FR2527604A1 - NEW FUNGICIDE COMPOUND - Google Patents

Abstract

A FUNGICIDAL COMPOUND IS DESCRIBED THAT IS PARTICULARLY ACTIVE: N- (2-METHYL-5-CHLOROPHENYL) -N-METHOXYACETYL-3-AMINO-1,3-OXAZOLYDIN-2-ONE AND ITS USE IN THE FIGHT AGAINST FUNGAL INFECTIONS OF USEFUL PLANTS.

Description

NEW FUNGICIDE COMPOUND

  The present invention relates to a fungicidal compound, and more particularly

  especially, N- (2-methyl-5-chlorophenyl) -N-methoxyacetyl-3-amino-1,3-

  oxazali Jre-2-u;, i, its use in the fight against fungal infections

  useful plant as well as fungicidal compositions

  containing as an active ingredient.

  In Belgian patent N o 895 117, filed in the name of the same application-

  resse, are described fungicidal compounds belonging to the class of Naryl-N-acyl-3-amino-1,3-oxazolidine-2-ones, among which are also found the compounds falling under the following general restricted formula: Ho \

CH 2 C = O

IHA / (I)

CH N

I

R N-C-CH 2-OCH 3

R 1 O

R 2

in which:

  R, RI and R 2 are either equal or different from each other and represent

  attempt a hydrogen atom, a halogen, an alkyl or a

  alkoxy having 1 to 4 carbon atoms.

  During our research on the compounds described in the Belgian patent cited above, and more particularly on the compounds of formula (i), it was found that the position of the substituents R, R 1 and R 2 on the aromatic ring is of particular importance and that among the compounds of formula (I), in which at least one of the ortho positions is unsubstituted and which are endowed with good fungicidal activity, the particular compound $: N- (2-methyl- 5-chlorophenyl) -N-methoxyacetyl-3-amino-1,3oxazolidin-2-one is surprisingly endowed with fungicidal activity

significantly superior.

  Thus, an object of the present invention is the compound of N- (2-

  methyl-5-chlorophenyl) -N-methoxyacetyl-3-amino-1,3-oxazolidie-2-one oe formula:

CH 2 C: O

y j x CHN (II)

CH I

N-C-CH 2-OCH 3

  il 2 O Cl Compound (II) has a particularly high fungicidal activity and can be used either as such or in the form of a

  suitable composition in the control of fungal infection of plan-

your agricultural importance.

  Thus, other objects of the invention are the use of the compound

  (II) in the protection of agricultural crops against the attack of cham-

  pine nuts and fungicidal compositions containing the compound

(II) as an active ingredient.

  The preparation of compound (II) is carried out according to the reaction

  tion already described in Belgian patent NO 885 117 By following a procedure analogous to that described in said patent above, and starting from 2-methyl-5-chloro-phenylhydrazine, the compound (II) is obtained with good yields in the form of a thick oil having an index of 50 C

refraction rn 50 = 1.5375.

  After crystallization from ethyl acetate plus ligro 7 ne, the compound (II) is obtained in the form of a white crystalline solid (poit

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melting = 69-70 'C).

  IR analysis (main absorption bands):

  2930, 1775, 1710, 1490, 1410, 1130, and 1035 cm- '.

  As already indicated above, the compound (II) has an activity

  high fungicidal rate which is particularly effective against fungi

  belonging to the class of phycomicetes.

  As the examples given below show, the activity

  gicide of the compound (II) is clearly superior to that of the compounds of

  formula (I) in which at least one of the ortho positions of the aro- cycle

matic is unsubstituted.

  Compound (II) is perfectly compatible with plants to pro-

  cover from the attack of phytopathogenic fungi and shows phytotoxi-

  cited lower than that of many compounds described in the Belgian patent cited above This compound develops, at the same time, a curative action also

  although preventive and it has remarkable systemic properties.

  Thanks to all these characteristics, the compound (II) can be used.

  used at the same time to prevent attacks on useful crops by farmers

  important phytopatogenic pinions belonging, in particular, to the species

these following:

  peronospora, phytophtora, plasmopara, pseudoperonospora and pythuim ,.

  as well as to cure diseases caused by these fungi when

the infection is already present.

  Because of the particular activity of this compound, applications

  very low doses are sufficient and, depending on the different fac-

  such as for example the type of crop to be protected, the type and the

  degree of fungal infection expected or already occurring, climatic factors

  ques (weather) and environmental conditions, can be in the

range from 1 to 100 g per hectare.

