MICROBIOCIDAL QUINOLINE DIHYDRO-(THIAZINE)OXAZINE DERIVATIVES

Abstract

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

##STR00001##

Claims

1. A compound of formula (I): ##STR00063## wherein: X is O or S; R.sup.1 is halogen, methyl or cyano; R.sup.2 is hydrogen or halogen; R.sup.3 and R.sup.4 are each independently hydrogen or methyl; R.sup.5 and R.sup.6 are each independently selected from hydrogen, C.sub.1-C.sub.5alkyl, C.sub.1-C.sub.5haloalkyl, cyanoC.sub.1-C.sub.5alkyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.5alkyl, C.sub.1-C.sub.3alkylthioC.sub.1-C.sub.5alkyl, C.sub.2-C.sub.5alkenyl, C.sub.2-C.sub.5haloalkenyl, cyanoC.sub.2-C.sub.5alkenyl, C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.5alkenyl, C.sub.1-C.sub.3alkylthioC.sub.2-C.sub.5alkenyl, C.sub.2-C.sub.5alkynyl, C.sub.2-C.sub.5haloalkynyl, cyanoC.sub.2-C.sub.5alkynyl, C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.5alkynyl, C.sub.1-C.sub.3alkylthioC.sub.2-C.sub.5alkynyl and C.sub.3-C.sub.6cycloalkyl, wherein cycloalkyl is optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkoxy and C.sub.1-C.sub.3alkylthio; or R.sup.5 and R.sup.6 together with the carbon atom to which they are attached represent C.sub.3-C.sub.6cycloalkyl, wherein the cycloalkyl group is optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano and C.sub.1-C.sub.3alkyl; R.sup.7 is hydrogen, C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.4cycloalkyl; A is C.sub.1-C.sub.5alkyl, C.sub.2-C.sub.5alkenyl, C.sub.3-C.sub.6cycloalkyl, C.sub.4-C.sub.6cycloalkenyl, C.sub.1-C.sub.5haloalkyl, C.sub.2-C.sub.5haloalkenyl, C.sub.1-C.sub.4alkoxy, C.sub.3-C.sub.5alkenyloxy, C.sub.3-C.sub.5alkynyloxy, C.sub.1-C.sub.4haloalkoxy, C.sub.3-C.sub.6cycloalkoxy and phenyloxy, wherein the C.sub.3-C.sub.6cycloalkoxy and phenyloxy is optionally substituted with 1, 2 or 3 substituents independently selected from R.sup.8; R.sup.8 is halogen, nitro, cyano, C.sub.1-C.sub.5alkyl, C.sub.1-C.sub.2haloalkyl, C.sub.1-C.sub.5alkoxy, C.sub.3-C.sub.5alkenyloxy, C.sub.3-C.sub.5alkynyloxy and C.sub.1-C.sub.5alkylthio; or an agronomically acceptable salt, an N-oxide and/or S-oxide or a stereoisomer thereof.

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

3. The compound according to claim 1, wherein R.sup.2 is hydrogen or fluoro.

4. The compound according to claim 1, wherein R.sup.3 is methyl and R.sup.4 is hydrogen, R.sup.3 is hydrogen and R.sup.4 is methyl, or R.sup.3 and R.sup.4 are hydrogen.

5. The compound according to claim 1, wherein R.sup.5 and R.sup.6 are each independently selected from hydrogen or C.sub.1-C.sub.5alkyl.

6. The compound according to claim 1, wherein R.sup.5 and R.sup.6 together form a (CH.sub.2).sub.n group bound to the carbon atom to which they are attached, wherein n is 2, 3, 4 or 5.

