DE2635967A1 - 2-CYANACETAMIDE DERIVATIVES AND THEIR PRODUCTION AND APPLICATION - Google Patents

Description

263596?

Patent attorneys:
Dr. Ina. WaÜer Äbitz

Dr DleterF.Horf - ¹⁰

Dr. Hans-A. Braun's BA-8123

Künchöii OC ₁ Pieozoiuiaaiär. 28

EI du Pont de Nemours and Company 10th and Market Streets ₃ Wilmington, Del. I9898, V.St.A.

2-cyanoacetaniide derivatives and their preparation

and application

The invention relates to fungicidal compounds and their use in combating plant diseases.

Many commercial formulations are available for combating fungus diseases in plants. But newx ¹ fungicide is needed to better combat specific plant diseases and also to be able to combat fungi strains that do not respond or do not respond correctly to products on the market. The compounds according to the present invention are particularly effective against certain Phycomycetes, e.g. B. with late blight in tomatoes and potatoes and downy mildew in vines. Unlike many commercially available products, the compounds according to the invention not only result in a compound of the fungus attack on plants, but they are also able to inactivate the fungus after the plant has been attacked.

The invention relates to compounds of the formula

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ORIGINAL

BA-8123/263596?

ο ο

E-IIH-C-NH-C-C-C] J

(I)

wherein E is CH ₅ OCH ₂ -, CH ₅ O (CH ₂ ) ^ -, cyclopropyl or cyclopropylmethyl and E ^, alkyl of 1 or 2 carbon atoms. These compounds are suitable for combating fungus diseases in plants. Disease control includes the prevention, inhibition and / or eradication of plant disease.

The compounds according to the invention can be applied to plants to prevent fungi from infesting the plants. The compounds are not in their effect only preventive, but also systemic and curative, d. H. the compounds are absorbed by plants and migrate in the plants. In this way, they are also able to inactivate a fungus that has already attacked the plant. Since the If compounds are systemic, they can not only be applied to the infected or threatened parts of the plant, but also on non-infested parts or on the floor in which the Plant grows. All of these application or delivery locations should be encompassed by the term "application to the plants".

The fact of being systematic makes the connections in accordance with of the invention particularly well suited for combination with conventional preventive fungicides. The fungicides according to of the invention can thus also essentially consist of a fungicidally active amount of a compound according to the invention plus consist of another fungicidally active ingredient. The agents can also contain conventional formulation substances.

Because of their fungicidal activity, the compounds according to the invention with E, are preferred. equal to methyl,

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263596?

2-cyano-2-methoxyimino-N-methoxymethyl carb amoyl acetamide, 2-cyano-2-methoxyimino-N- (3 ' -methoxypropyl) -carb amoylacetamide, 2-cyano-'li-cyclopropylcarbamoyl-2-met] ioxyiminoacetamide and 2-cyano-N-cyclopropylmethylcarbamoyl-2-methoxyimino acetamide.

The invention is described in detail below.

The new compounds according to the invention can be conveniently Manufactured in two different ways.

In the first way, 2-cyano-2-methoxyiminoacetamide (0. Diels and E. Borgwardt, Ber. 54, 1342 (1921) or a corresponding higher alkoxyimino homologue of this starting material is converted into the anion of the amide, e.g. using sodium methoxide or Sodium hydride in a suitable inert solvent such as tetrahydrofuran This anion is reacted with an isocyanate E-NCO, where E is CH ^ QCHo-, CH ^ OCCH ^) ^ -, £> - or £> -CH ₂ -. This reaction gives the anion of the product; the product is obtained by acidification in an aqueous medium.

The second way is an amine E-EB ^ by means of a cyanate, such as potassium cyanate, converted into the corresponding urea and the urea with cyanoacetic acid and acetic anhydride to form a cyanoacetylurea of the general formula

HH
-CN-

n ■
OO

HNCNC-CH ₀ -CN

ti "M £ -

implemented.

This intermediate compound is then converted into the oxime by methods known per se using sodium nitrite or an appropriate alkyl nitrite. The hydroxyimino group is alkylated according to methods known per se, e.g. Example, by converting to the sodium salt by means of sodium methoxide using dimethylformamide as solvent and additive

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BA-8123 ty 2635 96?

of the corresponding alkylating agent. To appropriate Alkylating agents include alkyl iodides and bromides. Dialkyl sulfates can also be used.

