WO1992011762A1

WO1992011762A1 - Fungicidal hydroxypyranones

Info

Publication number: WO1992011762A1
Application number: PCT/US1992/000010
Authority: WO
Inventors: Thomas Paul Selby; Mark Ewell Thompson
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1991-01-08
Filing date: 1992-01-02
Publication date: 1992-07-23
Also published as: AU1193292A

Abstract

Fungicidal hydroxypyranones of formula (I), agricultural compositions containing them, and a method for controlling fungus disease in plants.

Description

FUNGICIDAL HYDROXYPYRANONES

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of

U.S.S.N. 07/638,530, filed January 8, 1991.

BACKGROUND OF THE INVENTION

Structures of Formula I are known in the open literature and have been patented for medicinal purposes, For example, Laliberte (U.S. 3,707,482) discloses as pharmaceutical antibacterials, fungicides, and

coccidiostats compounds of Formula i

wherein:

R is Ph, 4-PhC₆H₄, 3,4-Me₂C₆H₃, PhCH₂OC₆H₄, Ph₂CH,

4'-chloro-4-biphenyl, and R¹ is H, ClCH₂, 3,4-Me₂C₆H₃, PhCH₂, PhCH(OH), Me, Et, Pr or RR¹ is (CH₂)₅.

Laliberte et al. (J. Afed. Chem. 1973, 16, 1084-1089) disclose as anticoccidial and antimicrobial agents compounds of Formulae ii and iii

wherein:

R is H, phenyl, alkylphenyl, biphenyl, substituted biphenyl; R¹ is H, methyl, phenyl, haloalkyl, R² is methyl, ethyl; and R³ is H, alkyl, (alkyl)CO, (alkyl)NHCO.

Further synthetic methods for the above compounds were reported by Georgiadis et al. (Chimika Chronika 1983, 12, 45-59).

Georgiadis et al. (J. Org. Chem. 1986, 51, 2725-2727) disclose compounds of Formula iv

wherein:

R¹ is H or methyl and R² is H, 4-PhSC₆H₄, 4-PhSOC₆H₄ or 4-PhSO₂C₆H₄.

JP 57,188,585 discloses as pharmaceutical fungicides compounds of Formula v

wherein:

R is H, alkyl, cycloalkyl, Ph; R¹ is H, halogen; and n is 1-3.

Takao et al. (U.S. 4,742,078, U.S. 4,840,957) disclose as agricultural miticides compounds of

Formula vi

wherein:

R¹ is hydrogen, lower alkyl, cycloalkyl or phenyl; R² is C₈-C₂₀ alkyl; R³ is hydrogen, halogen,

-CH₂NR⁴R⁵ or

R⁴ and R⁵ being lower alkyl or cycloalkyl, A being -CH₂-, oxygen or nitrogen, and forms five- or six-membered rings (these

rings may have no substituent or have at least one substituent selected from lower alkyl, lower alkoxy, andhalogen atom).

SUMMΑRY OF THE INVENTION

This invention pertains to a method of controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I,

wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸; pyridyl, thienyl, pyrazolyl, naphthalenyl, anthracenyl, phenanthrenyl or fluorenyl each optionally substituted with R⁷; or C₁ substituted with R⁹ and R¹⁰;

R² is H; trifluoromethyl; C₁-C₄ alkyl; phenyl

optionally substituted with R⁷ and R⁸; or pyridyl, thienyl or pyrazolyl each optionally substituted with R⁷; or

R¹ and R² can be taken together with the carbon to which they are attached to form structures such as

R³ is H or C₁-C₄ alkyl;

R⁴ is H, C₁-C₄ alkyl, allyl, propargyl, -C(=O)R¹⁴,

-C(=O)NR¹⁵R¹⁶, -C(=S)R¹⁴, -C(=S)NR¹⁵R¹⁶ or -SO₂R¹⁷; R⁵ is H or C₁-C₄ alkyl;

R⁶ is H, Cl, Br or C₁-C₄ alkyl;

R⁷ is 1-2 halogen, 1-2 methyl, methoxy, nitro, cyano or trifluoromethyl;

R⁸ is 1-2 halogen; C₁-C₆ alkyl; C₃-C₆ cycloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₁-C₄ haloalkyl; cyano; nitro; C₂-C₃ alkoxycarbonyl; C₂-C₃

alkylcarbonyl; -C(=O)NR¹⁸R¹⁹; -S(O)_mR²⁰; or phenyl, phenoxy, pyridyl, thienyl or pyrazolyl each optionally substituted with R⁷;

R⁹ is H; or phenyl optionally substituted with R⁷; R¹⁰ is phenyl optionally substituted with R⁷;

R¹¹, R¹² and R¹³ are independently H, C₁-C₄ alkyl,

phenyl or 4-chlorophenyl;

R¹⁴ is C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₂-C₄ alkoxyalkyl;

R¹⁵ and R¹⁶ are independently H or C₁-C₈ alkyl; or R¹⁵ and R¹⁶ can be taken together with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group;

R¹⁷ is C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄

alkoxyalkyl;

R¹⁸ and R¹⁹ are independently C₁-C₃ alkyl; or R¹⁸ and R¹⁹ can be taken together with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group;

R²⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄

alkoxyalkyl; or phenyl optionally substituted with R⁷;

J is (CH₂)_p, O, S(O)_p or CH₃N;

m is 0, 1 or 2; and

p is 0, 1 or 2.

provided that

1) when R¹ is C₁ substituted with R⁹ and R¹⁰, R² is H or C₁-C₄ alkyl;

2) the total number of carbon atoms in R¹ and R²

together is less than 24; and

3) the total number of carbon atoms in R¹⁵ and R¹⁶ together is no greater than 8. In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" denotes straight chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl or n-hexyl.

