NZ204342A - N-(2-methyl-5-chlorophenyl)-n-methoxyacetyl-3-amino-1,3-oxazolidin-2-one and fungicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £04342 204342 Priority Date(s}: . Cfcy. .'.9?.?......

Complete Specification Filed: Class: CQ.1£&@3a..F\C..

Publication Date: P.O. Journal, No: X&fZB.

Kf8 BSSJIl^^®' NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION FUNGICIDAL COMPOUND We, MONTEDISON S.p.A., of 31, Foro Buonaparte, Milan Italy, an Italian Company, hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is performed, to be particularly described in and by the following statement: (followed by page la) No. Date 204342 The present invention concerns a fungicidal compound and, more particularly, the compound N- (2-methyl-5-chloro-phenyl) -N-methoxyacetyl-3-amino-l,3-oxazolidin-2-one, its use in the fight against fungal infections in useful plants as well as to the fungicidal compositions containing it as active ingredient. 204342 2 In our New Zealand Patent Specification No. 196287 there are described fungicide com pounds belonging to the class of N-aryl-N"-acyl-3-amino--1,3— oxazolidin-2-ones, amongst which there are also the compounds falling under the ..restricted general formula: R (I) - C - CH0 - OCH. 1 2 wherein: R, R and R , either equal to or different from each other, represent a hydrogen atom, a halogen, or an alkyl or alkoxy with 1 to 4 carbon atoms.

During our researches on the compounds described in the above cited patent specification, and more particularly on the compounds of formula (I), we found that the position 1 2 of 3utrstituents R, R and R on the aromatic ring, is of 3 204342 particular importance, and that amongst the compounds of formula (I), in which at least one of the ortho positions is unsubstituted, and which are endowed with a good fungicide activity, the particular compound : N-(2-methyl-5-chlorophenyl)-N-methoxyacetylr-3-amino-J..^3- -oxazolidin -2-one is surprisingly endowed with a definitely superior fungicide activity.

Thus, the object of the present invention is the compound N- (2-methyl-5-chlorophenyl )-N-methoxyacetyl-3-amino-l ,3--oxazolidin-2-one of the formula: CH n - n cl Compound II is endowed with a particularly high fungicide activity and may be used, either as such or 4 204342 infection in plants of agricultural importance.

Thus, further objects of this invention are the use of compound II in protecting agricultural cultivations against the attack of phytopatho genie fungi and the fungicidal compositions contain -ing compound IIas active ingredient..

The preparation of compound II is carried out according to the reactions already described in New Zealand Patent Specification No. 196287. By following a process analogous to that described in the said patent specification and starting from 2-methyl-5-chloro-phenylhydrazine, compound II was obtained with good yields in the form of a thick oil show ing at 50°G a refraction index Tj = 1,5375.

After crystallization from ethyl acetate plus li-groin, compound II is obtained in the form of a white crystalline solid (m.p.= 69°-70°C) .

IR analysis (main absorption bands): 2930, 1775, 1710, 1490, 1410, 1130, and 1035 cin"1.

As already previously indicated, compound II is en dowed with a high fungicide activity which is exerted particularly against fungi belonging to the class •' 2 r 204342 of Phycomicetes.• As appears from the hereunder given examples, the fungicide activity of compound II is definitely superior to that oif the compounds of formula I in which at least one of the ortho-positions of the aranatic ring is unsubstituted.

Compound II is perfectly compatible with the plants to be protected from the phytopathogenic fungi attack, and shows a phyto-toxicity inferior to that of many compounds described in the above cited New Zealand Patent Specification. This compound develops both a curative as well as a preventive action, and is endowed with remarkable systemic properties.

Thanks to all these characteristics, compound II nay by used both for preventing attacks to useful cultivations by important phytopathogenic fungi belonging particularly to the following genera: Peronospora, Phytophtora, Plasmopara, Pseudoperonospo-ra and Pythium, as well as for curing the diseases caused by these fungi when the infection is already present.