The compounds according to the invention are suitable as agents to combat plant diseases. Most of them, when applied to the ground, to propagation pieces, on stalk or on foliage as qualities systemic and curative activity. Combinations with other fungicides, especially those with strong persistent properties provide particularly exceptional disease control. the systemic and curative effects of the control agents according to the invention make a unique contribution to such Combinations represent. One will for this reason means that besides a compound according to the invention also another youngicide contain, often prefer. The systemic property of the compounds according to the invention is more striking Way in the fight against late blight in potatoes and tomatoes appear when treatments with the compounds are applied to the root system alone. Further signs result from the curative effect against established ones Infestation by those responsible for late blight or downy mildew in grapes. The disease leaves inhibit even if treatments are delayed for hours after the plants are infected.

Of the fungi that cause diseases in agricultural crops cause, those of the Phycomycete class are among the most virulent. To those through this group Fungi-induced disorders include late blight from tomatoes and potatoes as well as downy mildew from Heben. Cabbage plants, legumes and pumpkins. By Diseases caused by Phycomycetes are particularly accessible to control by the compounds according to the invention.

The compounds according to the invention result on application to the right place according to the methods described later

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with sufficient dosage to achieve the desired effect, Protection against damage from certain fungi. They are suitable for protecting living plants by applying to the Soil in which these grow or in which they can then be introduced by sowing or planting, on seeds, Tubers, bulbs or other parts of the plant reproductive system before they are placed in the soil or on the foliage, The stem and / or the fruit. Soil applications are made with dusts, granules, pellets, solutions, emulsions or Slurries.

Preferred dosages for applying the compounds of the invention to soil in which plants grow or will grow range from 0.5 to 500 parts by weight per million parts (ppm) of the soil in which the roots are or will be grown. More preferred application dosages are in the range from 1 to 200 ppm, dosages in the range from 5 to 100 ppm are particularly preferred. Preferred dosages for application to seeds, onions, tubers or other parts of plant reproduction are in the range of 0.5 to 100 g of active compound according to the invention / kg of treated planting stock, with dosages in the range of 1 to 73 g of active compound / kg being more preferred and those im Range from 2 to 50 g / kg are particularly preferred. Applications of this type are made with dusts, slurries, emulsions or solutions.

Preferred dosages for applying the compounds according to the invention to the foliage, the stems and / or the fruit of living plants range from 0.05 to 20 kg active ingredient / ha. Dosages in the range from 0.1 to 10 kg / ha are more preferred. Dosages in the range from 0.2 to 5 kg / ha are particularly preferred. The optimal amount in this Range depends on a number of variables familiar to the crop protection specialist. The variables include the disease to be combated, the expected weather conditions, the type of hat culture, the stage of development

709811/1108

the culture and the time interval between applications, but this is not an exhaustive list. In the case of applications In this area, a single or multiple recovery time at intervals of 1 to 60 days may be necessary. The. Applications are made with dusts, slurries, Emulsions or solutions.

The agents according to the invention can be via the active ingredient according to the invention also conventional insecticides,

Mitesicides, Bacterialides, Nematicides, Fungicides or other chemicals for agricultural purposes, such as agents that affect fruit set, fruit thinning agents * « tel, fertilizer ingredients and the like. Combinations with other fungicides are often preferable, especially Maneb, Captafol and Chlorthalonil. The additional agricultural chemicals are in mixtures or Combinations are used in amounts ranging from one to twenty times that of the compound (s) according to the invention. A pest control specialist can make the right choice of the additional chemical and its quantities hit easily. Explanation of the agricultural chemicals that are in agents with the compounds submitted according to the invention or, in addition, the spray materials, the one or more of the active compounds according to the invention contain, can be added, serve.

Bis (dimethylthiocarbamoyl) disulfide or tetramethylthiuram disulfide (Thiram),

Metal salts of Ä'thylenbisdithiocarbamic acid or propylenebis-dithiocarbamic acids, e.g. B. Manganese, zinc, iron and sodium salts (Maneb or Zineb),
n-Dodecylguanidine acetate (Dodine)
■ N- (Trichloromethylthio) -phthalimid (Folpet) N- / CTrichloromethyl) -thio7-4-cyclohexene-1,2-dicarboximide (Captan) cis-IT- / £ i, 1,2,2-tetrachloroethyl) -thio7- 4-cyclohexene-1,2-dicarboximide (Captafol)

