.v.066 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.

(53) Glomerella lacenarium (Colletotrichum lacenarium)/Liquid Culture (Anthracnose)

(54) 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 3-4 days after application.

(55) Compounds I.a.010, I.a.015, I.d.006, I.j.001, I.j.010, I.j.011, I.k.012, I.k.014, I.k.015, I.k.075, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, I.v.006, I.v.010, I.v.011, I.v.066 and I.ah.001 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.

(56) Magnaporthe risea (Pyricularia Oryzae)/Rice/Leaf Disc Preventative (Rice Blast)

(57) 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 (5-7 days after application).

(58) Compounds I.a.006, I.a.010, I.a.015, I.k.012, I.k.014, I.k.075, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, I.v.066 and I.ah.001 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

(59) Monocraphella nivalis (Microdochium nivale)/Liquid Culture (Foot Rot Cereals)

(60) 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.

(61) Compounds I.a.001, I.a.006 I.k.006, I.a.010, I.a.015, I.d.006, I.j.001, I.j.011, I.k.012 I.k.014, I.k.015, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, I.v.006, I.v.066 and I.ah.001 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.

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

(63) 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.

(64) Compounds I.a.001, I.a.006, I.k.006, I.a.010, I.a.015, I.d.006, I.j.001, I.j.010, I.j.011, I.k.012, I.k.014, I.k.015, I.k.075, I.m.001, I.m.012, I.q.006, I.t.006, I.v.006, I.v.010, I.v.011, I.v.066 and I.ah.001 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.

(65) Mycosphaerella Raminicola (Septoria tritici)/Liquid Culture (Septoria Blotch)

(66) 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.

(67) Compounds I.a.001, I.a.006, I.a.010, I.a.015, I.d.006, I.j.001, I.j.010, I.j.011, I.k.006, I.k.012, I.k.014, I.k.015, I.k.075, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, I.v.006, I.v.010, I.v.011, I.v.066 and I.ah.001 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.

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

(69) 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).

(70) Compound I.a.001, I.a.010, I.a.015, I.k.006, I.k.012, I.k.015, I.k.075, I.m.001, I.v.006, I.v.066 and I.ah.001 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.

(71) Puccinia recondita f. Sp. Tritici/Wheat/Leaf Disc Preventative (Brown Rust)

(72) 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).

(73) Compound I.a.001, I.a.006, I.a.010, I.a.015, I.d.006, I.j.001, I.j.010, I.j.011, I.k.006, I.k.012, I.k.014, I.k.015, I.k.075, I.m.001, I.m.012, I.q.006, I.t.006, I.u.007, I.v.006, I.v.010, I.v.011, I.v.066 and I.ah.001 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.