CS207687B2 - Fungicide means - Google Patents

Abstract

New benzimidazole derivatives of the formula I <IMAGE> wherein R<1> stands for hydrogen or a group of the formula V <IMAGE> wherein X stands for oxygen or sulphur and R<2> represents C1-4 alkyl, phenyl or substituted phenyl Y<-> is an organic or inorganic acid anion, are disclosed. The compounds have use as agricultural fungicides.

Description

(54) Fungicidal product

SUMMARY OF THE INVENTION The present invention is directed to an agricultural composition having the novel benzimidazole compound as an active ingredient and a process for the preparation of such novel benzimidazole compounds.

The use of various benzimidazole derivatives as fungicides is known from DE 1 956 157, British patent 1 238 977 and from Hungarian patent 167 242. Carbamoylated benzimidazole derivatives, such as methyl 1- (butylcarbmoyl) -2-benzimidazolecarbamate, are characterized by excellent efficiency.

It has now been found that the novel benzimidazole derivatives of formula I,

(I) wherein r 'is hydrogen or V,

0 = <- JNH-R ² where is

R 8 is C 1 -C 4 alkyl;

The anion of an organic or inorganic acid, (V), is characterized by a better fungicidal activity than the known benzinidazole derivatives. Said novel compounds, which are salts of alkylcarbamoyl derivatives of aminobenzimidazole, or merely alkylcarbamoyl derivatives of aminobenzimidazole, are particularly active against Fusarium graminearium, Fennelium expansum, Trichothecium roseum, Helminthosporium carborum, Aspergillus flavus.

The novel salts of formula (I) as the active ingredient of the composition of the invention may be prepared by:

а) for the preparation of compounds of the general formula II,

(II) wherein Y is as defined above,

2-Aminobenzimidazole of formula III

AND

H is reacted with an acid of formula

H-Y, wherein Y is as defined above, or is

b) for the preparation of compounds of the general formula IV,

I 2

O = C-NH-n wherein R ² and Y are as defined above, reacting the salt of formula II wherein Y is as defined above, with a compound capable of introducing the group of formula V,

OC-NH-H ²

Where R ² is as defined above, or is

c) in the compound of the formula I, where Ϊ and R ¹ are as defined above, the anion Y is replaced by another anion.

The alkyl group R ² represents a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl group.

The symbol Y in formula (I) may be a chloride, bromide, iodide, sulfate, alkoxycarbonyl anion having 1 to 3 carbon atoms in the alkyl group or a formate, acetate, propionate, benzoate or salicylate anion.

Compounds of formula (II) within the scope of compounds of formula (I) may be advantageously prepared by varying a) by reacting compounds of formula (III) with an appropriate organic or inorganic acid in a dipolar solvent or solvent mixture at a temperature ranging from 0 ° to 50 ° C. Deň: 32 ° C. Water, alcohol or acetone are preferably used as solvents.

Compounds of formula (IV) within the scope of formula (I) may preferably be prepared according to variation (b) by reacting compounds of formula (II) with a reagent suitable for introducing a group of formula (V) such as isocyanate, carbamoyl chloride, an active ester, isothiocyanate, or active thioester chlorformylamin obseJmu ^ "or groups R ^2, on the amine not ^b and ^f osgen content compounding Sapin R ^{2 b} not on the amine and ^thio osgen obeabuu ^f ^ i R2 group.

Compounds of formula (IV) may also advantageously be prepared by reacting a compound of formula (II) obtained by process a) without isolation with a reagent suitable for introducing a group of formula (V).

The plasticizer compositions of the present invention contain as active ingredient at least one benzimidazole derivative of the Formula I together with an inorganic or organic carrier, diluent, filler, dispersing agent, emulsifying agent or surfactant. The composition according to the invention generally contains 0.1 to 95% by weight of active ingredient.

Suitable formulations of the compounds of formula (I) include solutions, dusts, suspensions, emulsions, oil dispersions, pastes or powders, and can be applied by spraying, sprinkling, dusting or aerosols, while ensuring finely dispersed active ingredients.

