WO1992004318A1 - Oxime carbonates as fungicides - Google Patents

Abstract

Selected oxime carbonates of formula (I), and their geometric and stereoisomers, agricultural compositions containing such compounds and their use as fungicides. In formula (I) Y is Cl or SO2R4; R1 is (a),(b), (c), or (d) wherein the aromatic rings of R1 are optionally substituted; R?2 and R3¿ are independently H or C¿1?-C4 alkyl; or R?2 and R3¿ can be taken together along with the nitrogen atom to which they are attached to form an optionally substituted heterocyclic ring; R4 is phenyl; naphthyl; cycloalkyl; or C¿1?-C12 alkyl optionally substituted with C1-C2 alkoxy, C5-C6 cycloalkyl, phenyl or naphthyl; Q?1¿ is alkylene, Q2 is alkylene or a direct bond.

Description

TITLE

OXIME CARBONATES AS FUNGICIDES BACKGROUND OF THE INVENTION

Bellina U.S. 3,819,700 claims compounds of Formula i as fungicides for crop protection.

Hubele CH 66-16,259 claims compounds of Formula ii as

fungicides for crop protection.

Compounds of Formula iii are disclosed in the patent literature as antidotes for herbicides in U.S. 4,416,686, U.S. 4,426,221, U.S. 4,453,969, U.S. 4,453,974, and U.S. 4,475,945.

Compounds of Formula iv are disclosed in EP 293 667 A as fungicides for crop protection.

Compounds of Formula v are disclosed in U.S. 3,954,992 as fungicides for crop protection.

CIBA-Geigy, EP 0010588 (U.S. equivalents 4,449,999, 4,394,152, 4,451,279 and 4,382,893) discloses the use of compounds of Formula vi as herbicide safeners.

The compounds disclosed as safeners overlap the compounds claimed in Bellina (U.S. 3,819,700) wherein X is C(=O)NR¹R².

E. Merck A.-G. (Ger. 1,141,487) discloses compounds of Formula v ii as fungicides and fungistats

wherein R is H, Cl, F or C₁-C₃ alkyl.

Although the above mentioned compounds are useful as fungicides, the need continues for fungicides that have improved activity.

SUMMARY OF THE INVENTION

This invention pertains to compounds of the Formula (I) including all geometric and stereoisomers, agricultural compositions containing them and their use as fungicides

wherein:

Y is Cl or SO₂R⁴;

wherein the aromatic rings of R¹ are optionally substituted with methyl, methoxy, nitro or 1-2 halogen; and

wherein designations such as:

indicate that substitution at any position is permissible; R² and R³ are independently H or C₁-C₄ alkyl; or R² and R³ can be taken together along with the nitrogen atom to which they are attached to form a pyrrolidino, piperidino or morpholino group, said pyrrolidino, piperidino or

morpholino group being optionally substituted with 1-2 methyl;

R⁴ is phenyl; naphthyl; C₅-C₈ cycloalkyl; or C₁-C₁₂ alkyl

optionally substituted with C₁-C₂ alkoxy, C₅-C₆ cycloalkyl, phenyl or naphthyl;

Q¹ is C₁-C₄ normal alkyl; and Q² is C₁-C₃ normal alkyl optionally substituted with 1-2 methyl, or a direct bond.

Preferred Embodiments

1) Compounds of the Formula (I) wherein:

R¹ is

2) Compounds of Preferred 1 wherein:

R⁴ is methyl, phenyl or benzyl.

3) Compounds of Preferred 2 wherein:

R¹ is naphthylmethyl or naphthyl(2-ethyl).

4) Compounds of Preferred 3 wherein:

R² and R³ are both methyl or R² and R³ are taken together along with the nitrogen atom to which they are attached to form a piperidino group.

5) Compounds of Preferred 4 wherein:

Y is Cl.