709811/1108

2,4-dichloro-6- (o ~ chloroaniline) - s-triazine ("Dyrene") 3,3'-Ethylenebis (tetrahydro- ^, 6-dimethyl-2H-i, 3? 5-thiadiazin-2-thione) (Milneb)

Triphenyltin hydroxide (fentin hydroxide) Triphenyltin acetate (etin acetate)

N '-Dichlorofluoromethylthio-N, N-dimethyl-N' -phenyl sulfamide (Dichlofluanid)

Tetrachloroisophthalonitrile (chlorothalonil) tribasic copper sulfate

fixed copper

sulfur

Methyl 1- (butylcarbamoyl) -2-ben2; imidazole carbamate (benomyl) Methyl 2-benzimidazole carbamate

Ί, 2-bis- (3-Hethoxycarbonyl-2-thioureido) -benzene (methylthiophanate)

The above agricultural chemicals are merely exemplary of the compounds that are used with the Active compounds according to the invention can be mixed, and the invention is not limited to them »-

When using pesticides in combination with a compound within the scope of the invention occurs variously a strong increase in the activity of the active compound according to the invention in appearance. If another pesticide is used in the method according to the invention, one is variously unexpected activity level observed.

Formulations with the compounds according to lOrmel (I) are can be produced in conventional ways. They include dust, Granules, pellets, solutions, suspensions, emulsions, wettable Powders, Emulsifiable Concentrates, and the Like · Many these formulations can be applied directly. Injectable ! Formulations can be used with appropriate media extended and in injection volumes from a few liters up to several hundred liters / ha can be used. Highly concentrated

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Agents serve primarily as intermediate materials for further formulation. In general, the formulations contain about 1 to 99% by weight of active ingredient (s) and a) about 0.1 to 20 % surface-active agents and / or b) about 5 to 99% solid or liquid diluents . Specifically, the formulations may contain these ingredients in the following approximate proportions:

Active ingredient Weight%
Dilution
middle Surface
chenakti
ve ^) with
tel Wettable powders 20-90 0-74 1-10 Oil suspensions, emul
sions, solutions
(including emul-
yawable concentrates) 5-50 40-95 0-15 Aqueous suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and pellets 1-95 5-99 0-15 Highly concentrated means 90-99 0-10 0-2

Naturally, depending on the intended purpose and the physical properties of the compound also present larger or smaller amounts of active ingredient. Once in a while higher ratios of surfactant to active ingredient are desired; you can do them by presenting them in the wording or mixing in the tank, oils and humectants can also be included in the formulation or mixed in the tank.

Typical solid diluents are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers," 2nd Ed., Dorland Books, Caldwell, N.J. - described. For wettable powders become the more absorbent diluents and for. Dusts the denser ones preferred. Typical liquid diluents and solvents are in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. For Sus-

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BA-8123

pension concentrates a solubility of less than 0.1 % is preferred; Solution concentrates are preferably resistant to phase separation at 0 ° G. Surfactants and application recommendations can be the "McCutscheon ¹ s Detergents and Emulsifiers Annual," MC Publ. Corp., Bidgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents," Chemical Publ. Co., Inc. , Hew York, 1964-. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion and microbiological growth, to control pH, etc.

The methods of forming such funds are familiar. Solutions are made by simply mixing the ingredients. ! Fine solids are made by mixing and usually grinding, as on a hammer or jet mill. Suspensions are made by wet milling (see e.g. U.S. Patent 3,060,084). Korngut and pellets are available by the active material is sprayed onto pre-formed grain carriers or using Agga diner techniques. In this respect be on J. E. Browning, "Agglomeration," Chemical Engineering, Dec. 4, 1967, pp. 14-5 ff., and "Perry's Chemical Engineer's Handbook, "4th Ed., McGraw-Hill, N.Y., 1963, pp. 8-59 ff.

For more information on the formulation technique, see

z. B. referred to:

U.S. Patent 3,576,834, column 5, line 36 through column 7, line 70, and Examples 1 to 4, 17, 106 and 123 to 140, U.S. Patent 3,560,616, column 3 ,. Line 48, to column 7, line 26, and Examples 3 to 9 and 11 to 18, .. ·

Chapter 6 (E. Somers, "Formulation") in Torgeson, "Fungicides", Vol. I, Academic Press, New York, 1967 · ·

The following examples serve to further illustrate the invention. All parts and percentages relate to the weight.