Because of the particular activity o'f this compound, • 6 204342 very low applicative doses are sufficient which, depending on different factors such as for instance the type of cultivation to be protected, the type and the matical (weather) factors and environmental conditions, may range from 1 to 100 g/ha.

For practical purposes it is useful to employ suitable compositions that contain the active principle, and which will be diluted with water before use- According to the usual fonnulatiye practice, with compound II as active ingredient,there may be prepared compositions in the form of either a liquid concentrate, emulsifiable concentrate, dry powder, wettable powder, etc.

Said compositions, besides compound II, will contain inert liquid .or solid carriers and optionally other, additives such as emulsifiers, surfactants, wetting a-gents, suspending agents, etc.

When desired, it is possible to mix with the fungicide compositions also other active substances effective in the agricultural field and compatible with degree of fungal infection foreseen or under way, cli- 2 i 't£i5i9S6 7 204342 compound II, such as herbicides, fertilizers, biostimu-lants, other fungicides, etc.

Particularly useful for certain specific types of application is the co-formulation together with j ' compound II of other,so-called "coverage", fungicides.

These fungicides belong to the following classes: alky-lene-bis-dithiocarbamates, copper salts or oxides, H--haloalkylthio-imides; significant examples of such fungicides are the compounds known by the following common names: Zineb, Maneb, Mancozeb, Nabamj copper oxychloride, Captan, Captafol, Folpet, etc.

With the purpose of even further illustrating the invention there will now be given the following set of Examples: EXAMPLE 1 : Curative activity against Plasmopara viticola on vine plants General methodology: The leaves of cv. Dolcetto vine plants, grown in pots5 in a conditioned environment at 25°C and a 60% relative humidity, were besprinkled on their lower face with an aqueous suspension of conidia of Plasmopara viticola 8 204342 (B. et C.) Berl et de Toni (200.000 conidia/cc).

After a dwelling time of 24 hours', in a humidity saturated environment at 21.°C, the plants were subdivided into three groups. The plants of each group were then treated, by besprinltling both leaf faces, with the product under examination, dissolved in a hydroacetonic solution (acetone - 20% by volume), re- . spectively after 1, 2 and 3 days from the infection date.

At the completion of the incubation period (7 days), the degree of infection was evaluated accoi'ding to a value scale ranging from 100 (for a healthy plant) to 0 (for a completely infected plant).

In following TABLE 1 there have been recorded the data for the curative activity against P. viticola of compound II by comparison with the data of other seven compounds (A, B, C, D, E, P and G) of formula I, Prom the data on Table I there clearly appears that compound II possesses a fungicide activity that is definitely superior to that of the comparison compounds. Moreover, the fungicide activity of compound II is particularly high in an absolute sense in as 204342 9 much as at extremely low doses (0.0005ft) this compound still displays a full activity (with a 100% reduction of the fungal infection).

TABLE 1 Curative activity against Plasmopara viticola on vine at the indicated doses, expressed as percentage reduction of the fungal infection. (Table I on following sheet). table . COMPOUND R • R1 R2 DOSE (in %) 0.01 0.005 0.001 0.0005 ii 2-CH3 -Cl 1 H 100 100 100 100 A 2-CH3 H H 100 - 7 i B 3-Cl : H _ H 100 85 74 - c H H H 100 100 23 - D 3-Cl -Cl H 100 - - E 3-CH3 H H 100 - 52.

- P 3-P H H 100 G 2-Cl -Cl H 100 90 70 Is) O hO 204342 11 EXAMPLE 2 : Curative action against Peronospera tabacina on tobacco plants.