6) Specifically preferred is a compound of Preferred 5 that is 2-(dimethylamino)-N-[[[(2-naphthalenyl)methoxy]- carbonyl]oxy]-2-oxoethanimidoyl chloride.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

Compounds of Formula (I) can be prepared by either of two methods (A and B): tho

Method B

In Method A (Y=Cl, SO₂R⁴) the carboxamide II reacts with the chloroformate llI in an inert solvent in the presence of an acid scavenger (base). Suitable solvents include polar aprotic solvents such as acetonitrile and ethyl acetate; ethers such as tetrahydrofuran (THF), dimethoxyethane and diethyl ether; ketones such as acetone and

2-butanone; hydrocarbons such as benzene, toluene and xylene; and halocarbons such as chloroform and dichloromethane. Suitable bases include triethylamine, N,N-diisopropyl-N-ethylamine, pyridine,

N,N-diethylanilin

d N,N-dimethylaniline. The reaction temperature can range from about -20 to +50°C, and the reaction time from about 5 minutes to several days depending on choice of reactants, solvent and temperature. In Method A the carboxamide II can be made as described in U.S.

Patents 3,557,089, 3,557,190, 3,560,555, or 3,819,700. The

chloroformates III can be made by methods well-known in the art and exemplified in this specification. However, it is also known in the art that some chloroformates are unstable, readily generating relatively stable cations [(R¹)⁺ in this case], most generally for the compounds llI wherein R¹ is a secondary or tertiary benzylic-type group, with loss of CO₂ and formation of alkyl chloride. In those cases Method B is preferred.

In Method B (Y=Cl) the oxime chloroformate IV reacts with the alcohol V in the presence of an acid scavenger (base) to form the product (I), with Y=Cl. Reaction conditions are much as described for Method A. The oxime chloroformates IV can be made by reaction of a carboxamide II with phosgene in an inert solvent (such as toluene, benzene, xylene or THF) in the presence of a base (such as N,N-diethylaniline, N,N- dimethylaniline, pyridine, triethylamine and N,N-dϋsopropyl-N- ethylamine). The alcohols V, many of which are commercially available, can be made by one or more methods known to those skilled in the art. For example, a halo compound can be hydrolyzed:

It is recognized by those skilled in the art that compounds of Formula (I) are O-substituted oximes and, as such, may exist in the syn or antiform, or mixtures thereof. The scope of this invention includes both the syn and antiforms and mixtures thereof as they are likely to occur.

The following Examples represent the preparation of novel oxime compounds of Formula (I) and intermediates thereto. Reported temperatures are in degrees centigrade. Thin-layer chromatography (TLC) was performed with silica-gel-coated plates and the indicated eluent.

EXAMPLE 1

Preparation of 2-(bromomethyl)naphthalene

[For other preparative methodology for (bromomethyl)naphthalenes see, e.g., Synlett (1), 55 (1989)]

A solution of 2-methylnaphthalene (6.08 g) in carbon tetrachloride (100 ml) was heated to boiling, and N-bromosuccinimide (7.62 g) was added. light from a 275-watt GE sunlamp was shone on the hot reaction solution for 1 hr. The mixture was cooled and filtered, and the solvent evaporated under vacuum, leaving an off-white residual solid. The solid was dissolved in hot hexane, the solution treated with activated carbon, and filtered. From the cooled filtrate was filtered the title product, 6.95 g (73% of theoretical), as a white solid, m.p. 52-54°. The product was homogeneous by TLC (hexane; R_f 0.55).

EXAMPLE 2

Preparation of 2-(hydroxymethyl)naphthalene A solution of 2-(bromomethyl)naphthalene (4.36 g) in dioxane

(50 ml) was diluted with IN NaOH (75 ml) and the stirred mixture boiled under reflux for 1.5 hrs. The cooled mixture was diluted with water, the solid filtered off, and recrystallized from hexane, providing the title product as a solid of m.p. 79-80.5°.

EXAMPLE 3

Preparation of 2-naphthylmetbyl chloroformate liquid phosgene (20 ml) was dripped into a stirred suspension of 2-(hydroxymethyl)naphthalene (16.47 g) in toluene (200 ml) at -3°. A solution of N,N-diethylaniline (16.6 g) and pyridine (5 drops) in toluene (20 ml) was dripped in during a 10-min period while the temperature was kept at 5-10° by external cooling. After 4 hrs. the mixture was filtered and evaporated under reduced pressure to an oily solid. This was treated with ether and again filtered, and evaporated to a solid. Recrystaliization from hexane provided the title product as a white solid, m.p. 73-76°. TLC (chloroform) revealed one component, R_f 0.93.

