MICROBIOCIDAL 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): ##STR00054## wherein R.sup.1 is hydrogen, cyano, formyl, C.sub.1-C.sub.6alkylcarbonyl, C.sub.1-C.sub.6alkoxycarbonyl, C.sub.1-C.sub.6haloalkylcarbonyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6alkylcarbonyl, C.sub.3-C.sub.6cycloalkylcarbonyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkoxycarbonyl, C.sub.1-C.sub.6alkoxyoxalyl, C.sub.1-C.sub.6alkoxycarbonylC.sub.1-C.sub.4alkylC.sub.1-C.sub.6alkoxycarbonyl, C.sub.1-C.sub.6alkylsulfanylcarbonyl, or phenylcarbonyl; R.sup.2 and R.sup.3 are each independently hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, halogen, or C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.2alkyl; R.sup.4 is C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.8cycloalkylC.sub.1-C.sub.2alkyl, wherein the cycloalkyl groups are optionally substituted with 1 to 3 groups represented by R.sup.6, phenyl, phenylC.sub.1-C.sub.3alkyl, heteroaryl, heteroarylC.sub.1-C.sub.3alkyl, wherein the heteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, heterocyclylC.sub.1-C.sub.3alkyl, wherein the heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring comprising 1, 2 or 3 heteroatoms or groups individually selected from nitrogen, oxygen, sulfur, and S(O).sub.2, wherein the heterocyclyl groups are optionally substituted with 1 or 2 groups represented by R.sup.7, or a 5- to 10-membered non-aromatic spirocyclic carbobi- or carbotri-cyclyl ring system optionally comprising 1, 2, 3, 4 or 5 heteroatoms individually selected from nitrogen, oxygen and sulfur, and optionally bonded to the rest of the molecule through a C.sub.1-C.sub.2alkylene linker; R.sup.5 is phenyl or heteroaryl, wherein heteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, and wherein the phenyl or heteroaryl group is optionally substituted by 1, 2 or 3 substituents, which may be the same or different, selected from R.sup.6; R.sup.6 is halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, or C.sub.1-C.sub.4haloalkyl; R.sup.7 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 hydrogen, cyano, or C.sub.1-C.sub.3alkylcarbonyl.

3. The compound according to claim 1, wherein R.sup.1 is hydrogen, cyano or acetyl.

4. The compound according to claim 1, wherein R.sup.2 and R.sup.3 are each independently hydrogen, C.sub.1-C.sub.3alkyl, or halogen.

5. The compound according to claim 1, wherein R.sup.2 and R.sup.3 are each independently hydrogen, methyl, or fluoro.

6. The compound according to claim 1, wherein R.sup.4 is R.sup.4 is C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl, wherein the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R.sup.6, phenylC.sub.1-C.sub.3alkyl, heterocyclyl, heterocyclylC.sub.1-C.sub.3alkyl, wherein the heterocyclyl is a 5- or 6-membered non-aromatic monocyclic ring comprising 1 or 2 heteroatoms or groups individually selected from oxygen, sulfur, and S(O).sub.2, wherein the heterocyclyl groups are optionally substituted with a single group represented by R.sup.6, or a 6- to 9-membered non-aromatic spirocyclic carbobi-cyclyl ring system optionally comprising 1, or 2 heteroatoms individually selected from nitrogen, oxygen and sulfur.

7. The compound according to claim 1, wherein R.sup.4 is C.sub.3-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl, wherein the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R.sup.6, phenylC.sub.1-C.sub.3alkyl, heterocyclylC.sub.1-C.sub.3alkyl, wherein the heterocyclyl is a 4- to 6-membered non-aromatic monocyclic ring comprising a single heteroatom or group individually selected from oxygen, sulfur, and S(O).sub.2, wherein the heterocyclyl groups are optionally substituted with a single group represented by R.sup.6, or phenylC.sub.1-C.sub.3alkyl.sup.6.