"Alkylthio" denotes methylthio, ethylthio, and the different propylthio and butylthio isomers.

"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers.

"Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include CF₃, CH₂Cl, CH₂CF₃ and CF₂CF₃. Examples of "haloalkoxy" include CF₃O, Cl₃CCH₂O, CF₂HCH₂CH₂O and CF₃CH₂O.

The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 8. For example, C₂ "alkoxyalkyl" denotes CH₃OCH₂ and C₃ "alkoxyalkyl" denotes CH₃OCH₂CH₂ and CH₃CH₂OCH₂. C₂ "alkylcarbonyl" designates C(O)CH₃ and C₃ "alkylcarbonyl" designates C(O)CH₂CH₃. Examples of "alkoxycarbonyl" include CO₂CH₃ and CO₂CH₂CH₃.

Preferred for greatest fungicidal activity and/or ease of synthesis are:

1) A method of controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸; R² is H; C₁-C₄ alkyl; or phenyl optionally substituted with R⁷ and R⁸;

R³ is H or methyl;

R⁵ is H or methyl; and

R⁶ is H or methyl.

2) A method according to Preferred 1 wherein:

R² is H; C₁-C₂ alkyl; or phenyl optionally substituted with R⁷ and R⁸;

R⁴ is H, -C(=O)R¹⁴ or -C(=O)NR¹⁵R¹⁶; and

R⁸ is C₁-C₂ alkoxy; C₁-C₂ haloalkoxy; C₁-C₂ haloalkyl; cyano; nitro; C₁-C₂ alkylthio; or phenyl or phenoxy each optionally substituted with R⁷.

3) A method according to Preferred 2 wherein:

R¹⁵ and R¹⁶ are independently H or C₁-C₄

alkyl.

4) A method according to Preferred 3 wherein:

R² is methyl; or phenyl optionally substituted with R⁷ and R⁸;

R³ is H;

R⁵ is H;

R⁶ is H;

R⁸ is phenyl or phenoxy each optionally

substituted with R⁷;

R¹⁴ is C₁-C₄ alkyl;

R¹⁵ is H; and

R¹⁶ is H or C₁-C₄ alkyl.

Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:

1) 6-acetyloxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one;

2) 2-[1,1'-biphenyl]-4-yl-6-hydroxy-2-phenyl- 2H-pyran-3(6H)-one; and 3) 6-acetyloxy-2, 2-bis(4-chlorophenyl)-2H-pyran- 3(6H)-one.

This invention further pertains to compounds of Formula I including all geometric and stereoisomers and agricultural compositions containing them.

wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸; or pyridyl, thienyl, pyrazolyl, naphthalenyl, anthracenyl, phenanthrenyl or fluorenyl each optionally substituted with R⁷;

R² is phenyl optionally substituted with R⁷ and R⁸; or pyridyl, thienyl or pyrazolyl each optionally substituted with R⁷; or

R³ is H or C₁-C₄ alkyl;

R⁴ is H, C₁-C₄ alkyl, allyl, propargyl, -C(=O)R¹⁴,

-C(=O)NR¹⁵R¹⁶, -C(=S)R¹⁴, -C(=S)NR¹⁵R¹⁶ or -SO₂R¹⁷; R⁵ is H or C₁-C₄ alkyl; R⁶ is H, Cl, Br or C₁-C₄ alkyl;

R⁷ is 1-2 halogen, 1-2 methyl, methoxy, nitro, cyano or trifluoromethyl;

R⁸ is 1-2 halogen; C₁-C₆ alkyl; C₃-C₆ cycloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₁-C₄ haloalkyl; cyano; nitro; C₂-C₃ alkoxycarbonyl; C₂-C₃ alkylcarbonyl; -C(=O)NR¹⁸R¹⁹; -S(O)_mR²⁰; or phenyl, phenoxy, pyridyl, thienyl or pyrazolyl each optionally substituted with R⁷;

R¹¹, R¹² and R¹³ are independently H, C₁-C₄ alkyl,

phenyl or 4-chlorophenyl;

R¹⁴ is C₁-C₆ alkyl, C₂-C₄ haloalkyl, C₁-C₄ alkoxy or C₂-C₄ alkoxyalkyl;

R¹⁷ is C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄

alkoxyalkyl;

R²⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄

alkoxyalkyl; or phenyl optionally substituted with R⁷;

J is (CH₂)_p, O, S(O)_p or CH₃N;

m is 0, 1 or 2; and

p is 0, 1 or 2.

provided that

1) the total number of carbon atoms in R¹ and R²

together is less than 24; 2) the total number of carbon atoms in R¹⁵ and R¹⁶ together is no greater than 8; and

3) when R² is phenyl, R¹ cannot be 4-phenyl phenyl or 3,4-dimethyl phenyl.

Preferred for greatest fungicidal activity and/or ease of synthesis are:

1) Compounds of Formula I wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸;

R² is phenyl optionally substituted with R⁷ and R⁸;

R³ is H or methyl;

R⁵ is H or methyl; and

R⁶ is H or methyl.

2) Compounds of Preferred 1 wherein:

R⁴ is H, -C(=O)R¹⁴ or -C(=O)NR¹⁵R¹⁶; and R⁸ is C₁-C₂ alkoxy; C₁-C₂ haloalkoxy; C₁-C₂ haloalkyl; cyano; nitro; C₁-C₂ alkylthio; or phenyl or phenoxy each optionally substituted with R⁷.

