DE2604726A1 - S-TRIAZOLO SQUARE CLAMP ON 5.1-ANGLE CLAMP FOR BENZTHIAZOLE, METHOD OF MANUFACTURING AND USING IT - Google Patents

Description

PFENNING - MAAS - SdLSR MSNlG -LEMKE-Mockery

8000 MÖNCHEN 40 SCHLSSSHSMERSTR 299

Eli Lilly and Company, Indianapolis, Indiana, V.St.A.

s-Triazolo / 5,1-b / benzthiazoles, process for their preparation

and their use

The invention is in the field of agrochemistry and relates focus on new compounds, their preparation and their use in the control of phytopathogenic organisms.

The improvement of existing fungicides has long been one of the tasks of agrochemicals. There are already many Classes of organic compounds have been used and new compounds are constantly being made and evaluated. The following literature references are briefly discussed as examples of this.

U.S. Patents 3,764,681 and 3,839,659 treat the fungicidal activity of tetrazolo / 1,5-a / quinolines and s-triazolo / 4,3-a / quinolines. In BE-PS 803 098 and DT-OS 2 249 350 it is indicated that certain imxdazoquinoxalines also in the Agriculture are viable fungicides.

609834/0979

INSPECTED

Tamura et al., Novel Syntheses of Thiazolo / 3 ^ -by-s-Triazoles, J. Hetero. Chem. X, 947-51, 1973 describe a similar compound without substituents on the phenyl ring.

Potts et al., Synthesis of the Thiazolo / 2,3-c / -s-Triazole and the Thiazolo / 3,2-b / -s-Triazole Systems, J. Org. Chem. 36, 10-13 (1971) and JA-PS 71 26 500, CA. 75, 140863 (g) (1971) describe thiazolo ^ / 3,2-b / -s-triazoles, of which are given that they are useful as bacterial oids and as agrochemicals.

In US-PS 3,389,137 there is a tetrazolo / ^ 5, 1-b / benzthiazole, which is only mentioned as an intermediate for phosphenimide compounds.

The invention relates to compounds of the general formula

(D,

in which mean

R is hydrogen or a hydroxy or methyl group and

R is a methyl group, an ethyl group, chlorine or fluorine or a 5-position methoxy group.

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Another object of the invention is a method for Preparation of the compounds of formula I, which is characterized is that compounds of the general formula

> = NH

N-NH

where R has the meaning given above,

be implemented with a cyclization agent.

According to a preferred embodiment of this method become compounds of the general formula

R has the meaning given above and

R is hydrogen or a methyl or methoxy group

means,
reacted with a cyclizing agent.

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The isomers of the compounds of formula III, namely compounds the general formula

'= NH

i-NH-CR ^£

1 2

wherein R and R have the meanings given above,

can also be converted to the compounds of formula I in a comparable manner.

A group of compounds preferred in the context of the invention are those in whose formula I R is hydrogen.

The preferred substituents R are methyl, chlorine and fluorine, and preferably the radical R is in the 5 position.

Examples of the compounds of formula I are the following:

6-chloro-s-triazolo £ 5,1-b / benzthiazole, 7-fluoro-2-hydroxy-s-triazolo / 5,1-b / benzthiazole, 6-ethyl-s-triazolo / 5,1-b / benzthiazole, 7-ethyl-2-hydroxy-s-triazolo ^ 5,1-b / benzthiazole, 5-methoxy-2-hydroxy-s-triazolo / 5,1-b / benzthiazole, 7-chloro-s-triazolo / 5,1-b / benzthiazole, 8-fluoro-s-triazolo / 5,1-b / benzthiazole, 7-ethyl-2-methyl-s-triazolo / 5,1-b / benzthiazole.

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The preferred compounds of the formula I are 5-methyl-striazolo / ^ 5.1 -b / benzthiazole, 5-fluoro-s-triazolo / 5,1 -b / -benzthiazole, S-chloro-s-triazolo / S, 1-b / benzthiazole, 5-methoxy-s-triazole / 5,1-b / thiazole and 2,5-dimethyl-striazolo / 5.1 -b / benzthiazole.

The compounds of the formula I are prepared from the easily accessible 2-aminobenzothiazoles. The substituents R of the compounds go to the corresponding substituents of the 2-aminobenzothiazoles used as starting materials return.