  For practical purposes, it is useful to have suitable compositions.

  nables which will contain the active principle and which will be diluted with water before use According to the current practice of formulations, comprising the compound (II) as active ingredient, compositions can be prepared in the form of liquid concentrate or emulsifiable concentrate, dry powder, wettable powder, etc. These compositions, in addition to the compound (II), will contain an inert liquid or solid vectors and possibly other additives such as emulsifiers, surfactants, wetting agents, suspending agents, etc.

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  If desired, it is also possible to mix with the compounds.

  fungicides of other active substances, effective in the field of

  agriculture, and compatible with the compound (II) such as herbici-

  , fertilizers, biostimulants, other fungicides, etc. It is particularly useful for certain specific types

  applications, to co-formulate at the same time as compound (II), others.

  fungicides known as "cover" fungicides These fungicides belong to the following classes:

  alkylene-bis-dithiocarbamates, copper salts or oxides, N-haloalkyl-

  thioimides; significant examples of these fungicides are the compounds known by the following common names: Zineb, Maneb, Mancozeb, Nabam, copper oxychloride, Captan, Captafol, Folpet, etc. To further illustrate the invention, the following set of examples will now be given:

EXAMPLE 1

  Curative activity against P Lasmopara viticola on P vine Gloves h Methodoloi enrle: The leaves of cv Dolcetto vine plants, growing in pots, in an environment conditioned to 250 C and 60% relative humidity are sprayed on their lower faces with an aqueous suspension of Conidia of Plasmopara viticola (B and C) Berl and Toni (200,000 conidia / cc). After a 24 hour residence time, in a saturated environment

  in humidity at 210 C, the plants are divided into three groups.

  your groups are then treated by spraying on both sides

  leaves with the product to be examined dissolved in a hydro-

  acetone (acetone = 20% by volume), respectively after one, two and

  three days from the date of infection.

  At the end of the incubation period (7 days), the degree of infection is evaluated using a scale ranging from 100 (for a

  healthy plant) to O (for a completely infected plant).

  In the following table, the data for the curative activity of compound (II) against P-viticola Dar have been reported, compared with the

  data from seven other compounds (A, B, C, D, E, F and G) of formula (I).

  From the data in Table I, it clearly appears that the compound (II) has a fungicidal activity which is clearly superior

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  to that of the comparison compounds In addition, the fungicidal activity of the

  posed (II) is particularly high in the absolute sense, insofar as,

  at extremely low doses (0.005%) this compound still deploys a full

  no activity (100% reduction in fungal infection).

TABLE I

  Curative activity against Plasmopara viticola on the vine

  indicated doses expressed as a percentage reduction of the

fungal fection.

Compound R RI R 2 Dose (in%)

_ _ 0.01 0.005 0.001 0.0005

II 2-CH 3 5-Cl H 100 100 100 100

A 2-CH 3 H H 100 7 -

B 3-Cl H H 100 85 74 -

C H H H 100 100 23 -

1 _ 20

D

E 3-CH 3 H H 100 52 -

F 3-F H H 100 15

G 2-Cl 5-Cl H 100 90 70 -

EXAMPLE 2

  Curative action against Peronospera tabacina on Tobacco plants.

  Méthodotoie_ enéra Le: The leaves of Burley cv tobacco plants growing in pots, in a conditioned environment, are sprayed on the underside of the leaf with an aqueous suspension of Peronospera conidia

  tabacina Adam (200,000 conidia / ml).

  After a residence time of 6 hours, in an environment saturated with humidity, the tobacco plants are subdivided into two groups and placed in an environment conditioned at 20 ° C. and 70% relative humidity for

incubation of the fungus.

3-C 1 -Cl H

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  After 24 and 48 hours respectively, from the time of infection

  tion, the first and second processing are implemented respectively

  group by spraying both sides of the sheets with the product to be examined

  ner in hydroacetonic solution (acetone = 20% by volume) At the end of the incubation period (6 days), the degree of infection is evaluated according to an evaluation scale with values ranging from 100

  (for a healthy plant) to O (for a completely infected plant).

  In the following table II, the data of the curative activity against P tabacina of compound (II) are reported by comparison with the

  seven other compounds of formula (I) (from A to G).

  The data in this table II show, quite clearly,

  that the compound (II) has a fungicidal activity which is clearly superior

  lower than that of the comparison compounds and that the fungicidal activity of compound (II) is extremely high from an absolute point of view, in the measure

  o, at very low doses (0.0005%), it still has a

  full (100% reduction in fungal infection).

TABLE II

  Curative action against Peronospera tabacina at the indicated doses,

  expressed as a percentage reduction in fungal infection.