3) Compounds of Preferred 2 wherein:

R¹⁵ and R¹⁶ are independently H or C₁-C₄

alkyl.

4) Compounds of Preferred 3 wherein:

R³ is H;

R⁵ is H;

R⁶ is H;

R⁸ is phenyl or phenoxy each optionally

substituted with R⁷;

R¹⁴ is C₁-C₄ alkyl;

R¹⁵ is H; and

R¹⁶ is H or C₁-C₄ alkyl. Specifically preferred for greatest fungicidal activity and/or ease of synthesis is:

6-acetyloxy-2,2-bis(4-chlorophenyl)-2H- pyran-3(6H)-one.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

This invention is concerned with compounds of

Formula I

Compounds of Formula I in which R⁴ is H can be prepared by the procedures shown in Equation 1 as

described by Lefebvre et al. in J. Med. Chem. , 1973, 16, 1084. Alternative methods of oxidation for the

preparation of compounds of Formula III such as the use of pyridinium chlorochromate (Piancatelli, G. et al..

Tetrahedron Lett. 1977, 25, 2199), bromine in methanol (Achmatowicz et al., Tetrahedron 1971, 21, 1973), anodic oxidation (Shono, T. et al., Tetrahedron Lett. 1976, 17, 1363) oxidation with metal catalysts (Titanium: Sato, F. et al., J. Org. Chem. 1989, 54, 2085; Vanadium: Ho, T.-L. et al., Synth. Comm. 1983, 13, 207) and N-bromo-succinimide (Georgiadis, M. P. et al., J. Org. Chem.

1986, 51, 2725) can be used. EQUATION 1

Derivatives of III to give compounds of Formula I can be prepared by the procedures of Lefebvre in J.Med. Chem. 1973, 16, 1084 and Georgiadis, M.P. etal., J. Org. Chem. 1982, 47, 3054).

The furfuryl alcohols of Formula II are conveniently prepared from the appropriate ketones or esters and organometallic reagents as described by Holder (Chem. Rev. 1982, 82, 293).

EQUATION 2

Syntheses of the appropriately substituted furans have been reviewed by Donnelly, D. M. X. In

Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds.; Vol. 4; Pergamon Press: NewYork, 1984; pp 657-712; Livingston, R. In Rodd 's Chemistry of Carbon Compounds; Coffey, S., Ed.; 2nd Ed. Elsevier: Amsterdam, 1973, Vol. IVa, pp 83-120; 1984 IVa supplement pp.

119-213. Preparation of aromatic aldehydes and ketones used in Equation 2 are well known to one skilled in the art. Numerous methods and examples are presented in

collections of synthetic methods such as: Buehler, C. A. and Pearson, D. E., Survey of Organic Syntheses; Wiley: New York, 1970 (Vol. 1, pp 513-623, 1977: Vol. 2, pp 486-635); Laird, T. In Comprehensive Organic Chemistry; Barton, D. and Ollis, W. D., Eds.; Pergamon: New York, 1979, Vol. 1, pp 1105-1212; March, J. Advanced Organic Chemistry; Wiley: New York, 1985; Tatchell, A. R.

Vogel 's Textbook of Practical Organic Chemistry, 5th Ed.; Longman: New York, 1989.

Compounds of Formula I can be prepared by the procedures illustrated in the following Examples.

EXAMPLE 1

6-acetyloxy-2, 2-bis(4-chlorophenyl)- 2H-pyran-3(6H)-one

To a solution of 2,2-bis (4-chlorophenyl)-6-hydroxy-2H-pyran-3(6H)-one (1.0 g, 3 mmol) in benzene (50 mL) was added acetic anhydride (4.0 mL, 42.4 mmol) and sodium acetate (1.0 g, 12.2 mmol). The mixture was heated at 50°C for 5 h under an inert atmosphere.

On cooling, the product was isolated by extraction of the organic phase with, in succession, water, sodium bicarbonate solution, and water. The organic residue was purified by silica gel chromatography to yield 0.9 g (oil) of the title compound.

IR: 1740-1760, 1690 cm^-1.

NMR (CDCI₃) 6: 2.0 ppm, s, 3H; 6.4 ppm, d, 1H; 6.55 ppm, d, 1H; 6.9 ppm, dxd, 1H; 7.1-7.4 ppm, m, 8H. EXAMPLE 2

2,2-bis(4-chlorophenyl)-6- [[(methylamino)carbonyl]oxyl-2H-pyran-3(6H)-one

To a solution of 2,2-bis(4-chlorophenyl)-6-hydroxy- 2H-pyran-3(6H)-one (1.0 g, 3.0 mmol) in benzene (50 mL) was added methyl isocyanate (1.0 mL, 17 mmol) and

dibutyltin oxide (<0.1 g, catalyst). The mixture was stirred at 25°C overnight under an inert atmosphere. The organic phase was extracted with water, concentrated and purified by silica gel chromatography to give 0.92 g

(oil) of pure 2,2-bis(4-chlorophenyl)-6-[[(methylamino)- carbonyl]oxy]-2H-pyran-3(6H)-one.

IR: 3350, 1730, 1690 cm^-1.

NMR (CDCI₃) δ: 2.8 ppm, d, 3H; 4.45 ppm, broad s, 1H) ; 6.3 ppm, d, 1H; 6.49 ppm, s, 1H; 6.85 ppm, dxd, 1H, 7.1- 7.4 ppm, m, 8H.