For the preparation of ready-to-spray solutions, pastes and oil dispersions, medium-boiling and high-boiling fractions of mineral oils such as gas oil or kerosene, vegetable or animal oils, aliphatic and aromatic hydrocarbons and their derivatives, such as are benzene, toluene, xylene, paraffins, meth, ethanol, butaiol, acetone, chloroform, carbon tetrachloride, etc., strong polar solvents such as dimethylformamide, dimeephlsulfoxide, water, etc.

The aqueous form can be prepared from emulsifiable concentrates, pastes or wettable powders, oil dispersions by adding water. Emulsions, pastes, or oil dispersions may be prepared by dissolving the active ingredients, optionally dissolved in an oil or solvent, preferably in the presence of wetting agents, dispersing agents, adhesion-promoting additives and / or emulsifiers in water.

The surfactants which may be used are lignosulfonic acid, octylphosphonic acid, phenolsulfonic acids, their alkaline earth metal salts or their ammonium salts, glycol ether salts of fatty alcohols, sulphonated derivatives of oxalic acid salts, waste sulfide leaches, and the like.

Powders and dusts can be prepared by grinding and mixing the active ingredients with solid carriers. Silicas, silicagel, kaolin, kaolin, limestone, loess, chalk, dolomite, clays, magnesium oxide, calcium sulphate, magnesium sulphate, urine fertilizers such as ammonium sulphate, urea, as well as plant products can be used as solid carriers. such as corn flour, bran and other solids.

The invention is illustrated by the following non-limiting Examples. The percentages are always meant to be mono-ocot.

Example 1

(a) 46.55 g (0.45 mol) of 2-aminobenzimidazole are dissolved in 35 ml of ethanol and 41.5 g of concentrated hydrochloric acid are added dropwise to the resulting alcoholic solution. The mixture was stirred for 30 minutes and then evaporated to dryness. 56.5 g of 2-amino-benzimidazole hydrochloride of melting point 210 DEG-212 DEG C. are obtained.

b) 56.5 g (0.33 mol) of 2-aminobenzimidazole hydrochloride were dissolved in a mixture of 210 ml of acetone and 21 ml of water, and 32.6 g (0.33 mol) of butyl isocyanate were added thereto under stirring and cooling. The mixture was stirred at 20-25 ° C for 3 hours. The precipitate formed was filtered off, covered with a small amount of acetone and dried. There was obtained 74.8 g of 1-butylcarbamool-2-aminobenzimidazole hydrochloride, m.p. 122-125 ° C.

Example 2

133.0 g (1 mol) of 2-α-β-β (β-β (ε-β-5-α-β-α-β-β-α) were dissolved in 800 ml of acetone and the resulting solution was acidified 118 g of concentrated hydrochloric acid are added under stirring and cooling, the temperature should not exceed 45 [deg.] C. The reaction mixture is again cooled to 20-25 [deg.] C. and then 99 g (1 mol) of butyl isocyanate are added under stirring. Ethyl alcohol was added to the lightly oily reaction mixture until a clear solution was obtained (approximately 50 mL). The residue was filtered, washed and dried to give 193 g of 1-batyl-4-chloro-2-carboxylic acid hydrochloride. mp 123-125 ° C.

Example 3

133 g was dissolved while heating in water, and 49 g of chemically pure sulfuric acid and 50 ml of water were added to the solution with vigorous stirring, raising the temperature to 75-80 ° C. A precipitate formed from the clear solution. The reaction mixture was stirred at room temperature for 2 hours, cooled to + 10 ° C and the precipitate was filtered off. After stirring with a small amount of water, 175 g of 2-amino-benzoimidazole-phosphate, m.p. &gt; 250 DEG C., are obtained.

Example 4

66.5 g of 2-aminobenoimidazole, introduced into 100 ml of alcohol, are reacted with intensive stirring with a mixture of 49 g of chemically pure sulfuric acid with 100 ml of ethyl alcohol. The temperature is raised from 20 to 60 ° C, with the bulk of the 2-aminobenzioidazole dissolving to precipitate the product. The dense reaction mixture was diluted with 50 mL of ethyl alcohol and warmed slightly. The reaction mixture was then cooled to 20-25 ° C and covered with cold ethanol.