EXAMPLE 4

Preparation of N-r(chlorocarbonyl)oxy]- 2-(dimethylam ino)-2-ox oethanim idoyl chloride Liquid phosgene (45 ml) was added to a stirred suspension of

2-chloro-2-hydroximino-N,N-dimethylacetanιide (32.5 g) in toluene (150 ml) at -3°. During a 35-min. period a solution of N,N-diethylaniline (34.3 ml) and pyridine (6 drops) in toluene (20 ml) was added at -3 to +10°. After 5 hrs. solid was filtered from the reaction mixture and the filtrate evaporated in vacuum to an oil/solid residue. The residue was treated with ether, filtered and the solution evaporated to an oil. Further drying under a nitrogen stream provided solid product. The solid was heated with cyclohexane, filtered, the filtrate treated with activated carbon, and refiltered. Partial evaporation and cooling of the filtrate precipitated white solid product (24.05 g), m.p. 65-68°. An additional crop of product (2.02 g; m.p. 69-71°) was obtained by evaporation of the cyclohexane filtrate and crystallization of the residue from

1-chlorobutane, for a total yield of 56% of theoretical.

Other oxime chloroformates that can be similarly prepared include, but are not limited to:

Compounds IV, wherein R¹ is

Piperidino m.p. 69-71°

Pyrrolidino

N,N-Diethylamino

N-Butyl-N-methylamino

Morpholino

2,6-Dimethylmorpholino

EXAMPLE 5

Preparation of 2-(dim ethylamino)-N-[[[(2-naphtha- lenyl)methoxy]carbonyl]oxy]-2-oxoethan imdoyl chloride To a stirred solution of 2-naphthylmethyl chloroformate (8.56 g) in 150 ml of THF at -8°, was added 2-chloro-2-hydroximino-N,N-dimethyl- acetamide (5.84 g), followed by dropwise addition of triethylamine

(5.41 ml), with the temperature held to -2°; white solid precipitated. The mixture was stirred further for 2 hrs., filtered and the filtrate evaporated in vacuum to a white solid. The solid was recrystallized from ethyl acetate/hexane, providing 9.06 g (70% of theoretical) of the title

compound, m.p. 114-117°. TLC (chloroform/ethyl acetate, 9/1) showed only one spot, Rf 0.74.

EXAMPLE S

Preparation of 2-(dim ethylamino)-N-[[[(2- naphthalenyl)methoxy]carbonyl]oxy]-2-oxoet hanim idoyl chloride To a stirred solution of N-[(chl orocarbonyl)oxy]-2-dimethylamino-2- oxoethanimidoyl chloride (2.48 g) in THF (50 ml) was added 2-(hydroxymethyl)naphthalene (1.84 g). The solution was cooled to 5-10°, and triethylamine (1.62 ml) was pipetted in, producing an exotherm and precipitation of white solid. After 2 hours at room temperature the mixture was filtered and the filtrate evaporated in vacuum to a white solid. Recrystallization was effected from ethyl acetate/hexane, providing

2.86 g (74% of theoretical) of the title compound, m.p. 108-110°.

Analysis calculated for C₁₆H₁₅ClN₂O₄: C, 57.40; H, 4.52; N, 8.37%.

Analysis found: C, 57.29; H, 4.53; N, 8.37%. EXAMPLE 7

Preparation of 2-(m e th ylamino)-N-[[[(2-naphtha- lenyl)methoxy]carbonyloxy]-2-oxoethanimidoyl chloride Liquid phosgene (4 ml) was added to a suspension of 2-chloro-2- hydroximino-N-methylacetamide (2.08 g) in toluene (100 ml) at -5°. A solution of N,N-diethylaniline and pyridine (3 drops) in toluene was dripped in at -3° during a 10-min period. The mixture was allowed to warm to room temperature and stand overnight. Solid was filtered off and the filtrate evaporated in vacuum to tan oil (3.02 g, 89% of

theoretical), which is the chloroformate derivative N-[(chlorocarbonyl)- oxy]-2-methylamino-2-oxoethanimidoyl chloride. The IR spectrum of this compound showed absorption at 3296 cm^-1 (NH), 1811 cm^-1

(chlorocarbonyl) and 1692 cm^-1 (amide carbonyl).