7. The compound according to am claim 1, wherein R.sup.7 is hydrogen, methyl, ethyl or iso-propyl.

8. The compound according to claim 1, wherein A is selected from C.sub.1-C.sub.5alkyl, C.sub.2-C.sub.5alkenyl, C.sub.3-C.sub.6cycloalkyl, C.sub.4-C.sub.6cycloalkenyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.5haloalkenyl, C.sub.3-C.sub.6cycloalkoxy and phenyloxy, wherein the C.sub.3-C.sub.6cycloalkoxy and phenyloxy is optionally substituted with 1 or 2 substituents independently selected from R.sup.8, wherein R.sup.8 is halogen, nitro, cyano, methyl, ethyl, trifluoromethyl, 2,2,2-trifluoroethyl, methoxy, ethoxy, C.sub.3-C.sub.5alkenyloxy, C.sub.3-C.sub.5alkynyloxy and C.sub.1-C.sub.3alkylthio.

9. The compound according to a m claim 1, wherein A is selected from C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.5alkenyl, C.sub.3-C.sub.6cycloalkyl, C.sub.4-C.sub.6cycloalkenyl, C.sub.1-C.sub.4fluoroalkyl, C.sub.2-C.sub.5fluoroalkenyl, C.sub.2-C.sub.5chloroalkenyl, C.sub.3-C.sub.6cycloalkoxy and phenyloxy, wherein the C.sub.3-C.sub.6cycloalkoxy and phenyloxy is optionally substituted with 1 or 2 substituents independently selected from R.sup.8, wherein R.sup.8 is fluoro, chloro, bromo, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy and ethoxy.

10. The compound according to claim 1, wherein A is selected from one of: ##STR00064## ##STR00065## CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, C(CH.sub.3).sub.3, CF.sub.3 and CH.sub.2CF.sub.3.

11. The compound according to claim 1, wherein X is O.

12. An agrochemical composition comprising a fungicidally effective amount of a compound 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 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.

15. Use of a compound according to claim 1 as a fungicide.

Description

EXAMPLES

[0211] The Examples which follow serve to illustrate the invention.

[0212] 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, ? ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0213] 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).

[0214] 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 described below.

Formulation Examples

[0215]

TABLE-US-00003 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%

[0216] 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.

TABLE-US-00004 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

[0217] 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.

TABLE-US-00005 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%

[0218] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

TABLE-US-00006 Dusts a) b) c) Active ingredient [compound of formula (I)] 5% 6% 4% talcum 95% Kaolin 94% mineral filler 96%

[0219] 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.

TABLE-US-00007 Extruded granules Active ingredient [compound of formula (I)] 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%

[0220] 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.

TABLE-US-00008 Coated granules Active ingredient [compound of formula (I)] 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%

[0221] 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.

TABLE-US-00009 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%

[0222] 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.

TABLE-US-00010 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 0.5%.sup. in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup. Water 45.3%

[0223] 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.

Slow Release Capsule Suspension

[0224] 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.

[0225] 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.

[0226] The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Preparation Examples

List of Abbreviations

[0227] Aq=aqueous [0228] Ar=argon [0229] br s=broad singlet [0230] ? C.=degrees Celsius [0231] DCM=dichloromethane [0232] dd=doublet of doublet [0233] DMF=dimethylformamide [0234] d=doublet [0235] EtOAc=ethyl acetate [0236] equ.=equivalent [0237] h=hour(s) [0238] M=molar [0239] m=multiplet [0240] min=minutes [0241] MHz=megahertz [0242] mp=melting point [0243] ppm=parts per million [0244] RT=room temperature [0245] R.sub.t=retention time [0246] s=singlet [0247] t=triplet [0248] THE=tetrahydrofuran [0249] LC/MS=Liquid Chromatography Mass Spectrometry (description of the apparatus and the methods used for LC/MS analysis are given above)

Preparation Examples

Example A1: 4-[(4-fluorophenoxy)methyl]-2-(8-fluoro-3-quinolyl)-4,6,6-trimethyl-5H-1,3-oxazine (compound E.04)

Step 1:

[0250] To a solution of 4-fluorophenol (3.0 g, 26.5 mmol) in acetone (50 mL) at RT was added potassium carbonate (4.39 g, 31.8 mmol, 1.2 equ.), potassium iodide (0.44 g, 2.65 mmol, 0.1 equ.) and chloroacetone (2.66 mL, 31.8 mmol, 1.2 equ.). The mixture was warmed to 50? C. and was stirred at 50? C. for 2 h. The reaction mixture was then cooled to RT and partitioned between EtOAc and water. The organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: EtOAc) to give 1-(4-fluorophenoxy)propan-2-one as a colorless liquid.