EXAMPLE 3

2,2-bis(4-chlorophenyl)-6-methoxy-2H-pyran-3(-6H)-one

To a solution of 2,2-bis(4-chlorophenyl)-6-hydroxy-2H-pyran-3(6H)-one (1.0 g, 3 mmol) in acetone (50 mL) was added methyl iodide (6.8 g, 49 mmol) and silver (I) oxide (0.9 g, 3.9 mmol). The mixture was stirred for 55 h under an inert atmosphere at 25°C. Filtration to remove the silver salts, concentration of the organic solution and purification of the residue by silica gel

chromatography gave 1.04 g (oil) of pure 2,2-bis(4-chlorophenyl)-6-methσxy-2H-pyran-3(6H)-one.

IR: 1690 cm^-1.

NMR (CDCI₃) δ: 3.5 ppm, s, 3H; 5.2 ppm, s, 1H; 6.3 ppm, d, 1H; 6.9 ppm, d, 1H; 7.2-7.5 ppm, m, 8H. EXAMPLE 4

2,2-bis(4-chlorophenyl)-6- [(aminocarbonyHoxy1-2H-pyran-3(6H)-one To a solution of 2,2-bis(4-chlorophenyl)-6-hydroxy-2H-pyran-3(6H)-one (1.5 g, 4.5 mmol) in benzene (50 mL) was adeed trimethylsilyl isocyanate (0.6 g, 5.2 mmol) and dibutyltin oxide (<0.1g, catalyst). The mixture was stirred at 50°C for 18 h under an inert atmosphere.

Aqueous work-up followed by purification of the organic residue by silica gel chromatography gave pure 2,2-bis(4-chlorophenyl)-6-[(aminocarbonyl)oxy]-2H-pyran-3(6H)-one (0.4 g, mp 155-156°C).

IR: 3420 cm^-1, 3350 cm-1 shoulder.

NMR (CDCI3) δ: 4.6 ppm, s, 2H; 6.4 ppm, d, 1H; 6.5 ppm, d, 1H; 6.9 ppm, dxd, 1H; 7.2-7.4 ppm, m, 8H.

EXAMPLE 5

2-phenyl-2-(4'-biphenyl)-6-hydroxy-2H-pyran-3(6H)-one To a solution of α-phenyl-α-(4-biphenyl)furfuryl alcohol (16.3 g, 50 mmol) in dichloromethane (150 mL) was added m-chloroperbenzoic acid (12.1 g, 70 mmol, active ingredient) at 0°C. The mixture was allowed to warm to 25°C while stirring for 5 h.

The mixture was filtered to remove m-chlorobenzoic acid. The filtrate was treated with an aqueous solution containing potassium iodide, sodium bicarbonate, and sodium thiosulfate. Purification of the organic residue by silica gel chromatography (2:1 hexane-ethyl acetate eluent) gave pure 2-phenyl-2-(4-biphenyl)-6-hydroxy-2H-pyran-3(6H)-one after slurrying in n-butyl chloride

(10.9 g, mp 146-148°C).

IR: 3440, 1685 cm^-1.

NMR (CDCI₃) δ: 5.5, d, 1H; 6.3, d, 1H; 6.9, d, 1H; 7.2-7.6, m, 14H. EXAMPLE 6

a-phenyl-a-(4-biphenyl)-furfuryl alcohol To a solution of furan (4.68 g, 69 mmol) in THF (100 mL) at 0°C was added n-butyllithium (25 mL, 2.5 M, 62.5 mmol). The solution was warmed to 25°C and held for 1 h. The solution was then cooled to 0ºC and 4-benzoylbiphenyl (14.5 g, 56 mmol) was added in portions. After 3 h, water was added and the product extracted with ether.

The residue from evaporation of the ether was α-phenyl- α- (4-biphenyl) furfuryl alcohol (19.07 g, mp 114-115°C). IR: 3560 cm^-1.

NMR (CDCI3) δ: 3.22 ppm, s, 1H; 5.95 ppm, d, 1H; 6.35 ppm, d, 1H; 7.2-7.6 ppm, m, 15H.

(Contained 6.6% by weight of THF solvent as determined by NMR).

Examples of compounds of the invention are shown in Tables I-IV. One skilled in the art will recognize that compounds of this invention can exist as geometric and stereoisomers.

For each value of R⁴ in Table I (i.e., H, C (=O)CH₃, or C(=O)NHCH₃) R¹, R², R³, R⁵ and R⁶ may have the values recited therein. All of said compounds are specifically included within the scope of this invention.

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further

formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient (s) and at least one of (a) about 0.1% to 20% surfactant (s) and (b) about 1% to 99.9% solid or liquid inert diluent (s). More specifically, they will contain these ingredients in the following approximate proportions:

Weight Percent*

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10

Oil Suspensions, 3-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Aqueous Suspension 10-50 40-84 1-20

Dusts 1-25 70-99 0-5

Granules and Pellets 0.1-95 5-99.9 0-15

High Strength 90-99 0-10 0-2

Compositions

*Active ingredients plus at least one of a surfactant or a diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins et al., "Handbook of Insecticide Dust Diluents and

Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension

concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's

Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood,

"Encyclopedia of Surface Active Agents", Chemical

Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking,

corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by

blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example. Littler, U.S. Patent 3,060,084).