8. The compound according to claim 1, wherein R.sup.5 is phenyl or heteroaryl, wherein heteroaryl is a 5- or 6-membered aromatic monocyclic ring comprising 1, 2 or 3 heteroatoms individually selected from nitrogen and sulfur, and wherein the phenyl or heteroaryl group is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.7.

9. The compound according to claim 1, wherein R.sup.5 is phenyl or pyridyl, wherein each phenyl or pyridyl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R.sup.7.

10. The compound according to claim 1, wherein R.sup.6 is methyl.

11. The compound according tom claim 1, wherein R.sup.7 is chloro, fluoro, methyl, or methoxy.

12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according tom 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, is applied to the plants, to parts thereof or the locus thereof.

15. Use of a compound of formula (I) according to claim 1 as a fungicide.

16. The compound according to claim 2, wherein R.sup.1 is hydrogen, cyano or acetyl.

17. 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 a composition according to claim 12, is applied to the plants, to parts thereof or the locus thereof.

Description

EXAMPLES

[0215] 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.

[0216] 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

[0217] ° C.=degrees Celsius, CDCl.sub.3=chloroform-d, d=doublet, DIPEA=N,N-diisopropylethylamine, DMF=dimethylformamide, HAUT=1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate, m=multiplet, MHz=mega hertz, PyBOP=benzotriazol-1-yl-oxytripyrrolidino-phosphonium hexafluorophosphate, q=quartet, s=singlet, THF=tetrahydrofuran

Example 1: This example illustrates the preparation of 6-(3,5-difluoroanilino)-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide (Compound P-11)

a) Preparation of N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide

[0218] ##STR00023##

[0219] To a solution of 3-hydroxy-4-methoxy-pyridine-2-carboxylic acid (1.1 equiv.) and 2,2-dimethylcyclobutylamine hydrochloride (1.5 g, 12.2 mmol, 1.0 equiv.) in dichloromethane (110 ml), PyBOP (1.1 equiv.) and DIPEA (3.3 equiv.) were added in sequence. The reaction was stirred at room temperature overnight and then concentrated in vacuo. Direct purification of the crude by chromatography on silica gel (eluent: mixtures cyclohexane/ethyl acetate) afforded the desired N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide in 92% yield (2.55 g, 10.2 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.15 (s, 3H), 1.21 (s, 3H), 1.60-1.70 (m, 2H), 1.93-1.98 (m, 1H), 2.25-2.35 (m, 1H), 3.96 (s, 3H), 4.20-4.30 (q, 1H), 6.87 (d, 1H), 7.97 (d, 1H), 8.10-8.20 (m, 1H), 12.52 (s, 1H).

b) Preparation of 6-chloro-N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide

[0220] ##STR00024##

[0221] N-chlorosuccinimide (2.0 equiv.) was added portionwise to a stirred solution of N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide (2.55 g, 10.2 mmol, 1.0 equiv.) in DMF (51 ml). The reaction was stirred overnight at room temperature and then poured in sodium thiosulfate solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulphate and concentrated in vacuo. The desired 6-chloro-N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide (2.07 g, 7.27 mmol, 71% yield) was obtained after purification by chromatography on silica gel (eluent: mixtures cyclohexane/ethyl acetate). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.14 (s, 3H), 1.22 (s, 3H), 1.60-1.70 (m, 2H), 1.95-2.05 (m, 1H), 2.25-2.35 (m, 1H), 3.97 (s, 3H), 4.20-4.30 (q, 1H), 6.86 (s, 1H), 7.75-7.85 (m, 1H), 12.60 (s, 1H).

c) Preparation of 6-chloro-N-(2,2-dimethylcyclobutyl)-3,4-dihydroxy-pyridine-2-carboxamide