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example 1

Preparation of 2-cyano-ff-cyclopropylcarbamoyl-2-metho: ^ iiainoacetamide

57 g Cyclopropylharnstoff (Chem. Abstr., 62, 2319), 54 heated g "Gyanessigsäure and 115 ^m l of acetic anhydride were heated with stirring on a steam bath. Upon reaching a temperature of the mixture of 85 ° evolved heat of reaction and was cooled from the outside, After stirring for one hour on the steam bath, the mixture was cooled and the cyanoalkylurea recovered by filtration, washing with ether and drying, the yield was 66 g, mp 170-172 °.

63 1/2 g of the above urea was dissolved in 250 ml of acetic acid suspended. The suspension was cooled to 10 ° and added dropwise with stirring with a solution of 46 g of sodium nitrite in 68 ml ^ O. After stirring overnight, the thick suspension was added with stirring and cooling in ice 32 ml of concentrated hydrochloric acid were added dropwise 2-cyano-N-cyclopropylcarbamoyl-2-hydro2 ^ minoacetamide was filtered off, washed with water and ether and dried. The yield was 64 g; 210-212 ° F.

The above oxime was used in an amount of 3 »9 g in 30 ml Dissolved acetone, including 1.6 g of powdered, anhydrous potassium carbonate and 2.2 ml of dimethyl sulfate were added. The mixture was refluxed with stirring for 2 hours and then chilled in ice. The product was precipitated by adding ice water. After filtering, washing with water and ether and drying, the product weight was 3 »8 g. The recrystallization from absolute alcohol gave 3j2 g of 2-cyano-N-cyclopropylcarbamoyl-2-methoxyiminoacetamide, F. 181.5 to 182.5 °

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70981 1/1108

BA-8123 **

Example 2

Preparation of 2-cyano-l · ϊ-cyelopropylmethylcarbamoyl-2-methoxyiminoacetamide

50 g cyclopropylmethylamine HCl (Columbia Organic Chemicals Co.) were dissolved in 160 ml of water. With stirring was added in proportions Potassium cyanate added in an amount of 57 g. The solution was then heated on a steam bath 3 Ii. The mixture was evaporated to dryness in vacuo and the solid residue extracted exhaustively with boiling, absolute ethanol. The combined extracts were concentrated in vacuo; the desired Cyclopropylmethylurea has been used in consecutive Lots isolated. 116 to 118 °; Yield 27.5g

26 g of the above urea were stirred on the Steam bath for 1 h with 21.4 g of cyanoacetic acid and 46 ml of acetic anhydride heated. When the mixture reaches a temperature from 85 ° there was a certain heat development. the Mixture was then cooled, filtered, washed with ether and dried. The yield was 26 g; F. 156 to 158 °.

The above cyanoacetylurea was slurried in an amount of 24 x g in 100 ml of acetic acid. The slurry was stirred at about 15 and a solution of 16.5 g NaNOp in 24 ml H ₀ O was added dropwise. After stirring overnight at room temperature, the thick slurry was treated dropwise with 11 ml of concentrated hydrochloric acid while cooling. The desired hydroxyimino compound was collected on a filter, washed with ice water and ether, and dried. 25 g of ^ -Cyan-N-cyclopropylmethyl-.:. carbamoyl-2-hydroxyiminoacetamide. which melted at 200 to 202 °.

The above oxime was used in an amount of 3> 1 g generally 25 ml Dissolved acetone. Powdered, anhydrous KoCO, (1.2 g) and dimethyl sulfate (1.7 ml) added, and the mi

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BA-8123 * β 26359b /

The mixture was stirred and refluxed for 2 hours. The product was made by adding ice water to the cooled reaction mixture failed. After filtering, washing with ice water and ether and drying, 2.4 g of product were obtained. Uaeh Uracrystallization from absolute ethanol there were 2.2 g of product in the form of ^ -Cyan-II-cyclopropylmethylcarbamoyl ^ -metho ^ iiainoacetamide before which melted at 148.5 to 149.

Similarly, the following compounds are available:

2-cyano-N-cyclopropylcarbamoyl-2-etho: xyiminoacetamide, m.p. 136.5 to 138 °, and 2-cyano-H-cyclopropylmethylcarbamoyl-2-ethoxy ~ imino acetamide.