[0251] LC-MS (Method G), Rt=0.79 min.

[0252] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 6.96-7.06 (m, 2H), 6.80-6.91 (m, 2H), 4.53 (s, 2H), 2.29 (s, 3H).

Step 2:

[0253] To a solution of 1-(4-fluorophenoxy)propan-2-one (4.30 g, 25.6 mmol) in THF (40 mL) was added titanium ethoxide (8.20 mL, 33.2 mmol, 1.3 equ.) and 2-methylpropane-2-sulfinamide (3.83 g, 30.7 mmol, 1.2 equ.). The resulting solution was warmed to 60? C. and stirred at 60? C. for 2 h. The reaction mixture was cooled to RT and quenched by addition of NaHCO.sub.3solution. The resulting suspension was filtered over a pad of celite and the filter cake was washed with EtOAc. The filtrate was extracted with EtOAc, the organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: EtOAc) to give N-[2-(4-fluorophenoxy)-1-methyl-ethylidene]-2-methyl-propane-2-sulfinamide as a colorless liquid.

[0254] LC-MS (Method G), R.sub.t=0.97 min, (M+H)=272.

[0255] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 6.94-7.05 (m, 2H), 6.81-6.91 (m, 2H), 4.47-4.67 (m, 2H), 2.42 (s, 3H), 1.20-1.23 (s, 9H).

Step 3:

[0256] To 2-methylallyl magnesium chloride (0.5 M in THF, 20 mL, 10.1 mmol, 1.5 equ.), cooled to ?50? C. under argon, was added dropwise a solution of N-[2-(4-fluorophenoxy)-1-methyl-ethylidene]-2-methyl-propane-2-sulfinamide (2.60 g, 6.71 mmol) in DCM (20 mL). The resulting solution was gradually warmed from ?50? C. to ?10? C. over 3 h. Additional 2-methylallyl magnesium chloride (0.5 M in THF, 20 mL, 10.1 mmol, 1.5 equ.) was added and the reaction was gradually warmed to RT over 2 h. The reaction mixture was then quenched by addition of NH.sub.4Cl solution and was extracted with EtOAc. The organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: EtOAc) to give N-[1-[(4-fluorophenoxy)methyl]-1,3-dimethyl-but-3-enyl]-2-methyl-propane-2-sulfinamide (mixture of diastereoisomers) as yellow liquid.

[0257] LC-MS (Method G), R.sub.t=1.14 min, (M+H)=328.

Step 4:

[0258] To a solution of N-[1-[(4-fluorophenoxy)methyl]-1,3-dimethyl-but-3-enyl]-2-methyl-propane-2-sulfinamide (1.08 g, 3.3 mmol) in methanol (5 mL), cooled to 5? C., was added HCl (4M in dioxane) (1.6 mL, 6.6 mmol, 2 equ.) and the solution was stirred for 2 h at 0? C. The reaction mixture was then concentrated under reduce pressure to give a mixture of 1-(4-fluorophenoxy)-2,4-dimethyl-pent-4-en-2-amine hydrochloride and methyl 2-methylpropane-2-sulfinate was used without further purification for the next step.

[0259] LC-MS (Method G), R.sub.t=0.69 min, (M+H)=224.

Step 5:

[0260] To a solution of 8-fluoroquinoline-3-carboxylic acid (0.650 g, 3.4 mmol) and 1-(4-fluorophenoxy)-2,4-dimethyl-pent-4-en-2-amine hydrochloride (0.88 g, 3.4 mmol, 1 equ.) in acetonitrile (14 mL) at RT was added triethylamine (1.43 mL, 10.2 mmol, 3 equ.) and propanephosphonic acid anhydride (50% in EtOAc, 3.24 mL, 5.44 mmol, 1.6 equ.). The resulting solution was stirred for 2 h at RT, diluted with EtOAc and quenched with water. The mixture was extracted with EtOAc, the organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel: cyclohexane: EtOAc) to give 8-fluoro-N-[1-[(4-fluorophenoxy)methyl]-1,3-dimethyl-but-3-enyl]quinoline-3-carboxamide as yellow gum.