Compound R R 1 R 2 Doses (in%)

0.01 0.005 0.001 0.0005

II 2-CH 3 5-C 1 H 100 100 100 100

A 2-CH 3 H H 100 100 47 -

B 3-Cl H H 100 100 92 68

C H H H 100 74 0

D 3-Cl 5-Cl H 100 30 -

E 3-CH 3 H H 100 60 -

F 3-F H H 100 30 -

G 2-Cl 5-Cl H 100 100 75 -

1 00 I 100

EXAMPLE 3

  Preventive action against Plasmopara vitico La on The vine Methodo Logie Généra Le: The vine leaves of CV Dolcetto, growing in pots in a conditioned environment, are sprayed on their su-

  with the product to be examined dissolved in a hydroaceous solution-

  tonic with 20% acetone (volume / volume).

  The plants are then placed in a conditioned environment.

  Two series of plants are sprayed separately on the underside of their leaves, 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 of residence time in an

  environment saturated with humidity, they are replaced in a suitable environment

  added. At the end of the incubation period (7 days), the degree of infection is evaluated according to an evaluation scale, lying in the range

  from 100 (for a healthy plant) to O (for a completely infected plant).

  Compound (II) has a preventive action superior to that

  comparison compounds listed in Table I (see Example 1).

  The preventive activity against the Plasmopara viticola of the compound (II) proves, moreover, extremely high from an absolute point of view, insofar as at very low doses (0.0005%), the compound (II ) is capable

  completely inhibit fungal infection (100%) at a time when the

  artificial fection is carried out after one day as well as after

seven days from treatment.

EXAMPLE 4

  Preventive activity against Peronospera tabacina on Tobacco

Generate methodology: -

  Burley cv tobacco plants growing in pots in an environment-

  ment conditioned, are treated by spraying the two sides of their leaves with the product to be examined, in a hydroacetonic solution

% acetone (volume / volume).

  Two series of plants are treated respectively after 1 and 7

  days by spraying the underside of the leaves, with a

  aqueous board of conidia of Peronospora tabacina Adam (200,000 coni-

  dies / cc). After 6 hours of residence time in a saturated environment

  in humidity, the treated plants are placed in a suitable environment.

  at 20 ° C and 70% relative humidity for incubation of the fungus.

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  At the end of the incubation period (6 days) the degree of infection is evaluated according to an evaluation scale ranging from 100 (for a healthy plant)

  to O (for a completely infected plant).

  In this type of test, the compound (II) also exhibits a fungicidal activity clearly superior to that of the indicated comparison compounds.

on table I (see example 1).

  The preventive activity against Peronospora tabacina of the compound (II) is, moreover, extremely high, absolutely, insofar as even

  used at very low doses (i.e. 0.0005%), the compound is

  core capable of completely inhibiting fungal infection (100% reduction

  tion) whether the artificial infection is communicated after one day or after

seven days after treatment.

  In the following, a series of examples will be given concerning fungicidal compositions containing, as active ingredient, the compound (II)

  alone or compound (II) associated with Mancozeb (common name of ethylene-

  zinc and manganese bis-dithiocarbamate) In these examples,

  will be the following abbreviations: DMF = N, N-dimethylformamide; xylene = commercially available mixture of xylene isomers; Ca-DBS = calcium dodecylbenzenesulfonate, for example the product marketed by ROL-Montedison under the brand "Emulson AG / Ca L";

  COH-ETO = hydrogenated polyoxyethylated castor oil, for example-

  a full product marketed by ROL-Montedison under the brand name "Emulson COH";

  SO-ETO = polyoxyethylated sorbitan oleate, for example the

  product put on the market by ROL-Montedison, under the brand "Emulson 20-OM"; NF-ETO = polyoxethylated nonylphenol, for example the product placed on the market by ROL-Montedison, under the brand "Emulson 10 B";

  NA-DSS = sodium dialkylsulfosuccinate, for example the

  product put on the market by ROL-Montedison, under the brand name Madeol V 40 "; NA-LS = sodium lignosulfonate, for example the product put

  on the market by Borregard, under the brand "Ultrazi-

  na NA "and the product put on the market by Cartiere di Tolmezzo under the brand" Bretax "; Na-NS = sodium alkylnaphta 11 nesulfonate, for example the products put on the market by ROL-Montedison, under

  the brands "Mladeol W 90" and "Madeol 934".

EXAMPLE 5

  Compositions in the form of an emulsifiable concentrated concentrate (EC) Ingredients by weight: A Compound (II) 5-40% B Solvent 40-90% C Surfactant 5% The suitable solvents (B) are: aromatic hydrocarbons

  and alkylaromatics, ketones, esters, DMF and mixtures thereof.

  Suitable surfactants (C) are: nonylphenol polyoxy-

  ethylated, polyoxyethylated triglycerides, polyoxyethylated fatty acids, dodecyl-

  sodium, calcium or triethanolammonium benzenesulfonate and their

mixtures.