96.5 g of 2-azinobenzioidazole hydrosulphate having a melting point of 167 DEG-169 DEG C. are obtained.

Example 5

133 g of 2-aminobenzimidazole are dissolved in 1,300 ml of water, and a solution of 150 g of D-tartaric acid in 300 ml of water is added under vigorous stirring at a temperature between 50 and 60 ° C. The reaction mixture was cooled slowly and, if very thick, diluted by adding 300 ml of water. The mixture was stirred for 2 hours at 20-25 ° C, the crystallized material was filtered off, covered with water and dried. 272 g of 2-aminobenzimidazole hydrovinate having a melting point of 194 DEG-197 DEG C. are obtained.

example

266 g of 2-aminobenzimidazole are dissolved in 60 ml of methanol with heating, and a solution of 244 g of benzoic acid in 600 ml of methanol is added to the obtained solution with stirring. The product crystallizes during the addition. The resulting thick slurry was stirred at 20-25 ° C for 6 hours, filtered, washed with methanol and dried. 474 g of 2-aminobenzimidazole benzoate having a melting point above 250 DEG C. are thus obtained.

Example 7

133 g of 2-aminobenzimidazole are dissolved in 800 ml of methanol at 50 DEG C. and a solution of 138 g of salicylic acid in 400 ml of methanol is added thereto at 50 DEG. The reaction mixture was stirred for 6 hours then cooled to 20-25 ° C. The precipitate formed is filtered off, covered with cold methanol and then dried. 230 g of 2-aminobenzimidazole salicylate having a melting point above 250 DEG C. are obtained.

Example 8

133 g of 2-aminobenzimidazole are suspended in 900 ml of acetone. The suspension is acidified by the addition of 115 g of concentrated hydrochloric acid, the temperature may rise up to 45 ° C. The reaction mixture is then stirred for 30 minutes, then cooled to 20 ° C and 62 g of methyl isocyanate are added. After 30 minutes, the product precipitated from the clear solution and the temperature was meanwhile raised to 25-30 ° C. The mixture was stirred for 6 hours and the precipitate formed was filtered off, washed with acetone and dried. There was thus obtained 1-methylcarbamoyl-2-aminobenzimidazole hydrochloride (181 g), m.p. 139-140 ° C.

Example 9

In a mixture of 350 ml of acetone and 20 ml of water, 66.5 g of 2-aminobenzimidazole are dissolved while heating, and a solution of 69 g of salicylic acid in a mixture of 100 ml of acetone and 20 ml of water is added to the solution. The resulting salt precipitated and the resulting suspension was cooled to 20 ° C. 52 g of butyl isocyanate are added dropwise to the cooled suspension at a rate such that the temperature does not exceed 235 ° C. The thick reaction mixture was diluted by addition of 200 ml acetone. The diluted mixture is stirred for 4 hours, the precipitate formed is filtered off, covered with a small amount of acetone and dried.

146 g of 1-butylcarbamoyl-2-amine-benzimidimidol salicylate of melting point 150 DEG-155 DEG C. are thus obtained.

Example 10

Biological example

The activity of the compounds prepared by the process of the invention was tested by the poisoned agar plate method at concentrations of 100, 250 and 500 ppm. Agar with 2% potato dextrose is used. The test results are summarized in the following tables.

I. Organism used in the test:

Fusarium graminearům

Active ingredient 100 ppm Wheel diameter n i e 250 ppm 500 ppm AND 0 G 0 В 0 0 0 C 0 0 0 Benomyl control standard 0 C 0 untreated control 35 36 35

II. Penicillium expansum

Active ingredient 100 ppm Colony diameter 250 porn 500 ppm AND 0 G 0 В 0 0 0 C 0 0 0 Benomyl control standard 0 3 0 untreated control 30 32 31

III. Aspergillus flavus

Active ingredient 100 ppm Colony diameter 250 ppm 500 ppm AND 0 0 0 В 0 0 0 C Benomyl control 0 0 0 standard 0 0 0 untreated control 39 40 39