[0261] LC-MS (Method G), R.sub.t=1.15 min, (M+H)=397.

[0262] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 9.26 (d, 1H), 8.58 (s, 1H), 7.73 (d, 1H), 7.44-7.63 (m, 2H), 6.86-7.06 (m, 4H), 6.53 (s, 1H), 5.03-5.07 (m, 1H), 4.88-4.93 (m, 1H), 4.31 (d, 1H), 4.17 (d, 1H), 2.92 (d, 1H), 2.64 (d, 1H), 1.89 (s, 3H), 1.69 (s, 3H). .sup.19F NMR (CDCl.sub.3) ? ppm: ?123.23 (s, 1F), ?124.61 (s, 1F).

Step 6:

[0263] To a solution of 8-fluoro-N-[1-[(4-fluorophenoxy)methyl]-1,3-dimethyl-but-3-enyl]quinoline-3-carboxamide (0.670 g, 1.69 mmol) in acetonitrile (8 mL) was added trifluoroacetic acid (1.30 mL, 16.9 mmol, 10 equ.) at RT, the resulting solution was warmed to 80? C. and stirred at 80? C. for 20 h. The reaction mixture was then cooled to RT, diluted with EtOAc and carefully quenched with aq. NaHCO.sub.3solution. The neutralized mixture (pH>8) was extracted with EtOAc, the organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: EtOAc) to give 4-[(4-fluorophenoxy)methyl]-2-(8-fluoro-3-quinolyl)-4,6,6-trimethyl-5H-1,3-oxazine as yellow gum.

[0264] LC-MS (Method G), R.sub.t=1.18 min, (M+H)=397.

[0265] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 9.51 (d, 1H), 8.68 (br s, 1H), 7.70 (d, 1H), 7.43-7.55 (m, 2H), 6.95-7.02 (m, 2H), 6.85-6.95 (m, 2H), 3.95 (d, 1H), 3.82 (d, 1H), 2.23 (d, 1H), 1.97 (d, 1H), 1.53-1.57 (d, 6H), 1.51-1.53 (s, 3H). .sup.19F NMR (CDCl.sub.3) ? : ?123.84 (s, 1F), ?125.19 (s, 1F).

Example A2: 2-(8-fluoro-3-quinolyl)-4,6,6-trimethyl-4-(2-methylallyl)-5H-1,3-oxazine (compound E.019)

Step 1:

[0266] To a solution of acetonitrile (0.51 mL, 9.74 mmol) in diethyl ether (30 mL) at RT was added dropwise 2-methylallyl magnesium chloride (0.5 M in THF, 58 mL, 29.2 mmol, 3 equ.). The resulting solution was stirred at RT for 30 min, titanium isopropoxide (3.0 mL, 9.74 mmol, 1 equ.) was added dropwise and the solution was stirred for additional 5 h at RT. The reaction mixture was then slowly poured into a mixture of DCM (200 mL) NaOH (1 M, 50 mL) and NaHCO.sub.3 solution (50 mL). The resulting mixture was vigorously stirred for 20 min, filtered through celite and the phases were separated. The organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated in vacuo to give 2,4,6-trimethylhepta-1,6-dien-4-amine as a yellow liquid, which was used as such for the next step.

[0267] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 4.70-5.06 (m, 4H), 2.11-2.20 (m, 4H), 1.79-1.91 (m, 6H), 1.01-1.17 (s, 3H).

Step 2:

[0268] To a mixture of 8-fluoroquinoline-3-carboxylic acid (0.192 g, 1 mmol) and 2,4,6-trimethylhepta-1,6-dien-4-amine (0.20 g, 0.91 mmol) in DCM (7 mL) at RT was added triethylamine (0.32 mL, 2.28 mmol, 2.5 equ.), N-(3-Dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (0.197 g, 1 mmol, 1.1 equ.) and 1-[bis(dimethylamino)methylene]-1 H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (0.394 g, 1 mmol, 1.1 equ.). The resulting solution was stirred for 1 h at RT and was then quenched with NaHCO.sub.3 solution. The mixture was extracted with DCM, the organic phase was washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to give N-[1,3-dimethyl-1-(2-methylallyl)but-3-enyl]-8-fluoro-quinoline-3-carboxamide as a white solid.