Various production methods can be used for the synthesis of the new compounds. The above Author Taraura describes a process that begins with the production of 3-Amino-2-iminobenzthiazole, which he calls a 2,3-diamino compound referred to by reacting 2-aminobenzothiazcl with O-mesitylenesulfonylhydroxylamine at ice bath temperature in methylene dichloride. The as that Amino-imino compound formed from mesitylene sulfonate salt is heated to boiling under reflux with acetic anhydride, whereby 2-methyl-s-triazolo / _5,1 -b / benzthiazole in 80 percent yield is obtained.

However, the 2-acetylamino-3-acetylimino compound is used as a by-product educated.

The best way for the preparation of the compounds of the formula I, in which R is a methyl group, consists in the Cyclization of an intermediate, namely a 2-alkanoylimino-3-aminobenzothiazoline of formula III with phosphoric acid.

The compounds listed below are exemplary of the compounds of the formula III:

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2-acetylamino-3-amino-6-chlorobenzthiazoline, S-amino-V-ethyl ^ -methoxycarbonyliminobenzothiazoline, 2-acetylimino-3-amino-4-methoxybenzthiazoline, 2-acetylimino-3-amino-5-chlorobenzthiazoline, 3-amino -4-ethyl-2-methoxycarbonyliπιinobenzthiazoline _/ 2-acetylimino-3-ainino-4-fluorobenzothiazoline, 2-acetylimino-3-amino-6-ethylbenzthiazoline _/ S-amino ^ -methoxy ^ -methoxycarbonyliminobenzfchiazole, 2-acetyl-aminoaino -6-f luorbenzthiazoline.

The intermediates are made by reacting a 2-aminobenzothiazole with O-mesitylenesulfony! hydroxylamine in one aromatic or halogenated solvents such as methylene dichloride at a temperature between the freezing point of the reaction mixture and room temperature, preferably at ice bath temperature. This creates a 3-Amino-2-imino compound of a mesitylene sulfonate salt. The salt is made in by treatment with a strong base the free base converted with acetyl halide to the acylated intermediate is implemented. The acylation takes place at the same temperature as the amination in an aromatic, aliphatic or halogenated solvent or in an ether such as tetrahydrofuran in the presence of an acid acceptor such as triethylamine or another tertiary amine or a strong inorganic base, for example an alkali carbonate.

The amination step described above using O-Mesitylenesulfony! Hydroxylamine can also be using one of the following aminating agents can be carried out: chloramine, p-bromophenylsulfony! hydroxylamine, p-toluenesulfony! hydroxylamine, Methanesulfony! Hydroxylamine and Phenylsulfonyl hydroxylamine.

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The cyclization of the intermediate is carried out in pure polyphosphoric acid carried out. The reaction proceeds best at a relatively high temperature, for example 100 to 120 ° C, which leads to good yields in about 1 to 2 hours.

Those compounds of the formula I for which R is hydrogen can be easily obtained by cyclizing a 3-Amino-2-iminobenzothiazolines of the formula II with triethyl orthoformate Prepare in an inert solvent. Xylene is the preferred solvent, but can other aromatic solvents can be used. The mixture is slowly heated, and that released by the reaction Ethanol should be removed from the reaction vessel using a Dean-Stark trap or similar device will. Compounds with a 2-methyl group can be prepared in the same way by using triethyl orthoacetate or a mixed anhydride can be prepared in place of triethyl orthoformate.

Compounds for which R is hydrogen can also be prepared by cyclizing the amino-imino salt with pure formic acid be prepared at reflux temperature for 12 to 24 hours.

The compounds for which R represents a hydroxyl group are obtained by cyclizing a 2-methoxycarbonylimino-3-aminobenzothiazoline compound of the formula III produced. The intermediate is obtained by acylating a 3-amino-2-imino compound obtained with methyl chloroformate in the usual way. The intermediate will either thermally at the melting point or by treatment with an alkali hydride in an inert solvent, for example an ether, an alkane or an aromatic solvent, preferably tetrahydrofuran, at reflux temperature cyclized.

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A v / urther well useful method for preparing the compounds of the formula I starts from a 1-acyl-2-phenylhydrazine, which is reacted with an alkali metal thiocyanate in an aromatic solvent at an elevated temperature of 40 ⁰ C to the reflux temperature. The intermediate product is a 4-acyl-3-phenylthiosemicarbazide _f the with bromine in a halogenated solvent at a temperature of about 30 ⁰ C to the reflux temperature of the reaction mixture is cyclized to give 3-acylamino-2-iminobenzthiazolin is obtained as the HBr salt . The salt is converted into the free base of the formula IV using a strong base, as described above, and cyclized to the desired product by heating in acetic acid at reflux. Other agents that can be used in place of acetic acid are sulfuric acids, heat and acetic anhydride.