IV. Helminthosporitm carborim

Active ingredient 100 ppm Colony diameter 250 ppm 500 ppm AND 0 0 0 (B) 0 0 0 C 0 0 0 benomyy, control standard 0 0 0 untreated control 38 38 39

V. Trichothetics Rosei Active ingredient 100 ppm P r i □ * with t colony 250 ppm 500 ppm AND 0 0 0 (B) 0 íj 0 C 0 0 0 benoises, control. standard C· 0 untreated control ³⁰ 31 32

A = 1-butylktirbarooyl-4-aminobenzimidazole hydrochloride

B-1-methylcarbamool-2-aminobenzimidazole hydrochloride

C = salicylate 1-butylcarbamoyl-2-aminobenzimidazole benomyl = methyl-1-bulyababyl / -S-benzimidazolecarbemate

Example 11

Biological example

The fungicidal tests are performed in the laboratory (in vitro) and in the greenhouse (in vivo). Laboratory tests are carried out by admixing the compounds of the invention with the soil to obtain a concentration of 100 ppm active ingredient in the soil. The following fungi are used in the tests:

Botr.ytis cinerea

Fusarium Oxygen Link Stemplified radical HHlminthosporum turkeys Trichothecium rose Rhizoctonia saleni Alternaria tenuis.

In the in vivo tests, the plants were treated with a 1000 ppm solution of the test compounds and then infected. The following species of plant are tested:

Erysiphe gramini - wheat

Sphaerotheca fuliginea - cucumbers

Plhftophtora infestans - Tomatoes

Uromyces apatus - Bean.

Systemic activity against Erysiphe graminis is also tested. The results of the fungicidal tests are shown in the following table. The efficiency is graded on a scale of 0 to 4.

0 = 0 to 25% inhibition 1 = 26 to 50% inhibition 2 = 51 to 75% inhibition 3 = 76 to 99% inhibition 4 = 100% inhibition

Table

Test results

A. Labboat (in vitro) tests:

Compounds

ABC

Botrytis cinerea

Fusarium oxysporum

Helrninthosporium turcicim

Trichotheciím roseum

I like to do stemptylium

Rhizotonia solani

Alternaria ten

0 2

1 2

1 1

2 2

0 2

0 2

2. 1

1?

1

B. Greenhouse (in vivo) tests:

a) contact efficacy tests

S e t i n i n y c D E F G

Erysiphe graminis

Splhaerotheca fulginea

PíhKtophthora infestans

Uromyces appendiculatus

2c

00

22nd

00

10

00

33

11

22nd

00

23

02 /

(b) systemic efficiency tests AND (B) C Compounds D E F G H AND Erysiphe graminis 2 0 0 0 0 0 0 1 0

Compounds:

A = 2-aminobenzimidazole hydrochloride

B = 2-aminobenzimidazole sulphate

C = 2-aminobenzimidazole hydrosulfate

D = 2-aminobenzimidazole hydrovinate

E = 2-aminobenzimidazole benzoate

F with 2-aminobenzimidazole salicylate

G = 2-amino-1-butylcarbamoyl-2-aminobenzimidazole hydrochloride

H = 1-methylcarbamoyl-2-aminobenzimidazole hydrochloride

I = 1-butylcarbamoyl-2-aminobenzimidazole salicylate. .

Example 12

Preparation of 1-butylcarbamool-2-aminobenzimidazole hydrochloride% kaolin.

Example 13

Preparation of emulsifiable concentrates of 1-butylcarbemoyl-2- minobenzimidazole salicylate% rapeseed oil% naphthalenesulfonic acid% dimethyl orthoride% xylene.

Claims (2)

SUBJECT OF THE INVENTION 1. A fungicidal composition comprising as active ingredient at least one compound of formula (I): R (I) wherein R 'is hydrogen or a group of formula V, O = ^C -NH-R ² (V) wherein r 2 is C 1 -C 4 alkyl, and is an inorganic or oroanic anion, together with carriers and / or other excipients such as diluents and surfactants. 2. A composition according to claim 1, wherein the active ingredient is 1-butylcarbamcyl-4-aminobenzimidazole salicylate.