[0222] ##STR00025##

[0223] 6-chloro-N-(2,2-dimethylcyclobutyl)-3-hydroxy-4-methoxy-pyridine-2-carboxamide (2.0 g, 7.02 mmol, 1.0 equiv.) and pyridine hydrochloride (7 equiv.) were stirred at 150° C. for 10 hours. Then the reaction was cooled to room temperature, and the crude mixture directly purified by chromatography on silica gel (eluent: dichloromethane) to afford the desired 6-chloro-N-(2,2-dimethylcyclobutyl)-3,4-dihydroxy-pyridine-2-carboxamide in 80% yield (1.52 g, 5.61 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.15 (s, 3H), 1.22 (s, 3H), 1.60-1.70 (m, 2H), 1.95-2.05 (m, 1H), 2.25-2.35 (m, 1H), 4.20-4.30 (q, 1H), 6.98 (s, 1H), 7.70-7.85 (m, 1H), 12.61 (s, 1H).

d) Preparation of 6-chloro-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide

[0224] ##STR00026##

[0225] Under an argon atmosphere, cesium carbonate (2.0 equiv.) and dibromomethane (1.2 equiv.) were added in sequence to a solution of 6-chloro-N-(2,2-dimethylcyclobutyl)-3,4-dihydroxy-pyridine-2-carboxamide (700 mg, 2.59 mmol, 1.0 equiv.) in DMF (10.3 ml). The mixture was stirred at 110° C. for 1 h and then cooled to room temperature, quenched with water and the water phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulphate and concentrated in vacuo. The crude product was purified by chromatography on silica gel (eluent: mixtures cyclohexane/ethyl acetate) to afford the desired 6-chloro-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide in 78% yield (572 mg, 2.02 mmol). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.11 (s, 3H), 1.22 (s, 3H), 1.60-1.70 (m, 2H), 1.90-1.97 (m, 1H), 2.25-2.35 (m, 1H), 4.25-4.30 (q, 1H), 6.25 (s, 2H), 6.89 (s, 1H), 7.61 (m, 1H).

e) Preparation of 6-(3,5-difluoroanilino)-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide (Compound P-11)

[0226] ##STR00027##

[0227] Under an argon atmosphere, BrettPhos-G3-palladacycle ([(2-Di-cyclohexylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate methanesulfonate, 0.1 equiv.) and potassium tert-butoxide (2.5 equiv.) were added to a degassed, stirred mixture of 6-chloro-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide (100 mg, 0.354 mmol, 1 equiv.) and 3,5-difluoro aniline (1.1 equiv.) in THE (1.5 ml). The reaction was heated to 80° C. and stirred for 1 hour, then the mixture was cooled to room temperature. The volatiles were removed using a rotatory evaporator and the residue was dissolved in ethyl acetate. The organic phase was washed twice with water, dried over anhydrous sodium sulphate and concentrated in vacuo. Purification by column chromatography on silica gel (eluent: mixtures cyclohexane ethyl acetate) afforded the desired methyl 6-(3,5-difluoroanilino)-N-(2,2-dimethylcyclobutyl)-[1,3]dioxolo[4,5-c]pyridine-4-carboxamide (76 mg, 57% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.13 (s, 3H), 1.21 (s, 3H), 1.60-1.70 (m, 2H), 1.80-1.95 (m, 1H), 2.25-2.35 (m, 1H), 4.40-4.45 (q, 1H), 6.17 (s, 2H), 6.40-6.55 (m, 3H), 6.90-7.05 (m, 2H), 7.60-7.65 (m, 1H).

[0228] 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 m 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 m 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). Method C: ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C., Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A=Water/Methanol 9:1+0.1% formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75).

