DD139428A5 - PROCESS FOR THE PREPARATION OF NEW BENZIMIDAZOLE DERIVATIVES - Google Patents

Abstract

The invention relates to novel benzimidazole derivatives, to processes for their preparation and to their use as agrochemical agents. In formula I is hydrogen and a group of the formula

Description

- Λ

NEW BENZIMIDAZOLE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS AGROCHEMICAL AGENTS

Field of application of the invention

The present invention relates to novel benzimidazole derivatives, processes for the preparation of these compounds and their use as active ingredient of; the new connections

containing aarochemical means. Characteristics of the known technical solutions

' The use of various BenzlmxuaTbl' derivatives

as fungicides is known (German Offenlegungsschrift No. * 1 956 157, GB Patent Specification No. 1 238 977 and Hungarian Patent No. 167 242) o Among the known

2 08 585

Compounds have, especially the carbamoylated Benzi imidazol derivatives, for example, the M _e thyl-1- (butylcarbamoyl) -2-

T = S has now been found that the new benzimidazoles derivatives of general Forr.el

wherein

1 '

R is hydrogen or a group of the general formula

Ί ^Γ · ' ο

X = C - NH - R ^ V

means, in which,

X is oxygen or sulfur and

2 R is alkyl of 1-4 carbon atoms, phenyl or substituted phenyl and

Y an organic or inorganic anion means a better fungicidal activity than the known benzimidazole derivatives. The compounds are particularly effective against Fusarium graminearium, Penicillium expansum, Trichothecium roseum, Helminthosporium carborum ^ Aspergillus' f-lavues.

.. The invention further relates to processes for the preparation of the novel salts of the general formula I _1, characterized in that

a) compounds of the formula ^:

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C-NH,

with acids of the general formula HY - wherein Y is as indicated above - and thereby compounds of the general formula.

wherein Y is as indicated above, or b) salts of general formula II wherein Y is as indicated above, with one to introduce a group of general formula

X = C - 'NH -

wherein X and R are as indicated above - reacting suitable reagent and thereby compounds of the general formula

Y "

X = C-NH-R

in which X ₃ Y and R are as indicated above, or c) in compounds of general formula I - wherein Y and R

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As indicated above - replaced the anion Y with another anion Y.

*

Alkyl group having 1-4 carbon atoms in the meaning

2 "

R can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl, or tert-butyl stand. The phenyl group may be substituted once or more by halogen, or alkyl having 1-4 carbon atoms.

Y in the general formula I may preferably be chloride, bromide, iodide, sulfate, alkoxycarboxylate in the alkyl moiety having 1-4 carbon atoms, formate, acetate, propionate, benzoate or salicylate anion.

The compounds of the general formula II which fall within the scope of protection of the compounds of the general formula I can preferably be prepared according to process variant a) by reacting compounds of the formula III in a dipolar solvent or solvent mixture at 0-50 ° C. with a suitable organic or inorganic acid. The preferred solvents are water, alcohol or acetone.

The compounds of the general formula IV falling within the scope of the general formula I can be prepared according to process variant b) in such a way that an isocyanate, carbamoyl chloride, an active ester, R containing isocyanate suitable as the introduction of a group of the general formula V Isothiocyanates an active

2 ven thioester, chloroformylamine or R containing

Amine and phosgene, or an R-containing amine and thiophosgene with compounds of general formula II.

Another method for preparing the compounds of general formula IV is that the compounds prepared by the method a) of the general

my formula II without isolation with the means suitable for the introduction of the group of the general formula V means. · · · · ·

The invention further relates to an agrochemical

.5 agent, characterized by a content of one or more benzimidazole derivatives of general formula I mixed with the usual organic or inorganic carriers, diluents, extenders, dispersants / emulsifiers, or surface-active agents.

1.0 The formulations of the invention contain in

general between 0.1-95 wt .% Active ingredient.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, powders, suspensions, emulsions, oil dispersions, pastes, dusts and applied according to the intended use by spraying, scattering, dusting, pouring, spraying * and in any case the finest distribution is intended be secured.

For the preparation of ready-spray solutions, emulsions, pastes and oil dispersions to be used as carrier materials and solvents mineral oil fractions of medium and high boiling point such as G _a söl, or petroleum, oils of vegetable or animal origin, aliphatic or aromatic hydrocarbons, and the like. their derivatives, eg "

II

Benzene, toluene, xylene, paraffin, methanol, ethanol, butanol, acetone, chloroform, carbon tetrachloride, etc. strong polar solvents, such as dimethylformamide; Dimethylsulfoxid, as well as water etc. used »

The aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by addition of water. In the preparation of emulsions, pastes, or oil dispersions, if desired, the active compounds are dissolved in oil or in a solvent.