Example 3

Preparation of 2-cyano-2-methoxyimino-U- (methoxymethylcarbamoyl) -acetamide

A suspension of 2.70 g of 2-cyano-2-methoxyiminoacetamide in 10 ml of tetrahydrofuran was mixed with 1.20 g of a 55% suspension of sodium hydride in mineral oil while stirring offset. Subject to stirring for 15 minutes, 2.40 g of methoxymethyl isocyanate was added dropwise. To ensure a the mixture was at 50 ° C. for 3 min to complete the reaction touched. The mixture was then cooled in an ice bath and stirred rapidly with a solution of 1.9 ml of acetic acid added in 120 ml of ice water. After stirring for a further 25 min The duration was the 2-cyano-2-methoxyimino-II-methoxyπlethylcarbamoylacetamid collected on a filter, washed with water and ether and dried. The product was in a lot of 2.7 g before and melted at 163.5 to 165 ° C.

Example 4

Production of 2-cyano-2-methoxyimino-IT- (3 ^l -metho2ypropyl) -carbamoylacetamide __ __2

Methoxypropylamine and potassium cyanate became 3-methoxypropyl-

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βδ-8123 43 263596 /

urea produced. 76 g of this product was mixed with 43 g of cyanoacetic acid and 100 ml of acetic anhydride. The mixture was heated on a steam bath with stirring. When the mixture reached a temperature of 85 °, heat of reaction developed and was cooled from the outside in order to keep the temperature under control. ÜAfter stirring for one hour on the steam bath, the mixture was cooled. The cyanoacetylurea was recovered by filtration, washing with ether and drying. Yield 77> 5 g; S ¹ * "128.5 to 130.5 ° <

70 g of the above urea was dissolved in 560 ml of acetic acid suspended. The suspension was cooled to 5 to 10 ° C and slowly while stirring with a solution of 42 g of sodium nitrite added to 65 ml ILjO. Wake up stirring overnight were slow 35 ml of hydrochloric acid are added. The solution was concentrated to dryness in vacuo. The residue was about the same size Triturated volume of water and chilled in ice. Filtration, washing with ice water and drying made the 2-cyano-2-hydroxyimino-li (3'-methoxypropyl) carbamoylacetamide obtained that was sufficiently pure for use in the next stage.

The hydroxyimino compound was ia in an amount of 4.5 g Dissolve 25 sal acetone and add 1.6 g of powdered, anhydrous Potassium carbonate and 2.2 ml of dimethyl sulfate were added. The mixture was heated to reflux conditions and stirred for 2 hours and then chilled in ice and treated with ice water. The failing one Product was filtered off, washed with water and ether and dried. Yield 4 g; F. 126 to 127 °.

Example 5

The reaction of 2-cyano-2-hydroxyiminoacetamide with a Ethylating agents, such as diethyl sulfate, in the presence of a base, like potassium carbonate, in an inert solvent like acetone, leads to 2-ethoxyimino-2-cyanoacetamide, by reacting it with methoxymethyl isocyanate according to the method of Example 3

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the 2-cyano-2-ethoxyimino-F-methox; 7-methylcarbamoylacetamide ₁ F. 124 to 125 ° G is obtained.

E.g. example 6

The reaction of 2-cyano-2-hydroxyimino-N- (3 '- methoxypropy) -carbamoylacetamide with diethyl sulfate according to the method of Example 4 gives 2-cyano-2-ethoxyimino-] J- (3 ^f -methoxypropyl) - carbamoylacetamide.

Example 7

A wettable powder formulation was prepared and used as follows:

2-cyano-U-cyclopropylcarb amoyl-2-

methoxyimino acetamide 50

Sodium alkyl naphthalene sulfonate 2

Mederviscose methyl cellulose 2

Kieselguhr 46

The ingredients were mixed, roughly hammer milled and then air milling to form active ingredient particles which were essentially all less than 20 microns in diameter. The product was before packing mixed again.

All compounds according to the invention are formulated analogously. bar.