The following examples illustrate the synthetic methods that can be applied for preparing the starting compounds of formulas II, _R III and IV.

Example A.

A slurry of 7.2 g of 2-amino-4-methoxybenzthiazole in methylene dichloride is cooled in an ice bath and treated with a Solution of 11g mesitylenesulfonylhydroxylamine in methylene dichloride offset by ice bath temperature. The reaction mixture is allowed to gradually come to room temperature over a period of 3 hours heat. Then it is diluted with ethyl ether and filtered off.

The solids obtained are slurried in 100 ml of chloroform. After adding a solution of 6 g of KOH in 75 ml of water in about 30 minutes, the solid crude product is separated off by filtration and the chloroform layer is evaporated to dryness in vacuo to give more product. These product components are combined

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and recrystallized from ethyl acetate. Are thus obtained 4.8 g of S-amino ^ -imino ^ -methoxybenzthiazolin, mp = 131-132 ⁰ C, identified by nuclear magnetic resonance analysis.

Example B.

1.7 g of 3-amino-2-imino-4-methylbenzthiazoline are dissolved in about 50 ml of tetrahydrofuran and treated with 1.1 g of triethylamine. The reaction mixture is cooled in an ice bath and a solution of 1 g of acetyl chloride in 2 ml of tetrahydrofuran is added dropwise with stirring. After the addition is complete, the reaction mixture is stirred for about 8 hours at ice bath temperature and then diluted with an equal volume of water. The tetrahydrofuran is removed in vacuo and the remaining aqueous mixture is filtered to recover the product. After recrystallization from ethanol the yield of purified product is 2.0 g of S-amino ^ -methyl ^ -acetyliminobenzthiazol, mp = 154-155 ⁰ C. The product is identified by nuclear magnetic resonance, ultraviolet spectrum and elemental microanalysis.

calculated found

C 54.28%, 54.59% H 5.01% 5.42%

N 18.99% 18.11%

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example

1.3 g of triethylamine are added to a slurry of 1.8 g of S-thiazoline in about 50 ml of tetrahydrofuran given. The reaction mixture is then cooled in an ice bath and added dropwise with 1.04 g of methyl chloroformate offset. After the addition is complete, the reaction mixture is stirred for about 4 hours at ice bath temperature and then worked up as described in Example B. The product is characterized by its nuclear magnetic resonance, its ultraviolet spectrum and by micro-elemental analysis as 3-amino-2-methoxycarbonylimino-4-methylbenzthiazoline identified.

calculated found

C. 50.26% 50.86% H 4.67% 4.91% N 17.71% 17.66%

Example D

Using 2.0 g of 3-amino-4-chloro-2-iminobenzothiazoline in 30 ml of tetrahydrofuran, the procedure described in Example C is carried out in the presence of 1.1 g of triethylamine. The starting compound is acylated with 1.5 g of methyl chloroformate in a reaction time of only about 2 hours. The product is identified by nuclear magnetic resonance, ultraviolet spectrum, mass spectroscopy and elemental microanalysis as 3-amino-4-chloro-2-methoxycarbonyliminobenzothiazoline, mp = 222 to 223 ^° C.

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calculated found C. * - 41.95% 41.92% H 3.13% 3.16% N 16.37% 16.10%

The preparation of the compounds of formula I is carried out by the following examples explain.

example 1

9.2 g of 3-amino-2-methoxycarbonyl-iraino-4-methylbenzothiazolin (prepared according to Example C) are heated in about 1 1/2 hours in a flask in a Woods metal bath to about 220 ⁰ C. The flask is then allowed to cool, and the product is recrystallized from dimethylformamide to give 5.9 g of 2-hydroxy-5-methyl-s-triazolo / 5,1-b / benzthiazole having a melting point of about 300 ⁰ C obtained v / earth. Micro elemental analysis:

calculated found

C. 52.67% 52.62% H 3.44% 3.59% N 20.47% 20.33%

Example 2

To a slurry of 4 g of 3 ~ amino-4-chloro-2-iminobenzothiazoline a solution of 3.7 g of triethyl orthoformate in about 10 ml of xylene is added to 50 ml of xylene. The mixture is then heated very slowly to reflux temperature. That

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Ethanol distilling off the mixture is collected in a Dean-Stark trap. After about 1 hour one leaves let the mixture cool down. The cooled reaction mixture is filtered off and the solids are washed with benzene. The yield is 2.8 g of S-chloro-s-triazolo / ^ j, 1-b / · benzthiazole, m.p. = 203 to 205 C, determined by nuclear magnetic resonance analysis and elemental microanalysis is identified.