General methodology: Leaves of tobacco plants of cv. Burley, grown in pots in a conditioned environment, were besprinkled on the lower leaf face with an aqueous suspension of .■-co-nidi a of Peronospera tabacina Adam (200.000 conidia/ml). After a dwell time of 6 hours in ahumidity.. saturated environment, the tobacco plants were subdivided into two groups and placed in an environment conditioned at 20°C and 70% of rel. humidity, for the incubation of the fungus. After 24 and 48 hours respectively from the moment of the infectionthere was respectively carried out the treatment of the first and the second group, by besprinkling both leaf faces with the product under examination in a hydroacetonic solution (acetone = 20$ by volume). At the end of the incubation period (6 days) the degree of infection was evaluated according to an evaluation scale with values ranging from 100 (for a healthy plant), to 0 (for a completely infected plant). 12 204342 In following TABLE 2 there have been recorded the data for the- curative activity against P. tabacina of compound II in comparison with the other seven compounds of formula I (from A to G).

Prom the data of this TA BLE 2 it appears quite evident that compound II possesses a fungicide activity that is decidedly superior to that of the comparison compounds and that the fungicide activity of compound II is extremely high in an absolute point of view, in as much as at very lew doses (0.0005%) it possesses 3till a complete activity (100% of reduction of the fungal infection).

TABLE 2: Curative action against Peronospera tabacina at the indicated doses, expressed as percentage reduction of the fungal infection.

\ \ \ \ V \ 21F£81986 i m Curative action against Peronospera tabacina at the indicated doses, expressed as a percentage reduction of the fungal infection. 1 Doses (in %): COMPOUND R R1 R2 0.01 0.005 0.001 0.0005 II 2-CH3 -Cl H 100 100 100 100 A 2-CH H H 100 100 47 - B 3-Cl H H 100 100 92 68 C H H H 100 74 0 i I D 3-Cl -Cl II 100 - E 3-CH3 H H : 100 P 3-P H H 100 . - G 2-Cl -Cl H 100 ■ 100 75 - 2043 42 14 EXAMPLE 3 : Preventive action against Plasmopara vitigola on vine. General methodology: The vine leaves of cv. Dolcetto, grown in pots in a conditioned environment, were besprinkled on the upper leaf face with the product under examination dissolved in a hydroacetonic solution at 20% of acetone (vol./vol.).

The plants were then placed in a conditioned environment. Two series of plants were separately besprinkled on their lower leaf faces, respectively after 1 and 7 days from the day of treatment, with an aqueous suspension of Plasmopara viticola conidia (200.000 conidia/cc) and, after 24 hours dwell time in humidity saturated environment, were placed back in a conditioned environment.

At the end of the incubation period (7 days) the degree of infection was evaluated according to an evaluation scale ranging from 100 (for a healthy plant) down to 0 (for a completely infected plant).

Compound II displayed a preventive action superior to that of the comparative compounds listed on TABLE I (see Example 1). : 204342 The preventive activity against Plasmopara viticola of compound II proved, moreover, extremely high in an absolute viewpoint in as much as at very low doses (0.0005%) compound II was able to completely inhibit the fungal infection (100$) both when the artificial infection was carried out after 1 day as well as after 7 days from the treatment. EXAMPLE 4 : Preventive activity against Peronospera tabacina., on to-bacco.

General methodology: cv. Burley tobacco plants grown in pots in a conditioned environment, were treated by besprinkling both leaf faces with the product under examination in a hydro-acetonic solution at 20°/o acetone (vol./vol.).

Two aeries of plants were treated respectively after 1 and 7 days, by besprinkling the lower leaf face with an aque -ous suspension of Peronospora tabacina Adam conidia (200.000 conidia/cc).

After 6 hours dwell time in a humidity saturated environment, the treated plants were placed into an environ- 204343 16 for the incubation of the fungus.

At the end of the incubation period (6 days), the degree of infection was evaluated according to an evaluation scale ranging from 100 (for a healthy plant) down to 0 (for a completely infected plant). Also in this type of test, compound II showed a fungicide activity decidedly superior to that of the comparative compounds reported on Table 1 (see Example 1). The preventive activity against Peronospora tabacina of compound II is, moreover, extremely high in an absolute way in as much as, even when used in very low doses (i.e. 0.0005$), the compound is capable to still inhibit in a total way the fungal infection (100$ reduction) whether the artificial infection is imparted after 1 day or after 7 days after the treatment.