TABLE-US-00011 TABLE 3 Melting point and LC/MS data (R.sub.t = Retention time) for selected compounds of Table 1 and Table 2. Compound Mp No. Name Structure (° C.) LC/MS P-1  6-anilino-N-(2,2- dimethylpropyl)-2- methyl- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00028] 171-176 R.sub.t = 1.09 min (A); MS: m/z = 342 (M + H) P-2  N-(2,2- dimethylpropyl)-6-(3- fluoroanilino)-2- methyl- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00029] 62-74 R.sub.t = 1.11 min (A); MS: m/z = 360 (M + H) P-3  6-(3,5-difluoroanilino)- N-(2,2- dimethylpropyl)-2- methyl- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00030] 192-198 R.sub.t = 1.15 min (A); MS: m/z = 378 (M + H) P-4  6-[(2,6-difluoro-4- pyridyl)amino]-N-(2,2- dimethylpropyl)-2- methyl- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00031] R.sub.t = 1.05 min (A); MS: m/z = 379 (M + H) P-5  6-(3,5-difluoroanilino)- N-(2,2- dimethylpropyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00032] R.sub.t = 1.10 min (A); MS: m/z = 364 (M + H) P-6  6-(3,5-difluoroanilino)- N-(2,2- dimethylcyclobutyl)- 2,2-difluoro- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00033] 176-179 R.sub.t = 1.24 min (A); MS: m/z = 412 (M + H) P-7  6-(N-cyano-3,5- difluoro-anilino)-N- (2,2- dimethylcyclobutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00034] 240-250 R.sub.t = 1.11 min (A); MS: m/z = 401 (M + H) P-8  N-(2,2- dimethylcyclobutyl)-6- (3-fluoroanilino)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00035] 162-167 R.sub.t = 1.10 min (A); MS: m/z = 358 (M + H) P-9  6-anilino-N-(2,2- dimethylcyclobutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00036] 145-150 R.sub.t = 1.08 min (A); MS: m/z = 340 (M + H) P-10 6-[(2,6-difluoro-4- pyridyl)amino]-N-(2,2- dimethylcyclobutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00037] 230-238 R.sub.t = 1.09 min (A); MS: m/z = 377 (M + H) P-11 6-(3,5-difluoroanilino)- N-(2,2- dimethylcyclobutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00038] 185-189 R.sub.t = 1.04 min (A); MS: m/z = 376 (M + H) P-12 6-[(2,6-difluoro-4- pyridyl)amino]-N- isopentyl- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00039] 202-205 R.sub.t = 1.02 min (A); MS: m/z = 365 (M + H) P-13 6-[(2,6-difluoro-4- pyridyl)amino]-N-(2,2- dimethylpropyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00040] 230-233 R.sub.t = 1.01 min (A); MS: m/z = 365 (M + H) P-14 N-(2,2- dimethylpropyl)-6-[(5- fluoro-3- pyridyl)amino]- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00041] 202-205 R.sub.t = 0.93 min (A); MS: m/z = 347 (M + H) P-15 N-(2,2- dimethylpropyl)-6-(3- fluoroanilino)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00042] R.sub.t = 1.08 min (A); MS: m/z = 346 (M + H) P-16 6-(3,5-difluoroanilino)- N-[1-(1,1-dioxothian- 4-yl)-1-methyl-ethyl]- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00043] R.sub.t = 1.40 min (C); MS: m/z = 468 (M + H) P-17 6-(3,5-difluoroanilino)- N-(1,1,3,3- [tetramethylbutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00044] R.sub.t = 1.99 min (C); MS: m/z = 406 (M + H) P-18 6-(3,5-difluoroanilino)- N-(1,1- dimethylpropyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00045] R.sub.t = 1.76 min (C); MS: m/z = 364 (M + H) P-19 6-(3,5-difluoroanilino)- N-(3-methylthietan-3- yl)-[1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00046] R.sub.t = 1.64 min (C); MS: m/z = 380 (M + H) P-20 6-(3,5-difluoroanilino)- N-(1-methyl-1-phenyl- ethyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00047] R.sub.t = 1.81 min (C); MS: m/z = 412 (M + H) P-21 N-tert-butyl-6-(3,5- difluoroanilino)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00048] R.sub.t = 1.67 min (C); MS: m/z = 350 (M + H) P-22 6-(3,5-difluoroanilino)- N-(1- methylcyclobutyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00049] R.sub.t = 1.69 min (C); MS: m/z = 361 (M + H) P-23 6-(3,5-difluoroanilino)- N-(3- methyltetrahydrofuran- 3-yl)-[1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00050] R.sub.t = 1.41 min (C); MS: m/z = 378 (M + H) P-24 6-(3,5-difluoroanilino)- N-(3-methyloxetan-3- yl)-[1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00051] R.sub.t = 1.30 min (C); MS: m/z = 364 (M + H) P-25 6-(3,5-difluoroanilino)- N-(1- methylcyclopentyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00052] R.sub.t = 1.79 min (C); MS: m/z = 390 (M + H) P-26 6-(3,5-difluoroanilino)- N-(1- methylcyclohexyl)- [1,3]dioxolo[4,5- c]pyridine-4- carboxamide [00053] R.sub.t = 1.87 min (C); MS: m/z = 390 (M + H)