calculated found C. 45.83% 45.99% H 1.92% 1.99% N 20.04% 19.94%

Example 3

16.4 g of sodium thiocyanate are added to a mixture of 15 g of 1-acetyl-2- (2-methy! Phenyl) hydrazine and 75 ml of benzene. After the reaction mixture has been heated to 45 ^° C., 16 g of trifluoroacetic acid are added. The mixture is then heated to reflux temperature and stirred at this temperature for 3 1/2 hours. After decanting off excess benzene, the pulpy residue is poured into water. An equal volume of ethyl acetate is added, the resulting mixture is filtered, and the separated solids are washed with ethyl acetate. This gives 4-acetyl-3- (2-methylphenyl) thiosemicarbazide.

This intermediate product is slurried in 70 ml of ethylene dichloride and a solution of 5.3 g of bromine in 3O ml of ethylene dichloride is added dropwise with stirring. The mixture is heated to reflux temperature and 1 1/2 hours at

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stirred at this temperature. Then it is brought to room temperature allowed to cool and stirred overnight. Then the reaction mixture is diluted with an equal volume of ethyl ether, and the white solid formed is filtered off and washed with more ethyl ether. The product is and nuclear magnetic resonance analysis identified as the HBr salt of 3-acetylamino-2-imino-4-methylbenzothiazoline.

The slurry of this product in 100 ml of water is _{neutralized with NH 4} OH and the 3-acetylamino-2-imino-4-methylbenzthiazoline formed is collected by filtration.

One gram of this product is dissolved in 50 ml of acetic acid and the solution is refluxed with stirring for 28 hours. Dioxane is then added and most of the acetic acid is removed by distillation as an azeotrope. The remaining reaction mixture is poured into a large amount of water, and the aqueous mixture is neutralized with potassium bicarbonate. The mixture is then extracted repeatedly with ethyl acetate and the combined ethyl acetate layers are evaporated in vacuo to an oil which partially solidifies on standing. The residue is triturated with ethyl ether / chloroform (4/1), whereupon it is filtered off. The filtrate is chromatographed on a silica gel column, eluting with benzene / ethyl acetate (2/1). The fractions containing the product are combined and evaporated in vacuo to give 2, S-dimethyl-s-triazolo / S, 1-b / benzthiazole, mp = 121 to 123 ⁰ C is obtained.

example

A slurry of 2.2 g of the intermediate product prepared as described in Example B in 15 ml of polyphosphoric acid is heated ^{to about 110 ° C. for about 11/2 hours.} The mix will

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allowed to cool to room temperature and diluted with a large amount of water. The aqueous mixture is neutralized with NH.OH and filtered to separate off the crude product. After recrystallization, 2,5-diiriethyl-s-triazolo / 5,1-b / -benzthiazole is obtained; F. = 121 to 123 ⁰ C.

According to the procedures described in Examples 1 to 4 the other compounds of the formula I are also prepared, for example the following:

Example 5 5-methyl-s-triazolo / 5,1-b / benzthiazole, mp = 134-135 ⁰ C.

Example 6 2,5-dimethyl-s-triazolo / 5,1-b / benzthiazole _f F. = 121 to 123 ⁰ C.

Example 7 5-Fluoro-s-triazolo / 5,1-b / benzthiazole, mp = 165 to 167 ⁰ C.

Example 8 5-fluoro-2-methyl-s-triazolo / ^ 5,1-b / b3nzthiazol, m.p. = 162 to 164 ⁰ C,

Example 9 5-methoxy-s-triazolo / 5,1-b / benzthiazole, mp = 142-143 ⁰ C.

Example 7-methyl-s-triazolo / 5,1-b / benzthiazole, mp = 156-158 ⁰ C.

Example 11 2,7-Dimethyl-s-triazolo / 5,1-b / benzthiazole, mp = 118-119 ⁰ C.

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Example 12 S-Chlor ^ - 'methyl-s-triazolo / Sji-b / benzthiazole, F. = 263 to 264 ⁰ C,

Example 13

S-chloro ^ -hydroxy-s-triazolo / ^ ib / benzthiazol, F. = 340 to 341 ⁰ C (dec.)

Example 14

5-methoxy-2-methyl-s-triazolo / ^ 5,1-b / benzthiazole _f F. = 146 to 147 ⁰ C.

Example 15 S-Ethyl-s-triazolo / ^ ib / benzthiazole, F. = 93 to 96 ⁰ C.