To a stirred solution of 2-naphthalenemethanol (2.15 g) and pyridine (1.15 ml) in THF (50 ml) at -5°, was added portionwise a solution of the above chloroformate (2.7 g) in THF (25 ml), with temperature rise to 2° and formation of white solid. After 1 hr. at room temperature the mixture was filtered and the filtrate evaporated in vacuum to an oily tan solid. This was dissolved in ethyl acetate and the solution washed with water, IN HCl, water, saturated sodium bicarbonate solution and saturated brine, then dried (MgSO₄) and evaporated in vacuum to an off-white solid. Recrystallization from 1-chlorobutane (containing a small amount of ethyl acetate) provided the pure title product, m.p. 153-156°. The infrared spectrum of the product showed absorption at 3305 cm^{- 1} (NH), 1794 cm^-1 (carbonyl of oxime carbonate), and 1675 cm^-1 (amide carbonyl). The product was also obtained by reaction of 2-chloro-2- hydroximino-N-methylacetamide with 2-naphthylmethyl chloroformate in THF with pyridine as the base.

EXAMPLE 8

Preparation of N,N-dimethyl-2-[(2-naphthalenyl- methoxy)carbonyloxyimino]-2-[(phenylmethyl)sulfonyl]ace tam ide

Into a stirred, nitrogen-blanketed solution of 2-chloro-2-hydroximino-N,N-dimethylacetamide (11.52 g) in THF (200 ml), cooled to 2°, was added benzyl mercaptan (8.95 g). At 0° triethylamine (10.7 ml) was pipetted in during a 7-min period, with precipitation of white solid and temperature rise to 10-15°. After 4 hrs. the mixture was filtered and the filtrate evaporated in vacuum to a white solid. Recrystallization of the solid from ethyl acetate-hexane provided the intermediate 2-hydroximino- 2-benzylthio-N,N-dimethylacetamide (15.95 g), m.p. 161-163°.

Into a stirred, nitrogen-blanketed suspension of the above-prepared benzylthio compound (9.93 g) in chloroform (200 ml), cooled to 15°, was added portionwise 32% peracetic acid (17.5 ml) during a 30-min. period, the temperature rising to 24° and a clear solution forming. During overnight stirring the mixture precipitated white solid. The solid was filtered off and recrystallized from acetonitrile, providing the intermediate 2-hydroximino-2-benzylsulfenyl-N,N-dimethylacetamide (7.50 g) as a white solid, m.p. 189-190°.

Into a stirred, nitrogen-blanketed suspension of the above-prepared benzylsulfonyl compound (2.32 g) in THF (75 ml), cooled to -5°, was added 2-naphthylmethyl chloroformate (1.89 g), followed by triethylamine (1.2 1). The mixture was stirred overnight, then filtered to remove white solid. The filtrate was evaporated in vacuum to an oil, the oil dissolved in n-butyl chloride with the aid of ethyl acetate, and the organic solution washed with water, IN HCl, water, saturated sodium bicarbonate solution and saturated brine. After drying (MgSO₄) the solution was evaporated in vacuum to an oil, which was crystallized from n-butyl chloride, providing the title compound as a white solid (2.00 g), m.p. 135-137°. Analysis calculated for C₂₃H₂₂N₂O₆S: C, 60.78; H, 4.88; N,

6.17%. Analysis found: C, 59.98; H, 4.64; N, 6.11%.

Representative compounds of this invention are fisted in the Table which follows. The compounds can be made according to one or more of the methods described in the preceding Examples. The Table is not intended to be all-inclusive.

(l)

Y = Cl

NR²R³ R¹ dimethylamino 1-naphthylmethyl

dimethylamino 2-naphthylmethyl

dimethylamino 2-(2-naphthyl)ethyl

dimethylamino 2-(l-naphthyl)ethyl

dimethylamino 3-(2-naphthyl)propyl

dimethylamino 4-(2-naphthyl)butyl

dimethylamino 2-methyl-1-naphthylmethyl dimethylamino 4-methyl-2-naphthylmethyl dimethylamino 6-methyl-2-naphthylmethyl dimethylamino 7-methyl-2-naphthylmethyl dimethylamino 8-methyl-2-naphthylmethyl dimethylamino 6-methoxy-2-naphthylmethyl dimethylamino 4-bromo-1-naphthylmethyl dimethylamino 5-chloro-2-naphthylmethyl dimethylamino 4-nitro-1-naphthylmethyl dimethylamino 6-fluoro-2-naphthylmethyl dimethylamino 6-iodo-2-naphthylmethyl