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dissolved and preferably in the presence of dispersants, wetting agents, adhesives ·) and / or emulsifiers in the water homogenized *

Suitable surface-active agents are essentially: 5. lignosulfonic acid, naphthalenic acid, phenolsulfonic acids, alkali metal, alkaline earth metal and ammonium salts thereof,

Glycol ether salts of fatty acid alcohol, condensed products of sulfonated naphthalene derivatives with formaldehyde, sulfite waste liquors, etc.

The powders, dusts and dispersants are prepared by comminution and mixing of the compounds of general formula I and the solid carriers. As solid carriers, silica, silica gel, kaolin, talc, KaIk _x chalk, dolomite, loess, clay, magnesium oxide, calcium sulfate, magnesium sulfate, artificial fertilizer, eg

Ammonium nitrate, ammonium sulfate, ureas, vegetable products such as ZeB. Meal flours, furfurol bran and other carriers are used ·

The further details of the invention can be taken from the following examples.

Exemplary embodiment .

Ex a jp ^ ie I _n Jl

a) 46 _r 55 g (0.45 mol) of 2-amino-benzimidazole are dissolved in 35 ml of ethanol, and 41.5 g of concentrated hydrochloric advertise dripping with vigorous stirring and cooling in the alkoholisehe solution. The mixture is stirred for thirty minutes and evaporated to give 56.5 g of 2-aminobenzimidazole hydrochloride * m.p .: 210-212C.

b) 56.5 g (0.33 mol) of 2-aminobenzimidazole hydrochloride are taken up in a mixture of 210 ml of acetone and 21 ml of water and are added dropwise with stirring and cooling at 18-20 ⁰ C 32.6 g ( 0.33 mol) of butyl isocyanate to the reaction mixture, the mixture is at 20-25 ⁰ C for 3 hours

The resulting product is filtered, covered with a little acetone and dried to give 74.8 g of i-butylcarbamoyl-Si-aminobenzimidazole hydrochloride. Mp. 122-125 ⁰ C,

Example 2

133.0 g (1 mol) of 2-amino-benzimidazole are dissolved in 800 ml of acetone, the mixture is acidified with 118 g of hydrochloric acid with stirring and cooling so that in the meantime the temperature does not exceed 45 C. The mixture is cooled again to 20-25 ⁰ C and are added to 99 g (1 mol) of butyl isocyanate with stirring and cooling to this. The weakly oily reaction mixture is added to so much ethanol that a clear solution is formed (50 ml). After stirring for 30 minutes, the crystallization begins. The mixture is stirred for 4 hours and allowed to stand until the following day. The product is filtered, washed and dried.

This gives 193 g of 1-butyl-carbamoyl-2-amino-benzimi "dazol hydrochloride mp". 123-125 ⁰ C.

Example 3

133 g of 2-amino-benzimidazole are dissolved in 250 ml of water with heating, after which, with vigorous stirring, a mixture of 49 g. pure sulfuric acid and 50 ml of water and the temperature increases in the meantime to 75-80 ° C. The product is precipitated from the clear solution. The reaction mixture is stirred for 2 hours at room temperature, cooled to + 10 ⁰ C, filtered, covered with a little water. This gives 175 g of 2-aminobenzimidazole sulfate ♦ Schmp «: over 250 C. ·

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Example 4

66.5 g of 2-amino-benzimidazole are taken up in 100 ml of alcohol and reacted with a mixture of 49 g of pure sulfuric acid and 100 ml of ethanol with vigorous stirring. The temperature increases from 20 ° C to 60 ° C, the majority of the 2-amino-benzimidazole dissolves and the product separates out. The thick reaction mixture is diluted with 50 ml of ethanol and heated slightly · The mixture is cooled to 20-25 ⁰ C, filtered and washed with cold

Ethanol covered. This gives 96.5 g of 2-amino-benzimidazole acid sulfate. M.p. 167-169 ⁰ C.

Example 5 .