Example 16 5-Ethyl-2-methyl-s-triazolo / _i 5 _/ 1-b / benzthiazole _f F. = 95 to 96 ⁰ C,

As has been shown in a series of tests carried out in vivo, the compounds of the formula I are capable of the disadvantageous Reduce the effects of leaf mushrooms. In the first group of the following examples the tests are described, with which the effectiveness of the compounds against fungi was determined.

For testing, solutions and suspensions of the compounds of the formula I are prepared as follows: About 3.5 percent by weight, each compound are introduced into a mixture of equal parts acetone and ethanol, which is about 10 g / 100 ml of a non-.ionic contains surfactant. The solution will be

60983A / 0979

then dispersed in deionized water in such an amount that the aqueous dispersions contain the in in the tables below in parts per million by weight. The dispersions are applied to the test plants with a fine air distributor sprayed on in such an amount that the plants become thoroughly wetted. Be for the bean rust tests the compounds prepared and applied differently, as will be described below. ·

The individual tests also include untreated infected and untreated normal control plants. The results are given using a rating scale from 1 to 5, where 1 means severe infestation and 5 means complete control of the infestation. A space in the tables indicates that the named compound has not been tested at the named concentration. In those cases where more than a test has been carried out against a given phytopathogenic organism, the results are averages specified. The compounds are identified by the example numbers given above.

The following test methods are used in detail:

T e s t 1

Helminthosporium leaf spots of wheat

Healthy wheat seeds are planted in sterile greenhouse soil. When the seed plants have reached a height of 10 to 13 cm, they are sprayed with dispersions of the compound to be tested. The day after treatment, the plants are given a suspension from spores of HeI minthosporium grown on potato dextrose agar sativum vaccinated. The plants are placed in a humid room for two days to prevent the pathogen

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begins to grow, and then brought into the greenhouse. The plants are examined about a week after treatment and noted the results.

test

Tomato blight

Four week old tomato seed plants are washed with water
Sprayed dispersions of the compounds to be tested. During the day
then the foliage is covered with an aqueous suspension of
Inoculated offshoots of Phytophthora infestans. The inoculum was grown on infected wheat seeds. The plants
are held and checked as described above.

test

Powder Meltau of Beans

The host plants are 10-day-old bean seedlings. After their foliage has been sprayed with aqueous dispersions of the test compounds and allowed to dry, the plants are inoculated in the greenhouse by letting them stand between other bean plants which are largely covered with powdered melt
(Erysiphe polygoni) are infected. After about 10 days, the plants are examined and the results are noted.

test

Anthracnose from cucumber

Aqueous dispersions containing test compounds are applied to healthy cucumber seedlings in sterile greenhouse soil. The next day the plants are coated with an aqueous suspension

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inoculated from conidia of Colletotrichum lagenarium. The fungus was grown in Petri dishes on potato dextrose agar. The plants are left to stand in a humid room for 2 days and then placed in the greenhouse. About 12 days after the Using the test compounds, the disease is examined and assessed.

test

Rice brandy

The dispersions of the test compound are on tightly in plastic Applied to pots and growing healthy rice seedlings. The next day the plants are grounded with Piricularia oryzae (on Rice husk agar grown) and left in a humid room for two days. After 5 to 7 days in the greenhouse the plants are examined.

test

Bean grate

Pinto bean sprouts are grown in plastic pots in the greenhouse drawn. One week after the seeds are planted, 10 ml of 400 parts / million of the test compound are added aqueous dispersion applied to the soil in which the individual plants grow, which corresponds to a ratio of 12.3 kg / ha. The next day, the plants are inoculated with traces of bean rust (Uromyces phaseoli var. Typica) which are found on pinto bean plants had been grown and applied as an aqueous dispersion to the test plants. After two days . The plants are brought into the greenhouse in a damp room and examined about 10 days after inoculation with the phytopathogenic organism.

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Test 7

Cercospora leaf spots of sugar beet

Sugar beet seedlings are placed in square plastic pots transplanted and allowed to grow for three weeks. Aqueous dispersions of the compounds to be tested are sprayed onto the leaf surfaces. After drying the dispersions, however within 24 hours, the plants are treated with a conidia suspension inoculated by Cercöspora beticola. The organism was grown on a sugar beet leaf agar. To The plants are placed in the greenhouse for two days in a damp room and will be examined two to three weeks later.

