DE2250077C2 - Pesticides based on an s-triazolo [3,4-b] benzoxazole or s-triazolo [3,4-b] benzthiazole and new s-triazolo [3,4-b] benzothiazole - Google Patents

Description

(I)

or a phytologically acceptable acid addition salt thereof, wherein

X for - O -, - S - or

stands,

R 'is identical or different and _{denotes hydrogen, halogen, C, -C 3} -alkyl, C, -C ₃ -AlkOXy or Ci-Cj-alkylthio, and

R ^{2 is} hydrogen, C 1 -C 1 -alkyl, chloromethyl, C 1 -C 1 -alkoxy, mercapto, C 1 -C 6 -alkylthio, propynylthio, halogen, amino, dimethylaminomethyl, thiocyanato, acetamido, trifluonmethyl or a group of the general formula

Il

- C - R '

represents, wherein R ^{1 is} Ci-Cj-alkoxy or amino,

with the proviso (t) that at least two radicals R ¹ or at least one radical R ¹ and the radical R ^{2 are} hydrogen and (2) that if both R ² and the radical R ^{1 are} in the 5-position, groups other than hydrogen mean, these groups together do not contain more than 6 carbon atoms.

2.3-chloro-s-triazolo [3,4-h] benzothiazole.

3.5-chloro-s-triazolo [3.4-b] benzthiazole.

4.5-fluoro-s-tr: azolo [3,4-b] benzthiazole.

5.5-methyl-s-triazolo [3,4-b] benzothiazole.

The invention relates to the new crop protection agents resulting from the patent claims, the s-triazolo [3,4-bjbenzoxazole] determined as the active ingredient or s-triazolo [3,4-b] benzothiazoles, and the new s-triazolo [3,4-bjbenthiazoles mentioned therein. The compounds mentioned are simplified in the following text as triazolo-benzoxazoles b / w. -benzthiazoles or as compounds of the formula I. designated.

The active ingredients contained in the present crop protection agent can be prepared, for example, by ring closure reaction according to J. Org. Chem. 24 (1959), pages 1478 to 1486, or by the further processes described herein.

The term halogen in the general formula resulting from claim 1 for the as Active ingredient to be used Triazolobenzoxazole and Triazolobenzthiazole refers to fluorine, chlorine, Bromine and iodine. The alkyl chains of those given therein

ίο Alkyl, alkoxy or alkylthio groups can be straight-chain or optionally also branched-chain. Phytologically acceptable acid addition salts are understood as meaning the salts of acids which are not phytotoxic. Otherwise, the choice of acid is not of critical importance, although in some cases a certain anion can lead to particular advantages, for example easier solubility or good crystallization. Examples of acids suitable for salt formation include hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, trifluoroacetic acid, acrylic acid, o-aminobenzenesulfonic acid, bromoacetic acid, citric acid, cyclohexane-U-dicarboxylic acid, formic acid, p. , Maleic acid, malonic acid -Toluenesulfonic acid or methanesulfonic acid.

The triazolobenzoxazoles to be used according to the invention or Triazolobenzthiazole and the new Triazolobenzthia / ole can by several processes some of which are generally applicable.

A first known process which can be generally used for the preparation of these compounds consists in the cyclization of a 2 - (- acylhydrazino) benzoxazole or 2- (2-acylhydrazino) benzthiazole of the general formula 11

R ¹

V) -NH-NH-CR ²

3 ■ /

R ¹

to the corresponding compound of the formula I. This reaction is particularly suitable for the preparation of compounds of the formula I in which X is oxygen or sulfur and R ^{2 is} hydrogen, C ₁ -C _n -AlCyI, trifluoromethyl or the group

- C - R ³

means in which R ^{3 is} Ci -Cs-alkoxy. In cases where R ² has another meaning, various other methods explained below are preferred. In general, this method is applicable ^{regardless of the meaning of R 1.} This cyclization leaves

mi easily by refluxing the respective 2- (2-acylhydrazino) benzoxazole or 2- (2-acylhydrazino) benzthiazole in phenol. It provides the desired compound and water as a by-product. Separation and, if necessary, cleaning of the

Fri nen connection are made in a conventional manner carried out.