In the following will be given a series of Examples concerning fungicidal compositions containing as active ingredient Compound II alone or Compound II in association with Mancozeb (Common name of zinc and manganese ethylene-bis-dithiocarbamate). In these Examples the following abbreviations will be used: DMF = N, N-dimethyl-formamide Xylene = commercially available mixture of xylene isomers _ Ca-DBS = calcium dodecylbenzenesulphonate, e.g. the product V 2 1 f£B198S 17 204342 marketed by ROL-Montedison with the trade name "Emulson AG/CaL" COH-ETO = polyoxyethylated hydrogenated castor oil, e.g. the product marketed by ROL-Montedison with the trade name "Emulson COH" S0-ET0 = polyoxyethylated sorbitan-oleate, e.g. the product marketed by ROL-Montedison with the trade name"Emulson 20-0M" .

NF-ETO = polyoxyethylated nonylphenol, e.g. the product marketed by ROL-Montedison with the trade name "Emulson 10 B" Na-DSS = sodium dialkylsulphosuccinate, e.g. the product marketed by ROL-Montedison with the trade name "Madeol V40" Na-LS = sodium lignosulphonate, e.g. the product marketed by Borregard with the trade name "Ultrazina NA" and the product marketed by Cartiere di Tolmezzo with the trade name "Bretax" Na-NS = sodium alkylnaphthalenesulphonate, e.g. the products marketed by ROL-Montedison with the trade names "Madeol W 90" and "Madeol 934".

Example 5 Compositions in emulsifiabLe concentrate (EC) / Ingredients (by weight) Vii \ A ...

'F£B19S6 18 204342 A - Compound II 5-40$ B - Solvent 40-90# C - Surfactant 5-20$ Suitable solvents (B) are: aromatic and alkyl-aromatic hydrocarbons, ketones, esters, DMF and mixtures thereof.

Suitable surfactants (C)'are: polyoxyethylated nonylphenol, polyoxyethylated triglycerides, polyoxyethylated fatty acids, sodium, calcium or triethanolammonium dodecylbenzensulphonate and mixtures thereof.

The preparation of the compositions is effected by dissolving compound II in the solvent and by then admixing the surfactant. Examples of compositions in emulsifiable concentrate are reported in the following Table 3.

Table 3 Compositions in emulsifiable concentrate (ingredients in percent by weight) 204342 19 Ingredients Compositions 1 2 3 4 A) Compound II 4° B) Xylene 63 90 70 40 40 B) Cyclohexanone 7 - - B) DMF - - 3 C) Ca-DBS 3 1 2.5 : 3 • C) C0H-ET0 3-5 - • ■ 6 ■ ~ ' C) S0-ET0 - 4 4.5 - 3 C) NF-ETO 3.5 - 4 Example 6 Compositions in wettable powder (WP) Ingredients (by weight): A- Compound II 5_50$ B- Wetting agent C- Suspending agent D-Carrier 0.5-5$ 1-5$ 40-93-5$ Suitable wetting agents (B) are: polyoxyethylated nonylphenol, sodium alkylnaphthalenesulphonate, sodium dialkylsulphosuccinate and mixtures thereof.

A 2lF£BJ9$&r 2,04342 Suitable suspending agents (C) are: sodium, calcium or aluminum lignosulphonate, sodium alkylnaphthalenesulphonate condensed with formaldehyde, maleic anhydridediisobutylene copolymers and mixtures thereof.

Suitable carriers (D) are: fossil meal (diatomaceous earth), kaolin, CaCO^, SiO^ and mixtures thereof.

The preparation of the compositions in wettable powder is carried out by grinding in a suitable mill the mixture of the ingredients up to the established particle size.

