Hubele CH 66-16,259 claims compounds of Formula ϋ as fungicides for crop protection.

11

Compounds of Formula ϋi 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.

X = halogen ϋi

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

l∑

Compounds of Formula y. 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 ^~ as herbicide safeners.

Ar-SO _n -C-X

N-O-Q

XI

The compounds disclosed as safeners overlap the compounds claimed in Bellina (U.S. 3,819,700) wherein X is C(=0)NR1R2.

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

∑ii

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

(I)

wherein: Y is Cl or S0 ₂ R ⁴ ;

wherein the aromatic rings of R**- 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 R*** ^* are independently H or C1-C4 alkyl; or R2 and R*-* 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

*-*- is C1-C3 normal alkyl optionally substituted with 1-2 methyl, or a direct bond.

Preferred Embodiments

1) Compounds of the Formula (I) wherein: R ¹ is

2) Compounds of Preferred 1 wherein: R"* is methyl, phenyl or benzyl.

3) Compounds of Preferred 2 wherein:

R! is naphthylmethyl or naphthyl(2-ethyl).

4) Compounds of Preferred 3 wherein:

R2 and R*- are both methyl or R*-*- and 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):

' O

\ II o

N- -c

/ :M N.-nOτHι + Cl-C-O-R ¹ + baβe (I)

K-

Mei cd.A

II III

M≤i cd.E

IV

In Method A (Y=C1, SO2R ⁴ ) the carboxamide II reacts with the chloroformate UI 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 zylene; and halocarbons such as chloroform and dichloromethane. Suitable bases include triethylamine, N,N-dϋsopropyl-N-ethylamine, pyridine, N,N-diethylaniline ^* nd N,N-dimethylaniline. The reaction temperature can range from ab _^ t -20 to +50°C, and the reaction time from about 5 minutes to several days depending on -hoice 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 [(R*) ⁺ in this case], most generally for the compounds HI wherein R 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=C1) the oxime chloroformate IV reacts with the alcohol V in the presence of an acid scavenger (base) to form the product (I), with Y=C1. 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-(bromomethvl)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; Rf 0.55).

EXAMPLE 2 Preparation of 2-(hvdroxymethyl)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-naphthvlmetbγl cfrlnrflfoπηp P 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, Rf 0.93.

EXAMPLE 4

Preparation of N-r(chlorocarbonvl)oxv1- 2-(dimethyl3τττino ⁾ -2-n ^* _rn ^p t.h _n n ^* i _T nidovl 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 R* is

Piperidino m.p. 69-71°

Pyrrolidino N _^ N-Diethylamino N-Butyl-N-methylamino

Morpholino 2 ,6-Dimethylmorpholino

EXAMPLE 5 Preparation of 2- ⁽ ^ ^* iτ ^* nethvlamino)-N-rrr(2-naphtha- 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 naphthalenvl)methoxv1carbonvnoxv1-2-oxo^b^niτηidovl chloride To a stirred solution of N-[(cMorocarbonyl)oxy]-2-dimethylamino-2- oxoethanimidoyl chloride (2.48 g) in THF (50 ml) was added 2-(hydroxy- methyl)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 evr urated in vacuum to a white

solid. RecrystaUization was effected from ethyl acetate/hexane, providing

2.86 g (74% of theoretical) of the title compound, m.p. 108-110°. Analysis calculated for CιρHi5ClN ₂ θ4: C, 57.40; H, 4.52; N, 8.37%.