A new and improved process especially for the preparation of the compounds of the formula I. wherein R ¹

has the meaning given above, X is oxygen or sulfur and R ^{2 is} hydrogen, C _{1 -C n} -alkyl, trifluoromethyl! or a group of the general forms mentioned! with R ³ = Ci- Or alkoxy, with the proviso (1) that at least two of the radicals R ¹ or "> at least one of the radicals R ¹ and the radical R ^{2 are} hydrogen, and (2) that if both R ² and R ¹ in the 5-position denote groups other than hydrogen, these groups together do not contain more than 6 carbon atoms, consists in that one i <> corresponding 2- (2-acylhydrazino) benzoaxole or 2- (2- acylhydrazino) benzothiazole is reacted with polyphosphoric acid at a temperature from 0 to 250 ⁰ C. to this end, combines the respective compounds of formula II simply with polyphosphoric acid. an inert liquid can be used as reaction medium. However, polyphosphoric acid is itself a liquid so that ma "only those preferably used in excess. The condensation to give the desired compound takes place at a reaction temperature of 0 to 250 ° C. The respective 2- (2-acylhydrazino) benzoxazole or 2- (2-acylhydrazino) benzothiazole and po are preferably mixed Hyphosphoric acid simply with one another and then heats the mixture to a temperature in the specified range, for example 100 to 200 ° C. Some of the desired compound is formed immediately after the reactants have been mixed in the given temperature range. However, higher yields are obtained if the mixture is allowed to react for a certain time, for example a few minutes to a few hours. The desired compound can easily be separated off by pouring the reaction mixture into water and filtering or extracting it. Other conventional methods of separation and purification can also be used as desired.

A second known process, which is also generally applicable for the preparation of the compounds of the formula I, consists in reacting a corresponding 2-hydrazinobenzoxazole or 2-hydrazinobenzothiazole (which, apart from the presence of a hydrazino group instead of an acylhydrazino group, corresponds to the aforementioned formula II) with an orthoester of the general formula R ² -C (OAI-kyl) 3. This process is particularly suitable for the preparation of compounds of the formula I in which X is oxygen or sulfur and R ^{2 is} hydrogen, methyl or ethyl. As in the case of the first method, the importance of the groups R ^{1 is} not important here either. In the reaction, the reactants are consumed in equimolar amounts and the desired compound and the corresponding alkanol are formed as by-products. Expediently, this reaction is carried out an inert liquid as a reaction medium in the presence Ά. The reaction takes place over a wide temperature range, for example between 25 and 200 ° C. However, better yields are achieved in a shorter time if one works at the reflux temperature of the t> o reaction mixture. The separation and, if appropriate, purification are again carried out in a conventional manner.

A third process which is generally applicable to the preparation of the compounds of the formula I consists in the condensation of a corresponding 2-hydrazinobenzothiazole or 2-hydrazinobenzoxazole, as it is also used in the above second preparation process, with an acid of the general formula R ² - COOH. This reaction is particularly suitable for the preparation of compounds of the formula I in which X is oxygen or sulfur and R ^{2 is} hydrogen, Ci - Cn -alkyl, trifluoromethyl or the group

O
- C - R ³

where R ³ = alkoxy with 1 to 3 carbon atoms If R ^{2 has} a different meaning, then other synthetic routes are preferred. In general, this synthetic route is also suitable ^{regardless of the meaning of R 1} the reactants are consumed in equimolar amounts and the desired compound and water are formed as a by-product.Although a separate inert solvent can be used, the acidic reactant is usually a liquid, so that it is expedient to work with an excess of it. The reaction runs within a wide temperature range. However, better yields in a shorter time are obtained if one works at the reflux temperature of the reaction mixture. Separation and, if necessary, purification are again carried out by conventional methods.

Various other processes are used to prepare compounds in the formula of which R ^{2 denotes certain groups.}

Compounds in which R ² stands for amino are prepared by reacting a corresponding 2-hydrazinobenzoxazole or 2-hydrazinobenzothiazole with cyanogen bromide.