dimethylamino 1-bromo-2-naphthylmethyl dimethylamino 2-methoxy-1-naphthylmethyl dimethylamino 4-methoxy-1-naphthylmethyl dimethylamino 6-methoxy-2-(2-naphthyl)-prop-1-yl NR²R³ R¹ piperidino 2-naphthylmethyl

piperidino 1-naphthylmethyl

piperidino 2-(2-naphthyl)ethyl

piperidino 2-(1-naphthyI)ethyl

pyrrolidino 2-naphthylmethyl

pyrrolidino 1-naphthylmethyl

pyrrolidino 2-(2-naphthyl)ethyl

pyrrolidino 2-(1-naphthyl)ethyl

morpholino 2-naphthylmethyl

morpholino 1-naphthylmethyl

morpholino 2-(2-naphthyl)ethyl

morpholino 2-(1-naphthyl)ethyl

2,6-dimethylmorpholino 2-naphthylmethyl

2,6-dimethylmorpholino 1-naphthylmethyl

2 ,6-dimethylmorpholino 2-(2-naphthyl)ethyl

2,6-dimethylmorphoHno 2-(1-naphthyl)ethyl

2-methylpiperidino 2-naphthylmethyl

2,5-dimethylpyrrolidino 2-naphthylmethyl

dimethylamino 1,2,3,4-tetrahydro-2-naphthyl dimethylamino 1,2,3,4-tetrahydro-2-naphthylmethyl piperidino 1,2,3,4-tetrahydro-2-naphthyl piperidino 1,2,3,4-tetrahydro-2-naphthylmethyl dimethylamino 1-indanyl

dimethylamino 1-methoxy-2-indanyl

piperidino 1-indanyl

dimethylamino 9-fluorenyl

piperidino 9-fluorenyl

dimethylamino 9-fluorenylmethyl

dimethylamino 2-(9-fluorenyl)ethyl NR²R³ R¹ dimethylamino 3-(9-fiuorenyl)propyl dimethylamino 1,6-dibromo-2-naphthylmethyl dimethylamino 1,6-dichloro-2-naphthylmethyl dimethylamino 2-indanyl

dimethylamino 6-bromo-1-indanyl

dimethylamino 6-chloro-1-indanyl

dimethylamino 6-methyl-1-indanyl

dimethylamino 6-methoxy-1-indanyl dimethylamino 6-nitro-1-indanyl

dimethylamino 5,6-dibromo-1-indanyl dimethylamino 2-bromo-9-fluorenyl

dimethylamino 3-methyl-9-fluorenyl

NR²R³ R¹ R⁴ dimethylamino 2-naphthylmethyl benzyl

dimethylamino 2-(2-naphthyl)ethyl methyl

dimethylamino 2-naphthylmethyl methyl

dimethylamino 2-(2-naphthyl)ethyl benzyl

dimethylamino 2-naphthylmethyl ethyl

dimethylamino 2-naphthylmethyl n-propyl dimethylamino 2-naphthylmethyl isopropyl dimethylamino 2-naphthylmethyl n-butyl

dimethylamino 2-naphthylmethyl n-dodecyl dimethylamino 2-naphthylmethyl 2-methoxyethyl dimethylamino 2-naphthylmethyl 2-ethoxyethyl dimethylamino 2-naphthylmethyl cyclopentylmethyl dimethylamino 2-naphthylmethyl cyclohexylmethyl dimethylamino 2-naphthylmethyl phenyl

dimethylamino 2-naphthylmethyl 1-naphthyl dimethylamino 2-naphthylmethyl 2-naphthyl dimethylamino 2-naphthylmethyl cyclopentyl dimethylamino 2-naphthylmethyl cyclohexyl dimethylamino 2-naphthylmethyl cycloheptyl dimethylamino 2-naphthylmethyl cyclooctyl piperidino 2-naphthylmethyl methyl NR²R³ R¹ R⁴ piperidino 2-naphthylmethyl benzyl