Granules and pellets may be made by spraying the active material upon preformed granular carriers or by

agglomeration techniques.. See J.E.Browning,

"Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-59ff. For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15,

1966, Col. 6, line 16 through Col. 7, line 19 and

Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14,

1967, Col. 5, line 43 through Col. 7, line 62 and

Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855,

June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John

Wiley & Sons, Inc., Ne York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control

Handbook", 5th Ed., Blackwell Scientific Publications,

Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example A

Wettable Powder

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 50%

sodium alkylnaphthalenesulfonate 2%

sodium liginsulfonate 5%

diatomaceous earth 43%

The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example B

Granule

oily active ingredient 5% attapulgite granules 95%

(U.S.S. 20-40 mesh; 0.84-0.42 mm)

An oily active ingredient is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. Example C

Oil Suspension

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 25%

polyoxyethylene sorbitol hexaoleate 5%

highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspensions may be applied directly, but preferably after being extended with oils or emulsified in water.

Example D

Wettable Powder

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 20%

sodium alkylnaphthalenesulfonate 4%

sodium liginsulfonate 4%

low viscosity methyl cellulose 3%

attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles

essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged. Example E

Low Strength Granule

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 1%

methylene chloride 9%

attapulgite granule 90%

(U.S.S. 20-40 sieve)

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. Example F

Aqueous Suspension

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 10%

polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol 5.0%

ether

disodium phosphate 1%

monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 82.2%

The ingredients are blended and milled together in a homogenizer to produce particles essentially all under 5 microns in size.

Example G

Low Strength Granule

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 0.1%

attapulgite granules 99.9%

(U.S.S. 20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example H

Emulsion Concentrate.

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 35%

blend of polyalcohol carboxylic 6%

esters and oil soluble petroleum

sulfonates

xylene 59%

The ingredients are combined and stirred together to produce a solution. The product can be extended with oils, or emulsified in water.

Example T

Emulsifiable Concentrate

6-acetoxy-2-[1,1'-biphenyl]-4-yl-2-methyl- 2H-pyran-3(6H)-one 20%

chlorobenzene 74%

sorbitan monostearate and polyoxy6%

ethylene condensates thereof The ingredients are combined and stirred to produce a solution which can be emulsified in water for

application. UTILITY

The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These

pathogens include, Venturia inaequalis, Cercosporidium personatum, Cercospora arachidicola, Cercospora beticola, Pseudocercosporella herpotrichoides, Uncinula necatur, Podosphaera l eucotricha , Puccinia recondita, Puccinia gramminis, Hemileia vastatrix, Puccinia striiformis,

Puccinia arachidis, Phytophthora infestans, Plasmopara viticola, Peronospora tabacina, Pseudoperonospora

cubensis, Pythium aphanidermatum, Botrytis cinerea,

Monilinia frueticola, Alternaria brassicae, Septoria nodorum, and other species closely related to these pathogens. Compounds of this invention are somewhat less efficacious against Erysiphe graminis and Pyricularia oryzae. They also control seed pathogens.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material. Suitable agents of this type are well-known to those skilled in the art. Some are listed below: Fungicides

methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1, 4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate

(benomyl)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide

(cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan) N-trichloromethylthiophthalimide (folpet)

dimethyl 4,4'-(o-phenylene) bis (3-thioallophanate) (thiophanate-methyl)

2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethylphosphonate) (phosethyl aluminum) tetrachloroisophthalonitrile (chlorothalonil)

2, 6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine

methyl ester (metalaxyl)

cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene- 1,2-dicarbioximide (captafol)

3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1- imidazolidine carboxamide (iprodione)

3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin)

kasugamycin

O-ethyl-S,S-diphenylphosphorodithioate (edifenphos) 4-(3-(4-(1,1-dimethylethyl)phenyl)-2-methyl)propyl- 2,6-dimethylmorpholine (fenpropimorph)

4-(3-4(1,1-dimethylethyl)phenyl)-2-methyl)propylpiperidine (fenpropidine)

1-(4-chlorophenoxy)-3,3-dimethyl-1-1H-1,2,4-triazol- 1-yl)butanone (triadimefon) 2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)hexanenitrile (myclobutanil)

1-[2-(4-chlorophenyl)ethyl]-1-(1,1-dimethylethyl)-1- (1H-1,2,4-triazole-1-yl)ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1-ylmethyl)- 1,3-dioxolan-2-yl]phenyl-4-chlorophenyl ether

(difenoconazole)

1-[2-(2,4-dichloroρhenyl)pentyl]1H-1,2,4-triazole

(penconazole)

2,4'-difluoro-1-(1H-1,2,4-triazole-1-ylmethyl)- benzhydryl alcohol (flutriafol)

1-[[[bis(4-fluorophenyl)]methylsilyl]methyl]-1H-1,2,4- triazole (flusilazole)

N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole- 1-carboxamide (prochloraz)

1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- ylmethyl]-1H-1,2,4-triazole (propiconazole)

1-(2-chlorophenyl)-1-(4-chlorophenyl)-1-(5-pyrimidin)- methanol (fenarimol)

1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole- 1-yl)butan-2-ol (triadimenol)

1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4- triazol-1-yl)pentan-3-ol (diclobutrazol)

copper oxychloride

methyl N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)- DL-alaninate (furalaxyl)

Bactericides

tribasic copper sulfate

streptomycin sulfate

oxytetracycline Acaricides

senecioic acid, ester with 2-sec-butyl-4,6- dinitro-phenol (binapacryl)

6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one

(oxythio-quinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol

(dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl)(dienochlor) tricyclohexyltin hydroxide (cyhexatin)

hexakis (2-methyl-2-phenylpropyl) distannoxane

(fenbutin oxide)