Still other compounds of the general formula I are produced from a cyclization product

Lower alkyl - OOC

obtained by conventional reactions. Such reactions include the hydrolysis of the Esters to the sodium or potassium salt

R ² = - CO sodium or potassium

and the aminolysis of the ester to the amide (R ² = carbamoyl). Acylation of the amide gives the acetamido group (R ² = acetamido) or other amides and the reduction of such amides leads to substituted amino groups (R ² = dimethylaminomethyl).

Compounds in whose formula R ² denotes halogen or thiocyanato are selected from the corresponding

Compound of the formula I in which R ^{2 is} hydrogen, obtained by reacting such a compound with a halogenating agent such as an N-halosuccinimide Halogen exchange reactions are produced, for example according to the so-called. Finkelstein reaction. The 3-halogen compounds can also be used as intermediates for the preparation of compounds of the formula I which are substituted in position 3 by amino.Ci-C3-alkoxy or by other substituents. For example, the 3-halogen compound can be reacted with NaSCN to introduce the 3-thiocyanato group. Those compounds in whose formula R ^{2 represents} a halomethyl group can easily be prepared by reacting compounds in which R ^{2 represents} methyl with a chlorinating agent. Compounds in which R ^{2 stands} for mono- or dimethylaminomethyl are prepared from the unsubstituted compound by a Mannich reaction. Regarding the implementation of these various reactions to form the substituents R ² , see Synthetic Organic Chemistry, Wagner and Zook (John Wiley and Sons, Ina, New York. 1956) and Advanced Organic Chemistry, Fieser and Fieser (Reinhold Publishing Co., New York , 1961).

The processes described above are suitable for the preparation of the compounds of the formula I, essentially regardless of the meaning of the radicals R ¹ . In general, it is preferred that substituents of the meaning given are already present in the starting material. In some cases, however, it is preferred to carry out the processes described above with a starting material which has a different substituent than the one ultimately desired and only then to convert the substituent of the triazolobenzoxazole or triazolobenzothiazole obtained into the desired substituent. Compounds which contain additional substituents, for example carboxyl groups, can also be used, since the carboxyl groups can then be removed by decarboxylation. In this context, too, reference is made to the above-mentioned references from Synthetic Organic Chemistry and Advanced Organic Chemistry.

The compounds of the formula I in which X is the group

O O

- s -

50

55

means, can be easily prepared by oxidation of the corresponding benzothiazole compound (X = S).

The compounds of the formula I form with acids <> o Acid addition salts. The salts are prepared in a conventional manner by adding a compound of the Formula I reacted as a free base in a suitable solvent with the desired acid. Separation and if necessary, cleaning is carried out in the usual way carried out.

The invention is further illustrated by the following examples.

A) Manufacturing

Example I.

s-triazolo [3,4-bjbenzthiazole

125 g (0.76 mol) of 2-HydrazinobenzthiazoI, 112.4 g (0.76 mol) of ethyl orthoformate and 2 1 of xylene are heated in a 5-1 three-necked flask with a 20 cm column equipped with a condenser, with stirring, to 105 ⁰ C. The solid substance soon goes into solution, which turns red. Ethanol begins to distill off and after about 125 ml of ethanol have been collected, the reaction is terminated and the mixture is allowed to cool to room temperature. A yellow precipitate therefore separates out, which is filtered off and triturated with diethyl ether. The s-triazolo [3,4-b] benzothiazole obtained in this way is recrystallized from chloroform and melts at 174.5 ° -7 ° C.

Example 2
3-trifluoromethyl-s-triazolo [3,4-b] benzthiazole

17.8 g of 2- (2-trifluoroacetylhydrazino) benzthiazole become mixed with 44.5 g of phenol and refluxed for 24 hours. The reaction mixture is then subjected to steam distillation to remove the phenol and the remaining Oil is extracted with chloroform / water. After removing the chloroform, the remaining Substance, the desired 3-trifluoromethyl-s-triazolo [3,4-b] benzthiazole recrystallized from ethyl acetate and melts at 140 to 14TC.