Test 8 Wine botrytis

Healthy grapes are sterilized by immersion in dilute sodium hypochlorite solution and washed thoroughly. The berries are placed on sieve racks in divided Pyrex containers. They are then marked and sprayed with dispersions of the test compound. The following day, the berries are inoculated by spraying 5 ml of a conidia suspension of Botrytis cinerea onto the plates each containing 12 berries. The inoculum was grown on frozen lima bean agar. After adding a small amount of water, a cover is attached over each container. After 48 hours at 25 ^° C., the berries are examined and the infestation ratings are noted.

test

Apple scab

Apple seedlings with 4 to 6 leaves are sprayed with aqueous dispersions of the compounds to be tested. During the day

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then the plants are sprayed with a suspension of fresh conidia from Venturia inaegualis. The conidia come from infected apple seedlings which are kept for the production of inoculation material. The plants are kept in a damp room for two days held at 20 C to initiate disease development and then placed in a greenhouse. About two weeks after applying the test compounds, the plants are examined, and the results are noted.

Test 10 Downy dew from grapevines

Young developing leaves are replaced by healthy ones on the day of the experiment Grapevines removed. They are grounded individually with the bottom side up on a spread out synthetic fiber mat in Petri dishes laid out of plastic. Water is added to each individual Petri dish and the stalks of the individual leaves are grounded with a surrounded by a cotton ball soaked in water. Each leaf is sprayed with an aqueous dispersion of the test compound.

After the dispersions of the test compound have dried, the leaves are inoculated over the entire leaf surface by finely distributing a conidia suspension of Plasmopara viticola (grown on infected leaf tissue). The dishes are then covered and ^{left to stand at about 18 °} C. and 100% relative humidity, whereby they are exposed to artificial light for 8 hours per day. After about a week, all leaves are examined and the symptoms of the disease are assessed.

The following table summarizes the results obtained when examining compounds of the formula I by way of example were obtained by the methods described above.

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Anthracnose

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Cercospora

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Anthracnose

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Botrytis

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Dry rot

Helminthosporium

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Apple scab

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Cercospora

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Anthracnosis

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Botrytis

Bonnenrost

Dry rot

Helminthosporium

Apple scab

LO fluff dew

Cercospora

Exemplary compounds of formula I are also, in a Way audited, which allows to evaluate their ability to systemically combat rice blight. The connections are either applied to the soil in which the rice plants are grown, or to rice seeds, and then the extent is examined up to which the artificially caused rice blight is fought by the connection.

Test 11

Seed impregnation

Dispersions of the test compounds are prepared as described above except that instead of acetone / ethanol Ethanol alone is used and the finally prepared aqueous dispersion regardless of the concentration of the active ingredient always contains 0.5% ethanol. Concentrations of the compounds of 250, 500 and 1000 parts per million are used.

20 ml of Nato rice and 20 ml of dispersion are shaken in a sealed flask for 48 hours. After that the rice seed Drained and rinsed thoroughly with tap water. The seeds are planted, and the seedlings are through Spraying the foliage inoculated with a P. oryzae culture. After 2 days in a damp room, the inoculated plants are examined.

Test 12 Application to the earth's surface

Preparations of the compounds are prepared as described before the first test and applied to the soil of pots, in which 10 cm of rice seedlings grow. The volume of the dispersion

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of the test compound is always 75 ml, and there will be ratios applied, which correspond to 28 kg / ha to 1.4 kg / ha. Two days after the application of the compounds, the plants are inoculated and held for examination as described in Test 11.

Test 13 placing in the earth

Sterile greenhouse soil is treated with solutions of the test compounds in ethanol, the treatment behavior from 1.4 to 28 kg / ha. The solutions are in a rotary drum mixer thoroughly mixed with the earth. Rice seeds are planted in the treated soil, and the rice seedlings are grown inoculated and examined as described above.

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Seed impregnation

link
from
Ex. applied
Quantity in T / M Disease
valuation 2 1000 4.3 500 4.3 250 3 5 1000 3.3 500 3 250 2.7 6th 1000 1.3 500 1.3 250 1.3 7th 1000 4th 500 4th 250 3 9 1000 3.3 500 1.3 250 1

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Sara impregnation 2604726 applied
Quantity in T / M (Continuation) link
from
Ex. 1000 Disease
valuation 12th 500 2 250 1.3 1000 1.7 15th 500 2.3 250 2 2.3

Treatment of the surface of the earth

link
from
Ex. applied
Amount in kg / ha Disease
valuation 2 5.6 4th 2.8 3.7 1.4 3 5 28 4.3 14th 4th 7th 4.3 5.6 4.3 2.8 3.7 1.4 2