piperidino 2-naphthylmethyl phenyl

methylamino 2-naphthylmethyl methyl

methylamino 2-naphthylmethyl benyl

methylamino 2-naphthylmethyl phenyl

pyrrolidino 2-naphthylmethyl methyl

pyrrolidino 2-naphthylmethyl benzyl

pyrrolidino 2-naphthylmethyl phenyl

morpholino 2-naphthylmethyl methyl

dimethylamino 1-naphthylmethyl methyl

dimethylamino 1-naphthylmethyl benzyl

dimethylamino 1-naphthylmethyl phenyl

dimethylamino 2-(1-naphthyl)ethyl methyl

dimethylamino 2-(1-naphthyl)ethyl benzyl

dimethylamino 2-(1-naphthyl)ethyl phenyl

dimethylamino 1,2,3,4-tetrahydro-2-naphthyl methyl

dimethylamino 1-indanyl methyl

dimethylamino 9-fluorenylmethyl methyl

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, NewJersey, 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 PubHshing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents",

Chemical Publishing Co., Inc., NewYork, 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., New 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.

One skilled in the art will recognize that Examples A, B, C, E, J, K, and L are inappropriate wherein the active ingredient is an oil.

Example A

Wettable Powder

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 80%

sodium alkylnaphthalenesulfonate 2%

sodium liginsulfonate 2%

synthetic amorphous silica 3%

kaolinite 13%

The ingredients are blended, hammer-milled until all the solids are substantially under 50 microns, reblended, and packaged.

Example B

Wettable Powder

2-(dimethylamino)-N-[[[(2-naphthalenyl) - methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 50%

sodium alkylnaphthalenesulfonate 2%

low-viscosity methyl cellulose 2%

diatomaceous earth 46%

The ingredients are blended, coarsely hammer-milled and then airmilled to produce particles substantially all below 10 microns in

diameter. The product is reblended before packaging.

Example C

Granule

Wettable Powder of Example A 5%

attapulgite granules 95%

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

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

Example D

Extruded Pellet

2-(dimethylamino)-N-[[[(2-naphthaIenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyI chloride 25%

anhydrous sodium sulfate 10%

crude calcium liginsulfonate 5%

sodium alkylnaphthalenesulfonate 1%

calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

Example E

Oil Suspension

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 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 F

Wettable Powder

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 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 substantially 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 G

Low-Strepgth Granule

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 1%

N,N-dimethylformamide 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 H

Aqueous Suspension

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 10%

polyacrylic acid thickener 0.3%

dodecylphenol polyethylene glycol ether 0.5%

disodium phosphate 1%

monosodium phosphate 0.5%

polyvinyl alcohol 1.0%

water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

Example l

Low-Strepgth Granule

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 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 comp'eted, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example J

Granule

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethaιrimidoyl chloride 80%

wetting agent 1%

crude Hgninsulfonate salt 10%

(containing 5-20% of the natural sugars) attapulgite clay 9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid-bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

Example K

High-Strength Concentrate

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 99%

silica aerogel 0.5%

synthetic amorphous silica 0.5%

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example L

Wettable Powder

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 90%

dioctyl sodium sulfosuccinate 0.1%

synthetic fine silica 9.9%

The ingredients are blended and ground in a hammer-mill to produce particles substantially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged. Example M

Wettable Powder

2-(dimethylamino)-N-[[[(2-naphthalenyl)- rnethoxy]carbonyl]ox y]-2-oxoethanim idoyl chloride 40%

sodium ligninsulfonate 20%

montmorillonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-m i lled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

Example N

Emulsifiable Concentrate

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 35%

blend of polyalcohol carboxyHc 6%

esters and ofi-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 O

Emulsifiable Concentrate

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]ox y]-2-oxoethanimidoyl chloride 20%

chlorobenzene 74%

sorbitan monostearate and polyoxy- 6%

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, Puccinia recpndita,

Puccinia gramminis, Hemileia yastatrix, Puccinia striiformis, Puccinia arachidis, Pyricularia oryzae, Phytophthora infestans, Plasmopara viticola, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Botrytis cinerea, Monilinia fructicola, and other species closely related to these pathogens. They also control seed pathogens. In particular the compounds of this invention are exceptional in their ability to provide control of diseases for an extended period of time after application.