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

EXAMPLE 7

Preparatø ^pp of 3-(m*?thylflτnin )-N-rrr(g-napht-ba- lenvl)methoxv1carbonvloxv1-2-oxoeth animidovl 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-[(chlorocarbonyD- oxy]-2-methylamino-2-oxoethanimidoyl chloride. The IR spectrum of this compound showed absorption at 3296 cm" (NH), 1811 cm"l (chlorocarbonyl) and 1692 cm- (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 HC1, water, saturated sodium bicarbonate solution and saturated brine, then dried (MgSθ4) and evaporated in vacuum to an off-white solid. RecrystaUization from 1-chlorobutane (containing a smaU amount of ethyl acetate) provided the pure title product, m.p. 153-156°. The infrared spectrum of the product showed absorption at 3305 cm"**- (NH), 1794 cm"--- (carbonyl of oxime carbonate), and 1675 cm"l (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-dimethvl-2-r(2-naphthalenvl- methoxv ⁾ carbonvloxvimino1-2-r ⁽ phenvlmethvl ⁾ sulfonvl1a ^p« ?tn ^π lf-i ^p

Into a stirred, nitrogen-blanketed solution of 2-chloro-2-hydrox- imino-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 soUd and temperature rise to 10-15°. After 4 hrs. the mixture was filtered and the filtrate evaporated in vacuum to a white solid. RecrystaUization 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 recrystaUized from acetonitrile, providing the intermediate 2-hydroxim__no-2-benzylsulf'nyl-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), foUowed 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 HC1, water, saturated sodium bicarbonate solution and saturated brine. After drying (MgSθ4) 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.

NR ² R3 K

piperidino 2-naphthylmethyl piperidino 1-naphthylmethyl piperidino 2-(2-naphthyl)ethyl piperidino 2-(l-naphthyI)ethyl pyrrolidino 2-naphthylmethyl pyrrolid no 1-naphthylmethyl pyrrolidino 2-(2-naphthyl)ethyl pyrrolidino 2-(l-naphthyl)ethyl morpholino 2-naphthylmethyl morpholino 1-naphthylmethyl morpholino 2-(2-naphthyl)ethyl morpholino 2-(l-naphthyl)ethyl

2 ,6-dimethylmorpholino 2-naphthylmethyl 2,6-dimethylmorpholino 1-naphthylmethyl

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

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

2-methylpiperidino 2-naphthylmethyl

2,5-dimethylpyrroUdino 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 l,2,3,4-tetrahydro-2-naphthylmethyl dimethylamino 1-indanyl dimethylamino l-methoxy-2-indanyl piperidino 1-indanyl dimethylamino 9-fluorenyl piperidino 9-fluorenyl dimethylamino 9-fluorenylmethyl dimethylamino 2-(9-fluorenyl)ethyl

dimethylamino 3-(9-fiuorenyl)propyl dimethylamino l,6-dibromo-2-naphthylmethyl dimethylamino l,6-dichloro-2-naphthylmethyl dimethylamino 2-indanyl dimethylamino 6-bromo-l-indanyl dimethylaπr 6-chloro-l-indanyl dimethylamino 6-methyl-l-indanyl dimethylamino 6-methoxy-l-indanyl dimethylamino 6-nitro-l-indanyl dimethylamino 5 ,6-dibromo-l-indanyl dimethylamino 2-bromo-9-fluorenyl dimethylamino 3-methyl-9-fluorenyl

2 3 l ⁴

Useful formulations of the compounds of Formula (I) can be prepared in conventional ways. They include dusts, granules, peUets, 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 wiU contain these ingredients in the foUowing approximate proportions:

Weight Percent* Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10

^♦ 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, CaldweU, 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 weU as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., NewYork, 1964, list surfactants and recommended uses. AU formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc. The methods of making such compositions are weU 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 peUets 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-HiU, 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.,

BlackweU Scientific Publications, Oxford, 1968, pp. 101-103.

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

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

E ample 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-miUed until aU the solids are substantially under 50 microns, reblended, and packaged.

fiγflτrιp

Wettable Powder 2-(dimethylamino)-N-[[[(2-naphthalenyD- 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 air- milled to produce particles substantially all below 10 microns in diameter. The product is reblended before packaging.