  The preparation of layers (II) in the solvent examples of compositions, indicated in the table Compositions under

in percent by weight).

  s compositions are carried out by dissolving the

  t and then adding the surfactant Des in the form of an emulsifiable concentrate, are

Next III.

TABLE III

  the form of emulsifiable concentrate (ingredients

EXAMPLE 6

  Compositions in the form of wettable powder (WP) Ingredients (by weight): A Compound (II) -50% B Wetting agent 0.5-5% z C Suspending agent 1-5% A D Vector 40-93.5 % Suitable wetting agents are: polyoxyethylated nonylphenol, sodium alkylnaphthalensulfonate, sodium dialkylsulfosuccinate and mixtures thereof. Suitable suspending agents are: sodium, calcium or aluminum lignosulfonate, sodium alkylnaphthalenesulfonate condensed with formaldehyde, maleic anhydride and diisobutylene copolymers

and their mixtures.

  Suitable vectors (D) are: fossil flour (earth of

  diatoms), kaolin, Ca C 03, Si O 2 and their mixtures.

  The preparation of the compositions in the form of a wettable powder is carried out by grinding, in a suitable grinder, the mixture of the ingredients

  until the desired particle size is obtained.

  In Table IV below, examples of compositions are given.

as a wettable powder.

TABLE IV

Powder compositions

hundred by weight).

  wettable (ingredients for Ingredients _________Compositions

I 1 2 3 4 5 6

A Compound (II) 25 5 15 30 40 50

B Na-DSS 2 1 2 -

B Na-NS 1 4 2 -

B NF-ETO 5

  C Na-LS 3 2 1 3 2 5 D Kaolin 70 92 60 61 10

D fossil flour _ 20 44 -

D If O 2 5 10 30

EXAMPLE 7

  Compositions in the form of wet powder Lab Le of the compound (II) in combination with Mancozeb Ingredients (by weight): A Compound (II) B Mancozeb 3-8%% C Wetting agent 0.5-5% D Suspending agent 1 -5% E Vector 17-30.5% Suitable wetting agents, suspending agents and

  suitable vectors are those listed in Table VI.

  The preparation of the compositions is carried out according to the method of process described in Example 6 In the following Table V,

  examples of compositions in the form of a wettable powder.

TABLE V

  Compositions in the form of a wettable powder of compound (II) in

  combination with Mancozeb (ingredients in percent by weight).

  I ngrédi ents _Compositions I ngrédi ents

1 2 3 4

  A Compound (II) 6 3 4 8 B Mancozeb 65 65 65 65 C -Na-DSS 2 5 0.5 C -Na-NS 2.5 1 I

C NF-ETO 0.5

  D -Na-LS 5 3 2 3 E Kaolin 18 26.5 16

E fossil flour _ 23 -

E If 02 4 6

EXAMPLE 8

  Compositions in the form of a cation with Mancozeb

* concentrated suspension of compound (II) in combination

  Ingredients (by weight): A Compound (II) 1.5-4% B Mancozeb 32.5% C Surfactant 5-20% D Solvent 43.5-61%

  Suitable surfactants and solvents are those listed below.

meres in example 5.

  The preparation of the compositions is carried out by dissolving

  the compound (II) in the solvent and by mixing therein the surfactant.

  In the resulting mixture, Mancozeb is suspended under agitation.

  tation until a homogeneous mixture is obtained.

  In Table VI below, examples of compositions are given.

  in concentrated suspension of compound (II) in association with riancozeb.

TABLE VI

  Concentrated suspension compositions (ingredients in percent by weight).

  The compositions of Examples 5 to 8 were tested for their ac-

  fungicide activity against Plasmopara viticola on vines in

outdoor conditions.

  All the compositions showed excellent fungal activity.

  cide in accordance with the high activity shown by the compound (II) in

laboratory experiments.

  Ingredients ___Compositions Ingrédients 1 | 2 | 3 | 4

_ _ _ _ _ _ _ _ _I 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 10 -

C NF-ETO 3.5 1 1

  D Xylene 54.5 61 53.5 47.5 D Cyclohexanone 10

Claims (3)

  1. Coi; lpose N- (2-methyl-5-chlorophenyl) -N-methoxyacetyl-3-amino-   1,3-oxazolydin-2-one. 2. Method for combating fungal infection on useful plants, characterized in that an effective quantity of the product as claimed in claim 1, either as   that, either in the form of a suitable composition.   3. Fungicidal composition characterized in that it comprises the compound according to claim i as active ingredient at the same time as inert liquid or solid vectors and, optionally, additives.