This formulation was in'Wasser in a sufficient amount dispersed to obtain a concentration of the active compound according to the invention of 400 ppm. The dispersion was up sprayed onto tomato plants in pots to run off and left to dry. Both. Treated and untreated plants were with a spore suspension of

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BA-8123 15

Phytophthora infestans inoculated and one day in a chamber incubated with a moisture-saturated atmosphere. Each f? Days further incubation in the greenhouse were all untreated Tomato plants died due to disease from late blight. The plants treated with the dosage of 400 ppm were healthy and showed little signs of illness. If you have the 2-cyano-H-cyclopropylcarbamoyl-2-metho: xyiminoacetamide by the N-cyclopropylmethyl-, N-methoxy-methyl- or replacing N-methoxypropyl compound, the same results. ■

Example 8

The formulation of Example 7 was in a spray tank mixed with the fungicide Benomyl. This wording was diluted to an active ingredient concentration of 500 ppm. The benomyl in the mixture should be at a concentration of 100 ppm are present. During the growth period, a cucumber field was sprayed weekly until it ran off to prevent the infestation due to downy mildew fungus (Pseudopersonospora cubensis), powdery mildew fungus (Erysiphe chichoracearum) and the gum stem rot fungus (Mycosphaerella citrullina) was exposed. The plants sprayed with this mixture were healthy and bore normal fruit, while the non-sprayed plants were damaged by one or more of the fungi mentioned.

B ei s ρ i e 1 9

Potted greenhouse grown tomato plants were used inoculated by spraying with a spore suspension of P. infestans and 20 h at 20 ° C in a chamber with moisture-saturated Atmosphere incubated * The infected tomato plants were for the time required for spraying with different Disease control was necessary out of the incubation skammer removed. The compounds named below were used in an active ingredient concentration of 400 ppm

'- 15 7 0 9 8 11/110 8

dispersed. Three infected plants were sprayed with enough dispersion to prevent runoff from dry plants to obtain. After the treatment, the plants were placed in a greenhouse for an additional five days for incubation. The untreated Plants had died due to disease from dry rot. The treated plants were on the Percentage of healthy foliage (disease control in%) assessed. The following table shows the curative effect of the compounds according to the invention.

Disease Control Compound, %

2- cyano-U-cyclopropylcarbeamoyl-2-methoxyiminoacetamide 100

2-cyano-2-methoxyimino-Itf-methoxymethylcarbamoylacetamide 96

2- cyano-N- cyclopr opylmethyl-

carb amoyl-2-methoxyimino ac et ami d 100

2- cyano-2-methoxyimino -ΪΓ-methoxypropylcarbamoylacetamide 99

Water treatment (control sample) 0

Example 10

A wettable powder formulation was prepared as follows:

2-cyano-H-cyclopropylcarbamoyl-2-ethoxyiminoacetamide 80

Sodium alkyl naphthalene sulfonate 2

Sodium lignosulfonate 2

synthetic amorphous silicon dioxide 3

Kaolinite '13

The ingredients were mixed thoroughly, passed through a hammer mill to an average particle size-of form below 40 microns, remixed and through one

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Sieve with 0.3 mm openings (US sieve row sieve No. 50) passes, before the packing took place.

This formulation was used as follows: A potato field was selected in which there was a uniform but slight infestation by the late blight pathogen and in which the older foliage of each plant had one or two lesions due to spore-forming Phytophthora infestans. While the plant damage at this point can be classified as slightly thin, the potential for the disease to spread is great. Plots were randomly distributed over the field, five were wide and 20 m long and were assigned certain treatments; Between treated plots, a large part of the field that was not treated remained as a buffer. To be carried out immediately after the onset of weather conditions favorable for the disease to spread, a number of treatments have been provided, including treatment with the formulation of the present example dispersed in water at a concentration of 300 ppm active ingredient. For other treatments, a representative selection of commercially available fungicides with their recommended application dosages was provided, such as maneb, captafol and chlorothalonil. In addition to these uses of isolated compounds, combinations of the formulation of the present example with each of the commercial fungicides were used in dosages equal to half the dosage when used alone. Spray applications were made immediately after overnight rain, which has the ability to spread the disease . After one to two weeks, the untreated foliage of the field was completely destroyed by disease from late blight. The plots treated with commercial fungicides showed severe disease and defoliation of about 80 %. The plots to which the formulation of the present example was added were protected from disease from late blight and showed only light foliage «

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loss of work. The parcels made with the combination of the formulation of the present example and a commercial fungicide were healthy and of active disease free.

The other compounds according to the invention can be found in use accordingly.

Example 11

A wettable powder was made as follows:

2-cyano-2-methoxyimino-M-methoxy-

methylcarbamoylacetamide 80

Sodium dioctyl sulfοsuccinate 1

Sodium lignin sulfonate 2

Attapulgite 17

The ingredients were blended and passed through a hammer mill fitted with a coarse sieve. After being mixed again, the material was finely ground on a hammer mill and packaged.