ETrømp)-? -

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.

ynm k P s -uded PeUet

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 peUets about 3 mm long. These may be used directly after drying, or the dried peUets may be crushed ϊo 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.

xgror F

OU Suspension

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]oxy]-2-oxoethanimidoyl chloride 25% polyoxyethylene sorbitol hexaoleate 5% highly aUphatic 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 ceUulose 3% attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles substantially aU 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 Granμl*? 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 aUowed to run for a short period and then the granules are packaged.

Example H

Aqueous Suspension

2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyljoxy]-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 essentiaUy aU under 5 microns in size.

fiftλmp ¹ -? T ow-§trepg h 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.

xample .7 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, optionaUy with heat, untU the water content is reduced to the desired level, generaUy 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.

F- ^y pm l ^p 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 aU 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 sUica 9.9%

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

Ex m le M

Wettable Powder

2-(dimethylam__no)-N-[[[(2-naphthalenyl)- rnethoxy]carbonyl]θ3ζy]-2-oxoethani_t_jidoyl chloride 40% sodium Hgninsulfonate 20% montmoriUonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-nulled and then air-milled to produce particles essentiaUy aU below 10 microns in size. The material is reblended and then packaged.

Exam le N ffmμlgifiabte CQflcenfrate 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.

Fyflrn l O

Emulsifiable Concentrate 2-(dimethylamino)-N-[[[(2-naphthalenyl)- methoxy]carbonyl]o- 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 Basidiomvcete. Ascomycete and Oomvcete 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. Cercospora arachidicola. Cercospora beticola. Pseudocercosporella herpotrichoides. Puccinia recpndita, Puccinia grnmminig. Hemileja vastatrix. Puccinia striiformis. Puccinia arachidis. Pyricularia oryzae _t Phvtophthora infestans. Plasmopara viticola. Peronospora tabacina. Pseudoperonospora cubensis. Pyt*bi p l-.--i-n-it-l rTnf_t.nm , Botrvtis 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) l,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan) N-trichloromethylthiophthalimide (folpet) dimethyl 4,4'-(o-phenylene) bis (3-thioaUophanate) (thiophanate-methyl) 2-(thiazol-4-yl)benzimidazole (thiabendazole) alumi iiiQ 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-[l ,1,2 ,2-tetrachloroethyl)thio]cyclohex-4-ene-l ,2-dicarbioximide (captafol)

3-(3 ,5-dichlorophenyl)-N-( l-methylethyl)-2 ,4-dioxo-l-imidazoUdine carboxamide (iprodione) 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedio ne (vinclozolin) kasugamycin

O-ethyl-S ,S-diphenylphosphorodithioate (edifenphos) 4-(3-(4-(l,l-dimethylethyl)phenyl)-2-methyl)propyl-2,6-dimet hyl- morpholine (fenpropimorph) 4-(3-4(l,l-dimethylethyl)phenyl)-2-methyl)propylpiperidine (fenpropidine) l-(4-chlorophenoxy)-3,3-dimethyl-l-lH-l,2,4-triazol-l-yl)but anone (triadimefon)

2-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-ylmethyl)hexanen itrile

(myclobutanil) l-[2-(4-chlorophenyl)ethyl]-l-(l,l-dimethylethyl)-l-(lH-l,2, 4-triazole- l-yl)ethanol (tebuconazol) 3-chloro-4-[4-methyl-2-(lH-l,2,4-triazol)-l-ylmethyl)-l,3-di oxolan-

2-yl]phenyl-4-chlorophenyl ether (difenoconazole) l-[2-(2,4-dichlorophenyl)pentyl]lH-l,2,4-triazole (penconazole)

2,4'-difluoro-l-(lH-l,2,4-triazole-l-ylmethyl)benzhydryl alcohol (flutriafol) l-[[[bis(4-fluorophenyl)]methylsUyl]methyl]-lH-l,2,4-triazol e (flusUazole) N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]__midazole-l-car boxamide (prochloraz) l-[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2-ylmethyl]- lH-