[0269] LC-MS (Method G), R.sub.t=1.11 min, (M+H)=328.

[0270] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 9.25 (d, 1H), 8.60 (s, 1H), 7.75 (d, 1H), 7.48-7.66 (m, 2H), 6.32 (br s, 1H), 4.76-5.08 (d, 4H), 2.91 (d, 2H), 2.53 (d, 2H), 1.88 (s, 6H), 1.51-1.66 (s, 3H).

Step 3:

[0271] A solution of N-[1,3-dimethyl-1-(2-methylallyl)but-3-enyl]-8-fluoro-quinoline-3-carboxamide (0.03 g, 0.09 mmol) in acetonitrile (0.5 mL) at RT was treated with trifluoroacetic acid (0.1 mL), the mixture was warmed to 80? C. and was stirred for 20 h at 80? C. The reaction mixture was cooled to RT and carefully poured on aq. NaHCO.sub.3solution. The neutralized mixture (pH>8) was extracted with EtOAc, the combined organic layers were washed with brine, dried over MgSO.sub.4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: EtOAc) to give 2-(8-fluoro-3-quinolyl)-4,6,6-trimethyl-4-(2-methylallyl)-5H-1,3-oxazine as yellow oil.

[0272] LC-MS (Method G), R.sub.t=1.03 min, (M+H)=327.

[0273] .sup.1H NMR (400 MHz, CDCl.sub.3) ? ppm: 9.56 (d, 1H), 8.69 (br s, 1H), 7.71 (br d, 1H), 7.41-7.55 (m, 2H), 4.72-5.00 (m, 2H), 2.28-2.46 (m, 2H), 1.98-2.06 (m, 1H), 1.87-1.91 (m, 3H), 1.78-1.86 (m, 1H), 1.50 (s, 6H), 1.43 (s, 3H).

Analytical Methods

Method G:

[0274] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150? C., Desolvation Temperature: 350? C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650 I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 ?m, 30?2.1 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.