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)

aluminu m 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-dimethyl- morpholine (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-dichlorophenyl)pentyl]1H-1,2,4-triazole (penconazolel 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-dim ethylphenyl)-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-[diethoxyphosphinylim ino]-1,3-diethietane (fosthietan)

S-m ethyl-1-(dim ethylcarbam oyl)-N-(miethylcarbainoyloxy)thio- formimidate (oxamyl)

S-m ethyl-1-carbamo yl-N-(m ethylcarbam oyloxy)thioform imidate

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

Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)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-dim ethylform amidine (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-chloro-alpha-(1-methylethyl)benzene- acetate (fenvalerate)

(3-phenoxyphenyl)methyl 3-(2,2-dichloro-ethenyl)-2,2-dimethylcyclo- propanecarboxylate (permethrin) dimethyl N,N'-[thiobis(N-methylimmo)carbonyloxy]]-bis[ethanimidothioate] (thiodicarb)

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

α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane- carboxylate (cypermethrin)

cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-α-(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]phosphoro- dithioate (azinphos-methyl)

5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate

(pirimicarb)

S-(N-formyl-N-methylcarbamoylmethyl)-O,O-dimethylphosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl) ( 5 )-α-cyano-3-phenoxybenzyl

(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate

(deltamethrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethyl- phenyl)alanine (fluvalinate)

APPLICATION

Disease control is ordinarily accomplished by applying an effective amount of the compound, pre-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 10 g/ha to 10,000 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

agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 hrs., and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.

TEST B

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 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 hrs., 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

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 wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccini a recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 hrs., and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.

TEST D

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 rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 hrs., and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.

TEST E

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 tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infesta ns (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hrs., and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

TEST F

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 wate

rcontaining 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 hrs., moved to a growth chamber at 20°C for 6 days.and then incubated in a saturated atmosphere at 20°C for 24 hrs., after which disease ratings were made.

TEST G

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 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 sa eurated atmosphere at 20°C for 48 hrs., and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Results for Tests A to G 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.

A

TABLE A

*Percent control at 40 ppm the highest concentration tested.

Claims

What is claimed is: 1. Compounds of Formula (I)

wherein:

Y is Cl or SO₂R⁴;

R¹ is

wherein the aromatic rings of R¹ are optionally substituted with methyl, methoxy, nitro or 1-2 halogen; and wherein designations such as:

indicate that substitution at any position is permissible; R² and R³ are independently H or C₁-C₄ alkyl; or R² and

R³ can be taken together along with the nitrogen atom to which they are attached to form a pyrrolidino, piperidino or morpholino group, said pyrrohdino, piperidino or morpholino group being optionally substituted with 1-2 methyl;

R⁴ is phenyl; naphthyl;, C₅-C₈ cycloalkyl; or C₁-C₁₂ alkyl optionally substituted with C₁-C₂ alkoxy, C₅-C₅ cycloalkyl, phenyl or naphthyl;

Q¹ is C₁-C₄ normal alkyl;

Q² is C₁-C₃ normal alkyl optionally substituted with 1-2 methyl, or a direct bond; and geometric and

stereoisomers of the foregoing.

2. Compounds of Claim 1 wherein:

R¹ is

3. Compounds of Claim 2 wherein:

R⁴ is methyl, phenyl or benzyl.

4. Compounds of Claim 3 wherein:

R¹ is naphthylmethyl or naphthyl(2-ethyl).

5. Compounds of Claim 4 wherein:

R² an d R³ are both methyl or R² and R ³ are taken together with the nitrogen atom to which they are attached to form a piperidino group.

6. Compounds of Claim 5 wherein:

Y is Cl.

7. A compound of Claim 1 that is 2-(dimethylamino)-N-[[[(2- naphthalenyl)methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride.

8. An agriculturally suitable composition comprising a fungicidally effective amount of a compound of any one of Claims 1-7 and at least one of the following: surfactant, solid diluent or liquid diluent.

9. A method for controlling fungus disease in plants which comprises applying to the locus to be protected an effective amount of a compound of any one of Claims 1-7.