Nematicides

2-[diethoxyphosphinylimino]-1,3-diethietane

(fosthietan)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl)

S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl]diester (fenamiphos)

Insecticides

3-hydroxy-N-methylcrotonamide (dimethyIphosphate) ester (monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with alpha-naphthol (carbaryl)

methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine

(chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenoxyphenyl)-methyl 4-chloroalpha-(1-methylethyl)benzeneacetate (fenvalerate) (3-phenoxyphenyl)methyl 3-(2,2-dichloro-ethenyl)-2,2- dimethylcyclopropanecarboxylate (permethrin) dimethyl N,N'-[thiobis(N-methylimmo)carbonyloxy]]- bis[ethanimidothioate] (thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos)

alpha-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)alpha-(methylethyl)benzeneacetate (flucythrinate) O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos)

O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)- methyl]phosphorodithioate (azinphos-methyl)

5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate (pirimicarb)

S-(N-formyl-N-methylcarbamoylmethyl)-O,O-dimethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl)

(5)-alpha-cyano-3-phenoxybenzyl (1R, 3R)-3-(2,2-dibromovinyl)-

2,2-dimethylcyclopropanecarboxylate (deltamethrin) cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4- trifluoromethylphenyl) alanine (fluvalinate)

APPLICATION

Disease control is ordinarily accomplished by applying an effective amount of the compound either preinfection or post-infection to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed, to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

TEST A

The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaequalis (the causal agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made. TEST B

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosporidium personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22°C for 24 h, a high humidity atmosphere at 22 to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made.

TEST C

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.

TEST D

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated

atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

TEST E

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made.

TEST F

suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made. Results for Tests A to F are given in

Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). NT indicates that no test was performed.

In Index Table A, the following abbreviations are used:

Ph - phenyl

OPh - phenoxy

c-hex - cyclohexyl

tBu - tertiary butyl

iPr - isopropyl

TABLE A

Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

1 89 38 52 96 86 NT

2 99 6 45 69 99 NT

3 81 22 57 26 78 NT

4 67 0 75 26 70 NT

5 35 54 10 0 0 NT

6 28 54 10 73 36 NT

7 65 0 10 87 80 NT

8 100 24 46 84 100 95

9 74 0 53 56 68 NT

10 100 24 68 80 97 NT

11 100 45 27 26 91 NT

12 96 14 14 0 98 NT

13 100 33 54 33 100 NT

14 17 0 0 86 66 NT

15 0 21 0 31 0 NT

16 17 16 0 31 24 NT

17 100 0 54 69 71 0

18 90 20 86 98 100 96

19 66 20 60 14 NT 40B

20 73 0 NT 0 NT NT

21 0 12 NT 0 NT NT

22 15 12 NT 0 NT NT 23 94 12 98 9 NT NT 24 100 9 18 64 78 NT25 93 23 63 79 91 28 26 82 0 NT 88 57 0 27 46 46 NT 96 82 0 28 68 0 NT 41 67 0 29 87 0 NT 39 91 0 Cmpd TEST TEST TEST TEST TEST TEST No. A B C D E F

30 90 0 NT 81 85 0

31 100 0 20 63 55 0

32 95 23 NT 95 100 0

33 100 26 50 99 99 90

34 100 26 50 87 99 27

35 98 0 50 62 97 0

36 98 26 94 95 100 10

37 88 23 NT 88 97 42

38 99 23 NT 93 100 0

39 96 14 85 96 100 0

40 99 37 95 96 100 7

41 100 34 30 49 100 9

42 0 0 NT 0 NT 0

43 43 0 NT 0 NT 0

44 44 34 81 17 100 0

45 97 29 NT 76 NT 96

46 100 10 0 96 100 5

47 100 28 85 96 100 0

48 93 43 NT 85 NT 35

49 49 0 NT 72 100 10

50 90 43 NT 93 NT 15B

51 98 11 0 24 NT 0

52 NT 0A 74A 0A 0A NT

53 69A 0A 48A 54A 39A NT

54 75A 58A 0A 0A 0A NT

55 93 0 NT 78 100 7

57 58 52 NT 0 NT 0

58 74 11 NT 0 NT 0 Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

59 58 11 NT 85 99 0

60 0 52 NT 0 NT 0

61 78 52 NT 24 NT 6

62 30 52 NT 24 NT 6

63 1 0 NT 0 NT 42

64 2 39 8 0 NT 0

65 100 0 77 85 100 5

66 99 0 77 60 100 84

67 51 35 90 75 100 5

68 100 0 79 85 100 5

69 100 35 80 73 100 0

70 100 35 71 50 100 0

71 100 35 71 26 100 5

72 100 83 85 17 100 5

73 96 32 46 94 100 5

74 90 0 NT 91 100 0

75 92 52 NT 86 NT 0

76 64 12 NT 0 NT 0

77 100 36 95 62 100 8

78 100 58 82 86 100 0

79 100 27 93 47 100 0

80 100 42 80 17 100 8

81 100 0 84 91 96 83

82 100 33 63 93 99B 31

83 64 64 88 68 100 0

84 90 36 91 0 100 0

85 100 0 91 40 100 0

86 100 36 NT 57 100 8

87 100 8 75 43 100 0 88 43 32 NT 93 100 0 89 100 0 NT 96 100 41 Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