133 g of 2-A _m ino-benzimidazole are dissolved in 1300 ml of water and mixed at 50-60 C with vigorous stirring with a solution of 150 g of D-tartaric acid in 300 ml of water. The Reaktionsgem'isch is cooled slowly, and if it is very dense, it is diluted with 300 ml of water · The mixture is stirred, filtered, crystallized Produk.t, covered with water, dried for 2 hours at 20-25 ⁰ C, "Man obtains 272 g of 2-aminobenzimidazole hemitartarate ·

Mp: 194-197 ⁰ C..

Example 6

266 g of 2-amino-benzimidazole are dissolved in 600 ml of methanol with heating, and to the 2-amino-benzimic.lazol solution with stirring, a solution of 244 g of benzoic acid in 600 ml of methanol. Already under the addition, the product begins to crystallize. The dense suspension is stirred at 20-25 ⁰ C, filtered, washed with methanol and dried. This gives 474 g of 2-amino-benzimidazole benzoate; M .: over 250 C.

^x 6 hours

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Example 7

133 g of 2 ~ amino ~ are dissolved at 50 ⁰ C in 800 ml of methanol and mixed with the solution of 138 g of salicylic acid in 400 ml of methanol at 50 ⁰ C benzimidazole. The reaction mixture is stirred for 6 hours, cooled to 20-25 ⁰ C, filtered and covered with cold methanol, dried. 230 g of 2-aminobenzimidazole salicylate are obtained. Mp .: 250 ⁰ C.

Example 8

133 g of 2-amino-benzimidazole are suspended in 900 ml of acetone, acidified with 115 g of concentrated hydrochloric acid and the temperature can thereby increase to 45 ⁰ C. The mixture is stirred for half an hour, cooled to 20 ⁰ C and is added dropwise 62 g of methyl isocyanate. From the initially clear solution, the product precipitates after about thirty minutes, and the temperature is now increased to 25-30 C. The mixture is stirred for 6 hours and the precipitated product is filtered, washed with acetone, dried to give 181 g i-methyl-carbamoyl-a-aminobenzimidazojt hydrochloride. Mp .: 139-140 ⁰ C.

Example 9

66.5 g of 2-amino-benzimidazole are dissolved in a mixture of 350 ml of acetone and 20 ml of water with heating and a solution of 69 g of salicylic acid in 100 ml of acetone and 20 ml of water is added. »The salt formed precipitates, and The resulting suspension is cooled to 20 C, is added dropwise 52 g of butyl isocyanate at such a rate that the temperature does not exceed 235 ⁰ C. The dense R _e reaction mixture is diluted with 200 ml of acetone. The mixture is stirred for 4 hours, filtered, covered with a little acetone, dried.

148 g of 1-butyl-carbamoyl-2-aminobenzimidazo3-salicylate are obtained. Mp: 150-155 ° C _e

· - 'ίο -

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Example 10 (Biological Example) The biological effect was carried out by means of the "poisoned agar plate" method at concentrations of 100, 250 and 500 ppm. 2% potato dextrose agar was used for the studies. The test results are shown in the following tables.

I · Test organism Fusarium graminearum

Colony diameter

Active ingredient · 100 ppm 250 ppm 500 ppm

A 0 0 0

B 0 | o 0

C 0 .00

Benomyl.control 0 0 0 untreated control · 35 36 35 II. Penicillium expansum

Colony diameter

Active ingredient 100 ppm 250 ppm 500 ppm

A 0 0 0

B O 0 0

C. 0 0.0

Benomyl stood. Control 0 0 0 untreated control 30 32 31 III. Test organism Aspergillus flavus

Colony diameter

Active ingredient 100 ppm 250 ppm 500 ppm

A ° ° 0

B 0 0 0

C 0 0 0

Benomyl stood. Control OOO untreated control 39 40 ³⁹

5

IV. Helminthosporium carborum

Colony diameter

active substance 100 ppm 250 ppm - 500 ppm 500 ppm A · O O O O B O O , O O C O O O O Benomyl stood. control O O O O untreated control 38 38 39 32 V. Trichohecium roseum Colony diameter active substance 100 ppm 250 ppm A O O B O O C O O ßenomyl stood. control O O untreated control 30 31

A = 1-butylcarbamoyl-2-aminobenzimidazole hydrochloride B = i-methylcarbamoyl-2-amiriobenzimidazole hydrochloride C = 1-butylcarbamoyl-2-aminobenzimidazole salicylate Benomyl = methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate

Example 11 (Biological B _e ispiel)

The fungicidal tests were carried out in laboratory (in vitro) and in a greenhouse in vivo). In the laboratory experiments, the compounds were mixed in the soil so that the concentration of the chemicals in the soil is 100 ppm. The following fungi were used in the experiment: Botrytis cinerea Fusarium oxysporum Stemphylum radicinum Helminthosporium turcicum

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Trichothecium roseum, Rhizoctonia solani Alternaria tenuis

During the in vivo experiments the plants were sprayed and infected with a 1000 ppm solution of the compounds. The experiments were carried out with the following species:

Erysiphe graminis - wheat

Sphaerotheca fuliginea - cucumbers,

Phytophthora infestans - tomatoes Uromyces appendiculatus - beans.

