CS205000B2 - Fungicide means - Google Patents

Description

The present invention relates to fungicidal compositions comprising as active ingredient at least one compound of the formula I or a salt thereof, wherein

R ¹ is a hydrogen atom or a group of formula II

or of formula III, -CO-NH-R ⁴ (III) wherein

R ^{4 is} C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl

Or a phenyl group substituted with 1 to 2 halogen atoms and

R ⁵ is C 1 -C 4 alkoxycarbonyl or a group of formula (II) above.

The term "alkyl radical" may mean straight or branched chain aliphatic groups having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, isobutyl, etc.). Preferred substituted phenyl groups are 3-chlorophenyl and 3,4-dichlorophenyl. The term "cycloalkyl radical" may mean groups having 3 to 6 carbon atoms, preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl).

Salts of a compound of formula I may be formed with inorganic or organic acids, for example hydrochloric, hydrobromic, sulfuric, acetic, formic, lactic, tartaric, etc. Salts to be used in therapy must be formed with pharmacologically acceptable acids.

Particularly preferred derivatives of formula I are the following compounds:

1- (5-nitrophuryl-2-carbonyl) carbomethoxyaminobenzimidazole,

N- (2'-benzimidazolyl) -5-nitro-2-fluorocarboxylic acid, 1 - [(3,4-dichlorophenylcarbamoyl) -2-5'-nitrofuryl-2'-carbonylamino] benzimidazole, 1'-butylcarbamoyl-2- (5-nitrophuryl-2-carbonylamino) benzimidazole, 1-phenylcarbamoyl-2- (5'-nitropuryl-2'-carbonylamino) benzimidazole, 1-propylcarbamoyl-2- (5'-nitrophuryl-2'-carbonylamino) benzimidazole,

1- [3'-chlorophenylcarbamoyl) -2- (5'-nitrofuryl-2'-carbonylamino) benzimidazole, 1-methylcarbamoyl-2- (5‘-mtrofuryl-2‘-carbonylamino) benzimidazole.

Compounds of formula I may be prepared by reacting 2-carbalkoxyaminobenzimidazoles or 2-aminobenzimidazoles with a reactive acid derivative containing a group of formula II.

In another method, compounds of formula (I) are prepared by reacting an N- (2-benzimidazolyl) -5-nitroph uranecarboxylic acid amide derivative with a reactive acid derivative, preferably an isokayate, containing the group of formula III, wherein R ⁴ is as defined above.

The compounds of formula I can be converted into their salts in a conventional manner by reacting a compound of formula I with an approximately equimolar amount of acid in the presence of an organic solvent.

The compounds of formula I and their salts are excellent fungicidal agents and can be used in both human and veterinary medicine as well as in agriculture.

According to the present invention, the fungicidal composition comprises at least one compound of the formula I or a salt thereof in a mixture with a suitable inert solid or liquid carrier or diluent.

These fungicidal compositions may be formulated as a powder, spray, granulate, emulsion, etc. Compositions containing carriers and diluents are typically used as a pest control formulation. The compositions may also contain a surfactant or other additive.

Fungicides include about 0.001 / _{0 and} 95% of active ingredient of formula I. Compositions suitable for direct use may contain usually 0.001 to 1% active ingredient. The concentrates may contain 20 to 80% active ingredient.

The fungicidal compositions according to the invention have an excellent action against Fusarium, Basidiomycetes or Helminthosporium strains. In particular, the compositions have an excellent action against Tillehia tritici on wheat germ, or against Fusarium nivale on rye germ, or against Cercospora beticola on sugar beet. The compositions can very advantageously be used as pickling agents.

The chemotherapeutic effect of the composition according to the invention is very good. The composition can be used primarily as a fungicidal agent, but also has a very good bacteriostatic and acaricidal effect. It prevents spore reproduction in pathogenic fungi and has a lasting effect. The compound is used as an active ingredient of fungicides, exerting its action through transfer in bast and leaf, through plant tissues. The new composition is used primarily for its lasting effect, but can also be used as an etching agent.

The novel composition of the invention counteracts the following species:

I. Ascomycetae:

Podosphaera,

P. leucotricha,

Erysiphe,

E. graminis,

E. clchoracearum,

Uncinulanecatox,

Endostigme,

Eclerotinia,

Sclerotium rolfafii,

Betxpotinia,

Botrytis cinexes,

Helminthosporium.