90 100 26 NT 98 100 41

91 100 0 NT 91 100 80

92 100 32 49 90 100 0

93 90 79 27 94 100 5

94 100 64 61 86 100 0

95 100 0 68 0 NT 0

96 30 0 NT 0 NT 0

97 100 23 4 0 NT 0

98 88 31 63A 99 99B 0B

99 100 31 NT 0 NT 0

100 95 31 18 94 96B 86

101 100 31 63 98 95B 14

102 97 0 NT 0 NT 4

103 98 33 5 76 100 55

104 100 0 NT 25 NT 0

105 100 33 78 46 79B 42

106 96 0 41 65 33B 0

107 53 33 63 99 99B 22

108 90 64 77 100 100B 9

109 40 33 NT 0 NT 42

110 100 33 74 94 100B 0

111 90 64 47 25 NT 3

112 96 64 55 54 73B 42

113 90 16 85 86 100B 42

114 100 51 64 99 97B 1

115 38B 28B NT 92 100B 6

116 95 81 NT 95 99B 3

117 41B NT 19 43 95B NT

118 82 26 42 100 98B 3

119 100 49 38 92 100B 8 Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

120 91 41 38 93 97B 8

121 91 42 38 96 100B 8

122 0 70 38 96 83B 0

123 62 36 38 96 NT 3

124 41 70 NT 90 81B 8

125 91 11 30 80 71B 0

126 100 49 49 99 99B 8

127 100 70 38 83 99B 8

128 99 70 15 31 98B 8

129 100 55 38 96 100B 8

130 98 70 49 81 98B 0

131 100 54 30 94 100B 0

132 100 11 38 82 100B 6

133 84 70 38 97 100B 8

134 91 0 38 68 86B 8

135 62 0 23 88 100B 0

136 62 5 38 0 95B 8

137 91 29 30 96 100B 8

138 94 42 30 62 99B 9

139 17 70 NT 40 87B 3

140 93 51 NT 82 96B 0

141 96 65 NT 91 100B 0

142 59 35 22 45 96B 0

143 100 62 96 19 95B 0

144 95 34 85 92 100B 0

145 89 40 79 93 100B 0

146 10 56 NT 0 NT 0

147 100 42 NT 73 100B 0

148 100 7 NT 98 100B 0

149 90 7 NT 92 100B 0

150 90 56 NT 67 97B 0 Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

151 88 2 NT 92 87B 0

152 100 42 NT 96 83B 4

153 100 20 NT 92 70B 0

154 89 47 61 99 100B 4

155 95 64 74 91 100B 4

156 98 39 NT 89 100B 11

157 89 0 NT 85 97B 0

158 100 39 61 91 100B 64

159 95 0 NT 88 100B 0

160 64 0 80 98 95B 11

161 95 58 88 0 99B 9

162 88 94 78 0 100B 0

163 90 0 NT 91 89B 7

164 68 3 NT 25 75B 0

165 0 0 NT 64 50B 0

166 93B NT 92 96 80B 97

167 67 NT 92 96 100B 0

168 71 NT 92 62 100B 0

169 76B NT 92 76 100B 0

170 67B NT 89 69 99B 0

171 82B NT 70 58 99B 0

172 24 NT 92 24 88A 0

173 96B NT 90 91 99B 0

174 89B NT 92 97 100B 0

175 99 NT NT 25 95B 0

176 65 NT 93 92 99B 0

177 89 NT 65 72 96B 0

178 89 NT 90 68 95B 0

179 89 NT 90 74 80B 0

180 100 NT 86 97 95B 0

181 99 NT 90 0 100B 0 Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

182 19 NT 86 25 95B 0

183 86B NT 90 99 99B 98

184 89B NT 83 100 100B 0

185 91 NT 83 0 72B 0

186 89B NT 90 92 100B 0

187 70B NT 99 87 100B 34

188 19 NT NT 0 86B 0

189 100 NT 83 93 99B 0

190 0 NT 90 0 43B 0

191 100 64A 52 92 86 NT

192 91A 64A 65A 82A 86A NT

193 46A 64A 28A 37A 49A NT

194 46A 29A 28A 0A 0A NT

195 94 0A 63 56 97 NT

196 10A 0A 0A 15A 14A NT

197 93A 36A 41A 8A 44A NT

202 90 8 NT 23 NT 16

204 NT NT 56 26 96B 0

205 NT NT 95 70 99B 0

206 NT NT 91 33 96B 0

207 NT NT NT 0 46B 0

208 NT NT 88 80 99B 0

209 NT NT 98 66 100B 1

210 NT NT 84 100 100B 40

Cmpd TEST TEST TEST TEST TEST TEST

No. A B C D E F

211 NT NT 96 99 100B 65

212 NT NT 96 99 100B 88

213 NT NT NT 97 100B 0

214 NT NT NT 96 100B 9

215 NT NT NT 97 100B 9

216 NT NT 86 97 97B 9

217 NT NT 56 94 100B 68

218 NT NT 61 97 100B 68

219 NT NT 61 97 99B 5

220 NT NT 52 90 95B 5

A. Percent control at 100 ppm, the highest concentration tested.

B. Percent control at 40 ppm, the highest concentration tested.

Claims

CLAIMS What is claimed is:

1. A method of controlling fungus disease in plants comprising the application of an effective amount of a compound of Formula I to the locus to be protected.

wherein:

R² is H; trifluoromethyl; C₂-C₄ alkyl; phenyl

R³ is H or C₁-C₄ alkyl; R⁴ is H, C₁-C₄ alkyl, allyl, propargyl, -C(=O)R¹⁴,

R⁶ is H, Cl, Br or C₁-C₄ alkyl;

R⁷ is 1-2 halogen, 1-2 methyl, methoxy, nitro, cyano or trifluoromethyl;