In the following Table 4, examples of compositions in wettable powder are reported.

Table 4 Compositions, in wettable powder (Ingredients in percent by weight). 21 204342 Ingredients Compositions 1 2 3 ' 4 6 A) Compound II 3° 40 50 B) Na-DSS 2 - - 1 2' - B) Na-NS - 1 4 * - ;' 2 - ;■ ■ ' - ;B) ;NP-ETO ;- ;- ;- ;' ;: 5 ;C) ;Na-LS ;3 ;2 ;1 ;" 3 • ;' : 2 v' ;5. ;D) ;Kaolin ;70 ;92 ;60 ;7 61 ;'■ ;: 10 ;D) ;Fossil meal ;- ;- ;20 ;•44 / ;- ;D) ;Si02 ;— ;— ;- ;5 ;10 ;;: 30 ;Example 7 ;Compositions in wettable powder of Compound II in association with Mancozeb Ingredients (by weight): ;A- Compound II 3-8$ B- Mancozeb 65% ;C- Wetting agent 0.5-5% ;D- Suspending agent 1-5% ;E- Carrier -17-30.'5*' 204342 22 Suitable Wetting agents, Suspending agents and Carriers are those listed in Example 6.

The preparation of the compositions is carried out according to the procedure described in Example 6.

In the following Talble 5, examples of composition-in wettable powder are reported.

Table 5 Compositions in wettable powder of Compound II in association with Mancozeb (ingredients in percent by weight) Ingredients Compositions 1 . 2 ■ . 3.. v': 4 A) Compound II . 6 3 4 8 B) Mancozeb 65 65 65 65 C) Na-DSS 2 - 0.5 ; C) Na-NS - 2.5 : 1 1 V C) NP-ETO - ... . 0.3 D) Na-LS 3 2 3 E) Kaolin 18 26.5 16 E) Fossil meal - - 2 3 E) 'Si0o 4 6 • 2 23 204342 Example 8 Compositions in Concentrated Suspension of Compound II in association with Mancozeb Ingredients (by weight) A- Compound II 1.5-4$ B- Mancozeb 32.5$ C- Surfactant -20# D- Solvent 43-5-61$ Suitable surfactants and solvents are those listed in Example 5.

The preparation of the compositions is carried out by dissolving Compound II in the solvent and by admixing the surfactant. To the' resulting mixture, Mancozeb is suspended under stirring until a homogeneous mixture is obtained.

In the following Table 6, examples of compositions in concentrated suspension of Compound II in association with Mancozeb, • are reported.

Table 6 Compositions in concentrated suspension (Ingredients in percent by weight) 24 204342 Ingredients Compositions 1 2 3 4 A) Compound II 3 1.5 2 4 B) Mancozeb 32.5 32.5 32.5 32.5 C) Ca-DBS 3 1 2 3 C) COH-ETO 3.5 - - . 2 . .■ C) SO-ETO - 3 . - ■ C) NF-ETO 3-5 1 ' 1 D) Xylene ^.5 6l 53-5 47-5 D) Cyclohexanone - — — The compositions of Examples 5 to 8 have been tested for fungicidal activity against Plasmopara viticola on vines in open-field conditions.

All the compositions have shown excellent fungicidal activity in accordance with the high activity shown by Compound II in laboratory experiments. 204342

Claims (3)

WHAT WE CLAIM IS

1. The compound N-(2-methyl-5-chlorophenyl)-N--methoxy-acetyl-3-amino-l, 3-oxazolidin-2-one.

2. A method for fighting fungal infections on useful plants, consisting in applying over the cultivated area, before the infection or while the infection is underway, an effective amount of the compound claimed in claim 1, either as such or in the form of a suitable composition.

3. A fungicidal composition containing the compound of claim 1 as an active ingredient, together with one or more liquid or solid inert carriers and optional additives. *;Dated this 17 day of February 1986 A J PARK & SON;Agents for the Applicant.;fen;21*