II. Basidiomycetae:

Tilleacesae,

Alternaria ep.,

Uromyces appendiculatus,

Rhizotonis solani,

Cercespora Reticola,

C. apii,

Fusarium nivale.

III. Phycomycetes:

Perenospoxaceae,

Plasmore viticola.

IV. Fungi imperfecti:

Septoria,

Verticillium,

Aspergillus etc.

The agrobiological importance of the composition according to the invention is emphasized by the fact that they block the most important pathogenic infestations in the field of harvesting cereals, root crops (potatoes, sugar beet), fruits, vegetables, cultural ornamental plants and gives control over the development of leaves, stalks and roots.

Thus, the compositions counteract pathogenic fungi existing in subtropical [Mediterranean] conditions, in horticultural crops and plantations, for example against Verti205000 cillium on cotton, Sigatoka disease, storage diseases c. G 'Glocesporium, Fusarium on bananas, Eleince fawcetti, Diplodia on species lemon trees, against Rhizoctonia solani, Thielaviopsis basicola on tobacco and against various pests on sugar cane.

Further details are set forth in the examples without limiting the scope of the invention to these examples.

He did

Test for Erysiphe graminis

This test evaluated the activity of mixtures containing 1- (3‘, 4‘-dichlorophenylcarbamoyl) -2- (5‘-nitrofurylcarbonylamino) benzimidazole as the active substance against Erysiphe graminis.

Method of testing: continuous infection in the greenhouse. '.

A pot of growing wheat (Bezostaya I) having a plant height of 12-14 cm was hand sprayed with the above composition and, in addition, wheat in the pot was heavily infected with mold powder. The spores necessary for infection were slightly shaken repeatedly. The evaluation was based on the plant infection index.

The results are shown in Table I.

Table I concentration infection index (w / w%)

0.01 3.23 0.05 2.28 0.10 1.26 0.20 1.01 control 4.75

Example 2

Test for Sclerotinium sclerotiorum

This experiment is used to evaluate the sustained effect of the composition of Example i against. Sclerotinia sclerotiorum. .

Test method: Translocation of effect was tested on carrots. The top of the 15 mm sterile carrot block surface embedded in the composition solution was infected with Sclerotonia sclerotiorum mycelium. After eight days of incubation period, the results were evaluated based on a scale of:

a) no effect, mycelial mass is 'lid' shaped, bj weak effect, part of the surface is covered with a layer of mycelium, cj mild effect, mycelium growth is already prevented, the surface is covered by less than 50 percent,

d) good effect, mycelium growth is negligible, its excellent systemic effect, mycelium growth is completely prevented.

The results of this experiment are shown in Table II below.

Table II

concentration (w / w ° / o) mycelium growth (empirical values) 0.01 1.0 0.05 3.4 . 0.10 4.8 0.20 5.0 control 1.0 Example 3 Aspergillus flavus test This test was used for evaluation

activity of 1- (3'-chlorophenylcarbamoyl) -2- (5'-nitrofury-2'-carbonylamino) benzimidazole against Aspergillus flavus.

Test Method: Diffusion agar method using filter paper discs. The spore suspension was sprayed onto a potato-derived dextrose plate and the 1 cm diameter filter paper discs impregnated with a composition of varying concentrations were placed on the plate. After six days of incubation period, evaluation was performed based on the average of inhibited zones. The results of this experiment are shown in Table III below.

Table III concentration of inhibited zone diameter (w / w%) (MM)

0.01 10.0 + 0 (no inhibition j

0.05 14.7 + 1.1

0.10 23.0 + 1.8

0.20 31.2 + 3.0 control 10.0 + 0 (no inhibition)

He did

Test for Fusarium oxisporum

This experiment was used to evaluate the activity of the composition described in Example 1 against Fusarium oxisporum.

Test method: diffusion agar method with injection of the composition into the culture medium.

Plates with a predetermined concentration are formed with a culture medium of maize agar. Of these cultures intertwined with mushrooms and of the same age, they were transplanted to 1X1 cm diameter plates. After six days of incubation period, results were evaluated based on mycelium averages.

The results of the experiment are shown in Table IV below.