1,2,4-triazole (propiconazole) l-(2-chlorophenyl)-l-(4-chlorophenyl)-l-(5-pyrimidin)methano l (fenarimol) l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazole-l-yl)b utan-2-ol (triadimenol) l-(2,4-dichlorophenyl)-4,4-dimethyl-2-(lH-l,2,4-triazol-l-yl )pentan-3-ol (diclobutrazol) copper oxychloride methyl N-(2,6-din_ιethylphenyl)-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-l,3-dithiolo[2,3-B]quinonoUn-2-one (oxythio-quinox)

2 ,2 ,2-trichloro-l , l-bis(4-chlorophenyl)ethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-l-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide)

Nematicides

2-[diethoxyphosphinylύ_αino]-l,3-diethietane (fosthietan) S-n_iethyl-l-(diinethylcarbanioyl)-N-(miethylcarbainoyloxy)t hio- formimidate (oxamyl) S-nιethyl-l-carban_u)yl-N-(nιethylcarbaπιoyloxy)t__ oforn__imidate N-isopropylphosphoramidic acid, 0-ethyl-0'-[4-(methylthio)-m- tolyl]diester (fenamiphos)

Insecticides 3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-d_lhydro-2,2-dimethyl-7-benzofuranol (carbofuran)

0-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, 0',0'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, 0,0-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-diπιethylforπιamidine (chlordimeform) 0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothi oate

(diazinon) octachlorocamphene (toxaphene) O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenox3 henyl)-methyl 4-chloro-alpha-(l-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[ethanimido- thioate] (thiodicarb) phosphorothiolothionic acid, 0-ethyl-0-[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) 0 ,0-diethyl-0-(3 ,5 ,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) 0,0-dimethyl-S-[(4-oxo-l,2,3-benzotriazin-3-(4H)-yl)methyl]p hosphoro- dithioate (azinphos-methyl)

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

(pirimicarb) S-(N-formyl-N-methylcarbamoylmethyl)-0,0-dimethylphosphoro- dithioate (formothion) S-2-(ethylthioethyl)-0,0-dimethyl phosphiorothioate (demeton-S-methyl) ( 5 )-α-cyano-3-phenoxybenzyl (lR,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxy late

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

APPLICATION

Disease contrt . 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 (soU 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 normaUy 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 normaUy be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

TESTA

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 foUowing day the seedlings were inoculated with a spore suspension ofVenturia inaequalis (the CF d agent of apple scab) and incubated in a saturated atmosphere at υ°C for 24 hrs., and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.

TEST ff 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 nf CfT ^R ftFPffrid,Hl ^m p rFftnqt"™ (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 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 foUowing day the seedlings were inoculated with a spore suspension of Purr-in..*, 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.

XESXJ 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.

_____ L

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 foUowing day the seedlings were inoculated with a spore suspension causal agent of potato and tomato late bUght) 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.

XESILE The test compounds were dissolved in acetone in an amount equal to 3% of the final volu ^m e and then suspended at a concentration of 200 ppm in purified water ~ ntaining 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The foUowing 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 foUowing 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 sε 'irated 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.

INDEX TABL D

£ EE NR ² fi ³ — -E ¹ -

1-naphthylmethyl

2-naphthylmethyl

2-(2-naphthyl)ethyl

2-(l-naphthyl)ethyl

2-methyl- 1-naphthylmethyl l-bromo-2-naphthylmethyl

2-naphthylmethyl

1-naphthylmethyl

2-(l-naphthyl)ethyl

2-naphthylmethyl

2-(2-naphthyl)ethyl

2-naphthylmethyl

2-(l-naphthyl)ethyl

2-naphthylmethyl l,2,3,4-tetrahydro-2-naphthyl

___________

Cmpd TEST TEST TEST TEST TEST TEST TEST flα _* - -. _E_ _£_ -Ω- _E_ _E_

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

*Percent control at 40 ppm the highest concentration tested.