Biological Examples

Example B1. Alternaria solani/Tomato/Leaf Disc (Early Blight)

[0229] 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 12/12 h (light/dark) 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 on untreated check disk leaf disks (5-7 days after application). 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: P-8, P-9, P-118, P-19, P-21, P-22, P-23, P-24, and P-25.

Example B2. Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

[0230] 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. The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-22.

Example B3. Glomerella Lagenarium (Colletotrichum lagenarium)/Liquid Culture (Anthracnose)

[0231] 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. The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-2, P-3, P-5, P-6, P-7, P-8, P-9, P-10, P-11, P-14, P-15, P-18, P-19, P-20, P-21, P-22, P-23, P-24, P-25, and P-26.

Example B4. Blumeria Graminis f. Sp. Tritici (Erysiphe graminis f. Sp. Tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)

[0232] 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 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). The following compounds gave at least 80% control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-9, P-11, P-14, P-18, and P-22.

Example B5. Phaeosphaeria nodorum (Septoria nodorum)/Wheat/Leaf Disc Preventative (Glume Blotch)

[0233] 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). The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-5, P-11, P-15, P-18, P-22, and P-25.

Example B6. Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot Rot Cereals)

[0234] 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. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-5, P-6, P-7, P-8, P-9, P-10, P-11, P-12, P-14, P-15, P-17, P-18, P-19, P-20, P-21, P-22, P-23, P-24, P-25, and P-26.

Example B7. Mycosphaerella arachidis (Cercospora arachidicola)/Liquid Culture (Early Leaf Spot)

[0235] 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. The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-8, P-9, P-11, P-15, P-18, P-19, P-21, P-22, and P-25.

Example B8. Puccinia recondita f. Sp. Tritici/Wheat/Leaf Disc Preventative (Brown Rust)

[0236] 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). The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-8, P-11, P-12, P-18, P-21, P-22, P-25, and P-26.

Example B9. Magnaporthe grisea (Pyricularia oryzae)/rice/leaf disc preventative (Rice Blast)

[0237] Rice leaf segments cv. Ballila 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 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). The following compounds gave at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-5, P-14, P-15, P-17, P-18, P-19, P-21, P-22, P-24, P-25, and P-26.

Example B10. Pyrenophora Teres/Barley/Leaf Disc Preventative (Net Blotch)

[0238] 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). 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: P-5, P-8, P-9, P-15, P-18, P-19, P-21, P-22, P-23, P-25, and P-26.

Example B11. Mycosphaerella graminicola (Septoria tritici)/Liquid Culture (Septoria Blotch)

[0239] 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. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2, P-5, P-7, P-8, P-9, P-10, P-11, P-12, P-13, P-14, P-15, P-17, P-18, P-19, P-20, P-21, P-22, P-23, P-24, P-25, and P-26.