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- 23 -

260A726

Treatment of the surface of the earth (continued)

link
from
Ex. applied
Quantity in T / M Disease
valuation 6th 28 1 14th 1.3 7th 1.3 5.6 5 2.8 4.3 1.4 3.7 7th 28 5 14th 5 7th 4.3 9 28 1.3 14th 1.7 7th 1.3 15th 28 2.7 14th 2 7th 2

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Bringing into the earth

link

of ex.

applied
Amount in kg / ha Disease
valuation 5.6 4th 2.8 4th 1/4 1 5.6 3 2.8 1.7 1/4 1.3 5.6 4.3 2.8 3.7 1.4 2 28 1/3 7th 1/3 28 3 14th 1 7th 1/3

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The method for reducing the adverse effects of fungi attacking the plant foliage is used in agrochemicals generally known working methods carried out. The procedure using the compounds of Formula I is as follows explained.

The method for reducing the adverse effect of fungi attacking plant foliage consists in bringing the fungi into contact with an amount of one of the new compounds of the formula I which effectively inhibits the fungus. The preferred use of the method is to reduce the adverse effects of P. oryzae on rice. The compounds with which the process is preferably carried out are 5-chloro-s-triazolo / 5,1-b / benzthiazole, 5-methyls-triazolo / 5, 1 -n / benzthiazole, 5-fluoro-s-triazolo / 5,1-b / benzthiazole and 2,5-dimethyl-s-triazolo / 5,1-b / benzthiazole.

The practical implementation of the procedure does not necessarily need to be lead to the killing of all fungi, as it otherwise has a beneficial effect on the treated plants. The application of the process results in the killing of part of the fungi and the inhibition of another part of the fungi through injury or slowing down the growth of organisms. The test results given above show that by application an amount of a compound sufficient to inhibit the fungus, the adverse effects of the disease independently of whether or not the entire fungus population is killed by the compound.

As usual with crop protection, the best results will be achieved by applying the compounds several times during growth at intervals of one to a few weeks depending on the weather and severity of infestation. The manufacture of preparations of the compounds and of dispersions of the preparations and the application of the dispersions of the compounds to the

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Plants to be protected are carried out according to methods customary in the field of plant protection. Some explanations of the Application methods only serve to spare the person skilled in the art corresponding own experiments. To combat that Fungi attacking foliage can apply the compounds of formula I either to the foliage of the plants, where they can be found directly come into contact with the fungi, or be applied to the earth, where they are taken up by the plant roots and through the Tissues of the plant are transported to the foliage, where they come into contact with the fungi and their adverse effects Reduce. Both types of application are common in crop protection.

When describing the use of plant protection products Foliage or foliage it is common to express the amount applied by the concentration of the dispersion that is applied. The amount used is expressed in this way because it is customary to apply the dispersion in such an amount that the foliage is covered with a thin film. The applied amount of the dispersion thus depends on the leaf area of the Plant off, and the amount of pesticide itself depends on his concentration in the dspersion.

Compound concentrations ranging from about 25 to 1500 parts of the compound per million parts of the dispersion, each on a basis by weight, are used in the practice of the invention when the mushrooms are applied by application of the compound to come into contact with the foliage. Of course, higher or lower concentrations can occasionally be expedient be; this depends on the severity of the infection and the properties of the particular compound used. In the specified However, the range is usually the optimal concentrations of the compounds.

If the compounds in the context of the invention are applied to the earth, in which the plants grow, then the application amount best than the ratio of the applied amount of

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Expressed in relation to the unit area of the Bpden. The connections according to the invention are used in practice in proportions of about 1 to 50 kg / ha in order to reduce the adverse effects of fungi attacking foliage. As already mentioned, application ratios that exceed or below the stated range may be useful occasionally.

The dispersions in which the compounds are applied to the foliage are mostly aqueous suspensions or emulsions, which are made from concentrated preparations of the compounds. Such suspendable in water or Emulsifiable preparations are either solids to be designated as wettable powders or as emulsifiable concentrates liquids to be designated. Wettable powders are intimate mixtures of active ingredient, inert carriers and surface-active substances Means. The concentration of the active ingredient is usually about 10 to 90 percent by weight. Examples of inert carriers are attapulgite clays, montmorillonite clays, diatomaceous earth and purified Silicates. Examples of effective surfactants which make up about 0.5 to 10% of the wettable powder, are sulfonated lignins, condensed naphthalene sulfonates, a wide variety of naphthalene sulfonates, alkylbenzenesulfonates, alkyl sulfates and non-ionic surfactants, for Example ethylene oxide adducts of alkylphenols.