Table IV

nutrient concentration diameter of mycelium soil (wt / wt ° / o) (mm) 0.01 15.2 + 1.8 0.05 10.0 no growth 0.10 10.0 no growth 0.20 10.0 no growth control 38.6 + 6.2

Other tests carried out on fungicidal activity:

Methods:

(a) Laboratory test (in vitro): the concentration of test compounds in the broth was 100 ppm. The following fungi were tested as test organisms:

Botrytis clnerea,

Fusarium oxysporum,

Stemphylium radicinum,

Helminthosporium turcicum,

Alternaria tenuis,

Rhizoctonla solani.

b) In-wave contact effect tests: The test plants were sprayed with a solution containing 1000 ppm of test compounds and then infected. The tests were carried out on the following test organisms:

Erysiphé graminis - on wheat

Sphaerotheca fuliginea - on cucumbers Phytophora Infestans - on tomatoes Uromyces.appendiculatus - on beans

(c) In addition, the systemic effect of Erysiphé graminis on wheat was tested. Evaluation :.

The results of the fungicidal tests were summarized in the table below. The potency of the test compounds was evaluated according to the following scale:

= 0 - 25% Inhibition = 26 - 50% Inhibition - 51 - 75% Inhibition = 76 - 99% Inhibition = 99 - 100% Inhibition

Test compounds:

A =

2- (5'-nitrophenyl-2'-carbamoylamino] benzimidazole

B = 1- (3‘, 4‘-dichlorophenylcarbamoyl) -2- (5‘-nitrophenyl-2-carbonylamino) benzimidazole c =

1- (Cyclohexylcarbamoyl) -2- (5'-nitrophenyl-2'-carbonylamino) benzimidazole

D =

1- (methylcarbamoyl) -2- (5'-nitrophenyl-2'-carbonylamino) benzimidazole

Results

and)

Botrytis clnerea Fusarium oxysporum (Stemphylium radicinum) Helminthosporium turcium Alternaria tenuis Rhizoctonla solani

(b)

Erysiphé graminis Sphaerotheca fuligines Phytophtora infestens Uromyces appendiculatus

C)

Erysiphé graminis

Compounds

A B C D

1; 0 3 3 2 2 12 4 3 0 1

3 2 1

3 11

--- 2 2

0 0 0 0 0 0 0 0 0 0 0 0 0

Table V

Comparative test

Test method:

detecting increasing in vitro inhibition (incubation time: 16 days)

Tested mushrooms:

I = Botrytis cinerea

II - Helminthosporium turcicum

III = Cladosporium cucumerium

Test compounds:

A =

1- (3‘, 4‘-dichlorophenylcarbamoyl) -2- (5‘-nitrophenyl-2‘-carbonylamino) benzimidazole

B =

1- (cyclohexylcarbamoyl) -2- (5‘-nitrofuryl-2‘-carbonylamino) benzimidazole

C =

1- (methylcarbamoyl) -2- (5‘-nitr of uryl-2‘-carbonylamino) benzimidazole Compound used for comparison:

FUNDAZOÍ? = methyl-1- (butylcarbamoyl) -2-benzimidazolecarbamate concentration 500 250 100 50 0 (PPm) tested I II III I II III I II III I II III I II III

compound AND 4 1 4 4 1 4 3 1 3 3 1 1 0 1 0 (B) 4 1 4 4 1 2 3 1 0 1 10 0 0 1 0 C 3 1 4 3 1 1 2 1 0 0 1 1 0 1 0 FUNDAZOL ^R 4 1 4 4 1 4 4 1 4 4 0 4 2 0 4 Scale: 0 = 1 = 2 = 3 = 4 = 0- 26- 51- 76- - 25% - 50% - 75% - 99% 100 94) inhibition inhibition inhibition inhibition inhibition

OBJECT OF THE INVENTION

Claims (1)

A fungicidal composition comprising, as an active ingredient, at least one compound of the formula I or a salt thereof, wherein R ¹ is a hydrogen atom or a group of formula II -OC NO, or formula III-CO-NH-R ⁴ (III), where it is R ^{4 is} C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or optionally phenyl substituted by 1 to 2 halogen atoms, and R ⁵ is C 1 -C 4 alkoxycarbonyl or a group of formula (II) above.