R⁸ is 1-2 halogen; C₁-C₆ alkyl; C₃-C₆ cycloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₂-C₄ haloalkyl; cyano; nitro; C₂-C₃ alkoxycarbonyl; C₂-C₃

R¹¹, R¹² and R¹³ are independently H, C₁-C₄ alkyl,

phenyl or 4-chlorophenyl;

R¹⁴ is C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or

C₂-C₄ alkoxyalkyl;

R¹⁷ is C_x-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄

alkoxyalkyl;

R¹⁸ and R¹⁹ are independently C₂-C₃ alkyl; or R¹⁸ and

R¹⁹ can be taken together with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group;

R²⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄

alkoxyalkyl; or phenyl optionally substituted with R⁷;

J is (CH₂)_p, O, S(O)_p or CH₃N;

m is 0, 1 or 2; and

p is 0, 1 or 2. provided that

2) the total number of carbon atoms in R¹ and R²

together is less than 24; and

3) the total number of carbon atoms in R¹⁵ and R¹⁶ together is no greater than 8.

2. A method according to Claim 1 wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸;

R² is H; C₁-C₄ alkyl; or phenyl optionally substituted with R⁷ and R⁸;

R³ is H or methyl;

R⁵ is H or methyl; and

R⁶ is H or methyl.

3. A method according to Claim 2 wherein:

R² is H; C₁-C₂ alkyl; or phenyl optionally

substituted with R⁷ and R⁸;

R⁴ is H, -C(=O)R¹⁴ or -C(=O)NR¹⁵R¹⁶; and

4. A method according to Claim 3 wherein:

R¹⁵ and R¹⁶ are independently H or C₁-C₄

alkyl.

5. A method according to Claim 4 wherein:

R² is methyl; or phenyl optionally

substituted with R⁷ and R⁸;

R³ is H; R⁵ is H;

R⁶ is H;

R⁸ is phenyl or phenoxy each optionally

substituted with R⁷;

R¹⁴ is C₁-C₄ alkyl;

R¹⁵ is H; and

R¹⁶ is H or C₁-C₄ alkyl.

6. A method of Claim 5 wherein the compounds are:

1) 6-acetyloxy-2-[1,1'-biphenyl]-4-yl-2- methyl-2H-pyran-3(6H)-one;

2) 2-[1,1'-biphenyl]-4-yl-6-hydroxy-2-phenyl- 2H-pyran-3(6H)-one; and

3) 6-acetyloxy-2,2-bis(4-chlorophenyl)-2H- pyran-3(6H)-one.

7. A compound of Formula I,

wherein :

R² is phenyl optionally substituted with R⁷ and R⁸; or pyridyl, thienyl or pyrazolyl each optionally substituted with R⁷; or R¹ and R² can be taken together with the carbon to which they are attached to form structures such as

R³ is H or C₁-C₄ alkyl;

R⁴ is H, C₁-C₄ alkyl, allyl, propargyl, -C(=O)R¹⁴,

R⁶ is H, Cl, Br or C₁-C₄ alkyl;

R⁷ is 1-2 halogen, 1-2 methyl, methoxy, nitro, cyano or trifluoromethyl;

R⁸ is 1-2 halogen; C₁-C₆ alkyl; C₃-C₆ cycloalkyl;

C₁-C₄ alkoxy; C₂-C₄ haloalkoxy; C₂-C₄ haloalkyl; cyano; nitro; C₂-C₃ alkoxycarbonyl; C₂-C₃

R¹¹, R¹² and R¹³ are independently H, C₁-C₄ alkyl,

phenyl or 4-chlorophenyl;

R¹⁴ is C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or

C₂-C₄ alkoxyalkyl;

R¹⁷ is C₂-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄

alkoxyalkyl;

R²⁰ is C₂-C₄ alkyl; C₂-C₄ haloalkyl; C₂-C₄

alkoxyalkyl; or phenyl optionally substituted with R⁷;

J is (CH₂)_p, O, S(O)_p or CH₃N;

m is 0, 1 or 2; and

p is 0, 1 or 2.

provided that

1) the total number of carbon atoms in R¹ and R²

together is less than 24;

2) the total number of carbon atoms in R¹⁵ and R¹⁶ together is no greater than 8; and

3) when R² is phenyl, R¹ cannot be 4-phenyl phenyl or 3,4-dimethyl phenyl.

8. A compound of Claim 7 wherein:

R¹ is phenyl optionally substituted with R⁷ and R⁸;

R² is phenyl optionally substituted with R⁷ and R⁸;

R³ is H or methyl;

R⁵ is H or methyl; and

R⁶ is H or methyl.

9. A compound of Claim 8 wherein:

R⁴ is H, -C(=O)R¹⁴ or -C(=O)NR¹⁵R¹⁶; and

10. The compounds of Claim 9 wherein:

R¹⁵ and R¹⁶ are independently H or C₁-C₄

alkyl.

11. The compounds of Claim 10 wherein:

R³ is H;

R⁵ is H;

R⁶ is H;

R⁸ is phenyl or phenoxy each optionally

substituted with R⁷;

R¹⁴ is C₁-C₄ alkyl;

R¹⁵ is H; and

R¹⁶ is H or C₁-C₄ alkyl.

12. The compound of Claim 11 which is:

6-acetyloxy-2,2-bis(4-chlorophenyl)-2H- pyran-3(6H)-one.

13. An agriculturally suitable composition of a compound of any of Claims 7-12 comprising a fungicidally effective amount of said compound and at least one of the following: surfactant, solid diluent or liquid diluent.