Exemplary emulsifiable concentrates of the compounds are solutions of the compounds in an inert carrier, a mixture from a water-immiscible organic solvent and emulsifying agents in concentrations of about 100 to 500 g / liter of liquid. Useful organic solvents include aromatics, in particular the xylenes and the petroleum fractions, especially the high-boiling naphthalene and olefin components of petroleum, for example aromatic Heavy naphtha. Other organic solvents can also be used

solvents are used, for example terpene solvents,

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such as natural resin derivatives and substituted alcohols such as 2-ethoxyethanol. Also highly suitable emulsifying agents for emulsifiable concentrates are the surface-active agents which are used in connection with the wettable powders can be used.

Often, auxiliaries are used to improve the property of the aqueous dispersion is used to coat and adhere to foliage. By such auxiliary materials, for example Natural gums, emulsified polybutenes, cationic surfactants and lignin derivatives can be used in certain cases the effectiveness of the treatment will be increased.

Occasionally, the compounds are turned away in the form of dust. Dust preparations from agrochemicals are in the Usually dispersions of the fine powdery active substance in a powdery inert carrier, for example a powdered clay, such as pyrophyllite, bentonite, volcanic deposits and montmorillonite. Dusts are usually produced in such a way that they contain the active substances in concentrations that in the uppermost part of the concentration range, for example 1500 T / M and above.

Dispersions of the compounds are applied to the foliage in the usual way. Low pressure spray devices, high pressure spray devices and small volume air blowers are suitable for the application of aqueous dispersions of the compounds of the formula I. Dust dispersions can be easily applied with the usual equipment, which they with fan in intimate Bring contact with the foliage.

The same dispersions that are used on plant foliage can also be applied to the earth. In addition, the active ingredients can be in the form of granules Preparations can be applied to the earth, which is economical and convenient. Such preparations used in the field of Agrochemicals are commonly known by dispersing the

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Active substance on an inert carrier with predetermined granulate properties manufactured. The carrier is often a coarsely ground clay, such as attapulgite or kaolin clay, with grain sizes in the range from 0.5 to 3 mm. Such granulated preparations can be applied to the earth easily with devices that are designed so that precisely adjusted amounts of the granules can be applied to the earth.

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Claims (7)

Pat e η t a η s ρ r ü c h e 1. Compounds of the general formula where mean: R is hydrogen or a hydroxyl or methyl group and R is a methyl or ethyl group, chlorine or fluorine or a 5-position methoxy group. 2. A compound according to claim 1, characterized that in their formula R is hydrogen 1
and R represents a methyl group or chlorine or fluorine. 3 .. As connections according to claim 1: 2-Hydroxy-5-methyl-s-triazolo / 5, Tb / benzthiazole, 5-chloro-s-triazolo / S, 1-b / benzthiazole, 5-fluoro-2-methyl-s-triazolo / 5,1- b / benzothiazole, 5-methyl-s-triazolo / 5, 1-b / benzthiazole, 2, 5-dimethyl-s-triazolo / 5,1-b / benzothiazole, 5-fluoro-s-triazolo / 5, 1- b / benzthiazole, 5-methoxy-s-triazolo / 5,1-b / benzthiazole, 7-methyl-s-triazolo / 5,1-b / benzthiazole, 609834/0979 2,7-dimethyl-s-triazolo / 5,1-b / benzthiazole, 5-chloro-2-methyl-s-triazolo / 5,1-b / benzthiazole, 5-chloro-2-hydroxy-s-triazolo / 5,1-b / benzthiazole, 5-methoxy-2-methyl-s-triazolo / 5., 1 -b / benzthiazole, 5-ethyl-s-triazolo / 5,1-b / benzthiazole, 5-ethyl-2 -methyl-s-triazolo / 5 , Tb / benzthiazole. 4. Process for the preparation of the compounds according to claim 1 , characterized in that a compound of the general formula is used (ID -N-NH wherein R has the meaning given in claim 1, reacts with a cyclizing agent. 5. Process for the preparation of the compounds according to claim 1, characterized in that a compound of the general formula = NCR ² (III) or its isomer of the general formula 609834/0979 R "ι η ι ο \ / 5 1 2 wherein R has the meaning given in claim 1 and R means a methyl or methoxy group or hydrogen, is reacted with a cyclizing agent. 6. Fungicidal agent containing 10 to 90 percent by weight a compound according to any one of claims 1 to 3 as an active ingredient, 7. Fungicidal agent according to claim 6, containing one or more of the compounds according to claim 3 as an active ingredient. 609834/0979