Greenhouse grapevines were inoculated with a trace suspension of Plasmopara viticola (downy mildew) by spraying. Subject of 20-hour incubation in a chamber at 20 ° C. with a moisture-saturated atmosphere, 6 plants were sprayed until they ran off with the above formulation dispersed in water to a level of Ϊ00 ppm of active ingredient. Analogous plants were treated with maneb at an active ingredient concentration of 2000 ppm. After two weeks of incubation in the greenhouse, the untreated plants and plants treated with maneb were severely infested with downy mildew (infestation of about 90 % of the susceptible leaves). Plants treated with the above formulation were disease-free, which shows the curative effect.

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B e i s ρ i e 1 12

Wettable powder %

2-cyano-N- (3'-methoxypropyl) -carbamoyl-2-methoxyiminoacetamide 40

Dioctyl sodium sulfosuccinate 1.5

Sodium lignosulfonate 3

Low viscosity methyl cellulose 1 »5

Attapulgite 54

The ingredients were thoroughly mixed by an air mill led to an average particle size of train below 15 microns, mixed again and through one Sieve with 0.3 mm openings passed before packing.

All compounds according to the invention can be formulated in this way.

Example 13

Wettable powder%

2-cyano ~ II-methoxymethylcarbamoyl-

2-methoxyimino acetamide 80

Sodium alkyl naphthalene sulfonate 2

Sodium lignosulfonate 2

Synthetic amorphous silica 3

Kaolinite 13

The ingredients were mixed and then passed through a hammer mill guided to form such a particle size, that 95% of the particles were finer than 44 microns (Net-Screen 325 of the US sieve series). After passing through a sieve with 0.3 mm openings (US No. 50 sieve series) the product was packaged. .

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Example 14-

oil suspension%

2-cyano-F-methoxymethylcarbamoyl-2-methoxyiminoacetamide 25th

Polyoxyethylene sorbitol hexaoleate 5

Strong aliphatic hydrocarbon oil 70

The ingredients were ground together on a sand mill, until the particulate matter was reduced to below about 5 microns. The resulting, thick suspension can be applied directly, but is preferably extended beforehand with oils or emulsified in water.

Example 15

Dust %

2-cyano-II-methoxypropylcarbamoyl-2-methoxyiminoacetamide 10

Attapulgite 10

Pyrophyllite 80

The active ingredient was mixed with the attapulgite and then through passed a hammer mill to obtain particles substantially all finer than 200 microns. The ground Concentrate was then mixed with the powdered pyrophyllite until homogeneous.

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Claims (8)

I " Claims Compound of the formula OO R-NH-G-NH-C-C-GN wherein E is CH ₅ OCH ₂ -, CH ₅ O (CH ₂ ) ^ - _r cyclopropyl or cyclopropylmethyl and E _{1 is} alkyl of 1 to 2 carbon atoms. 2. Compound according to claim 1, characterized in that E _{1 is} methyl. 3. An agent suitable for inhibiting fungal disease in plants, consisting essentially of a compound according to claim 1. 4-, means according to claim 3 * characterized in that E. Is methyl. 5. method of protecting plants from fungus disease, characterized in that one on the plants Applying a compound according to claim 1 in an amount sufficient to inhibit the fungus disease. 6. The method according to claim 5 *, characterized in that one works with E ₁ equal to methyl. 7. Process for the preparation of a compound of the formula 0 0 CN
E-NHCNHC-C = N-OR ₁ , wherein E is CH ₅ OCH ₂ -, ΟΗ, ΟζΟΗ ^ -, cyelopropyl or cyclopropylmethyl and E _{1 is} methyl or ethyl, thereby marked - 21 709811/110 8th draws that one is a compound of the formula O OCN R - NHCiJHCC = NOH where R has the above meaning with R ^ X or (R ^^ where R _{1 has} the above meaning and X is halogen, preferably iodine or bromine, is reacted. 8. Process for the preparation of a compound of the formula 0 0 CN RNHCNHC-C = NOR ₁ , wherein R is CH ₅ OCH ₂ -, CH ₅ O (CH ₂ ) ^ -, cyclopropyl or cyclopropylmethyl and R _{-1 is} methyl or ethyl, characterized in that a compound of the formula 0 CN H ₂ NC-C = NOR ₁ , where R _{1 is} methyl or ethyl, converted into an anion by a base and then with an isocyanate of the formula R-NCO, where R has the above meaning, and then acidifying the reaction mixture. - 22 - 7 0 9 8 11/110 8