TABLE-US-00011 TABLE E Melting point (mp) and/or LC/MS data (retention time (R.sub.t)) for compounds of Formula (I): R.sub.t [M + H] Meth- mp Entry IUPAC name STRUCTURE (min) (measured) od (? C.) E.01 4-[[2-(8-fluoro-3-quinolyl)- 4,6,6-trimethyl-5H-1,3- oxazin-4- yl]methoxy]benzonitrile [00043] 1.12 404 G E.02 4-[(2,4- dibromophenoxy)methyl]- 2-(8-fluoro-3-quinolyl)- 4,6,6-trimethyl-5H-1,3- oxazine [00044] 1.34 535 G E.03 4-[(4- bromophenoxy)methyl]-2- (8-fluoro-3-quinolyl)-4,6,6- trimethyl-5H-1,3-oxazine [00045] 1.26 457 G E.04 4-[(4- fluorophenoxy)methyl]-2- (8-fluoro-3-quinolyl)-4,6,6- trimethyl-5H-1,3-oxazine [00046] 1.18 397 G E.05 2-(7,8-difluoro-2-methyl- 3-quinolyl)-4,6,6- trimethyl-4- (phenoxymethyl)-5H-1,3- oxazine [00047] 1.17 412 G E.06 2-(7,8-difluoro-3-quinolyl)- 4,6,6-trimethyl-4- (phenoxymethyl)-5H-1,3- oxazine [00048] 1.22 397 G 105- 107 E.07 2-(7,8-difluoro-3-quinolyl)- 6,6-dimethyl-4- (phenoxymethyl)-4,5- dihydro-1,3-oxazine [00049] 1.17 383 G E.08 2-(8-fluoro-3-quinolyl)- 4,6,6-trimethyl-4- (phenoxymethyl)-5H-1,3- oxazine [00050] 1.17 379 G E.09 2-(7,8-difluoro-3-quinolyl)- 6,6-dimethyl-4-(2,2,2- trifluoroethyl)-4,5-dihydro- 1,3-oxazine [00051] 1.15 359 146- 148 E.010 2-(7,8-difluoro-3-quinolyl)- 6,6-dimethyl-4-(3,3,3- trifluoropropyl)-4,5- dihydro-1,3-oxazine [00052] 1.16 373 G E.011 2-(7,8-difluoro-3-quinolyl)- 4-(2,2-dimethylpropyl)- 6,6-dimethyl-4,5-dihydro- 1,3-oxazine [00053] 1.21 347 G 112- 113 E.012 2-(7,8-difluoro-3-quinolyl)- 4-isobutyl-6,6-dimethyl- 4,5-dihydro-1,3-oxazine [00054] 1.09 353 G 71- 72 E.013 2-(8-fluoro-3-quinolyl)-4- isobutyl-4,6,6-trimethyl- 5H-1,3-oxazine [00055] 1.06 329 G E.014 2-(7,8-difluoro-3-quinolyl)- 4-isobutyl-4,6,6-trimethyl- 5H-1,3-oxazine [00056] 1.11 347 G E.015 4-(cyclohexylmethyl)-2- (7,8-difluoro-3-quinolyl)- 4,6,6-trimethyl-5H-1,3- oxazine [00057] 1.28 387 G E.016 2-(7,8-difluoro-3-quinolyl)- 4,6,6-trimethyl-4-(2- methylallyl)-5H-1,3- oxazine [00058] 1.15 346 G E.017 2-(8-fluoro-3-quinolyl)-4- isobutyl-6-isopropyl-4,6- dimethyl-5H-1,3-oxazine [00059] 1.17 358 G E.018 6-ethyl-2-(8-fluoro-3- quinolyl)-4-isobutyl-4,6- dimethyl-5H-1,3-oxazine [00060] 1.12 344 G E.019 2-(8-fluoro-3-quinolyl)- 4,6,6-trimethyl-4-(2- methylallyl)-5H-1,3- oxazine [00061] 1.05 327 G E.020 4-ethyl-2-(8-fluoro-3- quinolyl)-6,6-dimethyl-4- (2-methylallyl)-5H-1,3- oxazine [00062] 1.19 342 G

Biological Examples/Test Methods

Botryotinia Fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

[0275] 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.

[0276] The following compounds (from Table E) 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:

[0277] E.01, E.02, E.03, E.04, E.05, E.06, E.07, E.08, E.010, E.011, E.012, E.013, E.014, E.015, E.016, E.017, E.018, E.019, E.020.

Glomerella lagenarium (Colletotrichum laqenarium)/liquid culture (Anthracnose)

[0278] 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.

[0279] The following compounds (from Table E) 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:

[0280] E.03, E.04, E.08, E.012, E.013, E.014, E.015, E.016, E.017, E.018, E.019, E.020.

Fusarium culmorum/Liquid Culture (Head Blight) 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 3-4 days after application.

[0281] The following compounds (from Table E) gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

[0282] E.04, E.06, E.07, E.08, E.014, E.015, E.018.

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

[0283] 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.

[0284] The following compounds (from Table E) 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:

[0285] E.01, E.02, E.03, E.04, E.05, E.06, E.07, E.08, E.09, E.010, E.011, E.012, E.013, E.014, E.015, E.016, E.017, E.018, E.019, E.020.

Septoria tritici Leaf Spot on Wheat/Preventative

[0286] 2-week old wheat plants cv. Riband are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying a spore suspension on them one day after application and then kept at 22? C./21? C. (day/night) in a greenhouse. Disease damage is assessed directly when an appropriate level of disease appears on untreated check plants and efficacy was calculated compare to untreated controls (16 to 19 days after application).

[0287] The following compounds (from Table E) gave at least 80% control of Septoria tritici at 60 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

[0288] E.025.