Against Erysiphe graminis also the systemic effect of the compounds was examined.

The fungicidal activity was shown in the following table. The efficiency was rated as follows

0 = inhibition of 0-25 %

1 = inhibition of 26-50 %

2 = inhibition of 51-75 %

3 = inhibition of 76-99%

4 = inhibition of 100 % ·,

Trial results

A) Laboratory experiments (in vivo) A e b i η d u η 9 e η H I V O B C D e F G 1 3 1 0 2 2 2 2 2 1 2 Botrytis cinerea 2 1 2 0 1 1 3 0 2 Fusarium oxysporum 1 1 1. 0 1 2 Helminthosporium turcicum 2. 2 1 Trichothecium roseum 0 2 2 2 2 1 3 2 2 Stemphylium radicinum 1 0 2 • 2 1 2 3 0 1 Rhizoctonia solani 0 2 1 1 1 1 Alternaria tenuis

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B) Greenhouse experiments (in vivo)

a) contact effect

links

"· A BCDEFGH

Erysiphe graminis »2 Sphaerotheca fulginea O Phytophthora infestans 2 Uromyces appendiculatus O

b) systemic effect

10 connections

ABCDEFG H I

Erysiphe graminis 2 0.000 0 0 1 0

2 2 1 1 0 1 2 2 0 0 0 0 0 0 0 0 2 2 2 3 3 2 2 3 0 0 1 1 1 1 0 2

The connections:

A = 2-aminobenzimidazole hydrochloride

B = 2-aminobenzimidazole sulphate

C = 2-aminobenzimidazole bisulphate

D = 2-aminobenzimidazole hemitartarate

E = 2 aminobenzimidazole benzoate

F = 2 amino-benzimidazole-salicylate

20 G = -l-butylcarbamoyl-2-aminobenzimidazole hydrochloride

H = '1-methylcarbamoyl-2-amino-benzimidazole hydrochloride

I = 1-butylcarbamoyl-2-aminobenzimidazole salicylate

Preparation of atomizers ^middle L ⁿ 25 60 G.ew.% i-butylcarbamoyl-a-amino-benzimidazole hydrochloride

40% by weight of kaolin

13

Preparation of Emulsifiable Concentrates 20% by weight of 1-butylcarbamoyl-2-aminobenzimidazole salicylate

3% by weight rapeseed oil 30% by weight% dimethylformamide

7% by weight of naphthalenesulfonic acid 40% by weight of xylene

Claims (2)

Claim - 14 - ZOdoDo J Process for the preparation of benzimidazole derivative salts of the general formula R ^{1 is} hydrogen or a group of the general formula X = C - NH - R ^{2 v} stands, - in which X is oxygen or sulfur and R is alkyl of 1-4 carbon atoms, phenyl or unsubstituted phenyl, and Y for an organic or inorganic anion is characterized in that a) compounds of the formula with acids of the general formula HY - in which Y. as indicated above - and compounds of the general formula - ¹⁵ - 2 08 5 85 in which Y is as indicated above.j contains j or b) salts of the general formula II - in which Y is as indicated above - with one for the introduction of the group of general formula my formula V - wherein X and R are as above indicated - suitable reactant, and compounds of the general formula C-NH ^ Y " ₂ ^Iv XBC-NH-R · ~. wherein X, Y and R are listed above - receives _f or c) in compounds of general formula I - wherein Y and R are as indicated above - an anion Y is replaced with another anion Y « 3, process according to point 2b), characterized in that as for the introduction of the group of the general formula V - wherein X and. R. as indicated above are suitable reagents, Isocyanate containing an R group, carbamoyl chloride, an active ester, isothiocyanates an active thioester, a chloroformylamine, or R group 2 containing amine and phosgene or R group containing amine and thiophosgene used.