Example 3
s-Triazolo [3,4-b] benzthiazole-3-thiol

300 g of 2-hydrazinobenzothiazole, 100 g of potassium hydroxide and 225 ml of carbon disulfide are in 60 hours 5500 ml of ethanol heated to boiling under reflux. Shortly after the reflux begins, one begins pale yellow solid substance to precipitate. This substance is filtered off and dissolved in water, which with 1500 ml 0.5 η hydrochloric acid had been added. The mixture thickens. The s-triazolo [3,4-b] benzothiazole-3-thiol formed is filtered off and melts at 242 ° C.

Example 4
3-Amino-s-triazolo [3,4-b] benzthiazole hydrobromide

275 g (1.64 mol) of 2-hydrazinobenzothiazole are suspended in 2.5 ml of methanol and partially suspended with stirring 174 g (1.64 mol) of cyanogen bromide were added. After all of the cyanogen bromide has been added, it thickens Reaction mixture and the temperature begins to rise. The reaction mixture is in an ice bath cooled and half of the contents of the flask are transferred to another flask. Each of the two parts 1 l of methanol is added and the mixture is heated to boiling under reflux while stirring. At the reflux temperature A clear red solution forms, and soon afterwards a light brown precipitate begins to be deposited. The reflux is set for 5 hours. Then the reaction mixture is cooled and freed from most of the solvent on a steam bath. After further cooling it will Diethyl ether was added, causing a yellow precipitate, the desired 3-amino-s-triazolo [3.4-b] benzthiazole hydrobromide is obtained, which is filtered off and washed with petroleum ether. The product will

purified by dissolving in as little boiling water as possible and filtering off the insoluble. When cooling down the product precipitates again from the filtrate. After recrystallization from methanol / diethyl ether and then from methanol alone the product melts at 260 to 262 "C.

Example5
3-methylthio-s-triazolo [3,4-b] benzthiazole

238 g (1.14 mol) of s-triazolo [3,4-b] benzthiazol-3-thiol, 50 g (1.25 mol) of sodium hydroxide and 325 g (2.30 mol) of methyl iodide are mixed with one another in 2500 ml of water and the mixture is refluxed for about 45 minutes. The heat input is then increased and the reflux condenser is removed to evaporate the excess methyl iodide. The desired 3-methylthio-s-triazolo [3,4-b] benzthiazoI precipitates and is filtered off. The aqueous solution is cooled. The solid obtained is dissolved in about 2500 ml of ethyl acetate and recrystallized. Another crop of the desired product crystallizes out from the aqueous solution. The combined shares melt at 129 to 13O ⁰ C.

to

15th

20th

25th

Example 6
3-Bromo-s-triazolo [3,4-b] benzthiazole

6.4 g (0.0366 mol) of s-triazolo [3,4-b] benzothiazole are suspended in 200 ml of carbon tetrachloride at room temperature with stirring and then heated. After adding 6.8 g of N-bromosuccinimide (0.0366 mol + 5%), the solution is heated to boiling under reflux and a trace of azobisisobutyronitrile is added to initiate the reaction. Filtration of the reaction mixture gives blackish crystals which are washed with carbon tetrachloride. After the carbon tetrachloride has evaporated, a purple-colored solid substance is obtained, which is chromatographed on a column filled with silica gel by elution with ethyl acetate. The second portion is checked by elemental analysis and NMR spectrum and thus proves to be the expected 3-bromo-s-triazolo [3,4-b] benzthiazole with a melting point of 166 -rc.

Example 8

3-methyl-s-triazolo [3,4-b] benzthiazole p-toluenesulfonate

2 g of 3-methyl-s-triazolo [3,4-b] benzothiazole are dissolved in 50 ml of ethanol, and 2 g of p-toluenesulfonic acid are added while stirring. After thorough mixing, the reaction mixture is ^{heated to 90 °} C. and kept at this temperature for 1 hour. The solvent is then removed under reduced pressure to give the desired salt as a solid which is recrystallized from ethanol. Melting point 163 to 164 ° C. The structure is confirmed by the NMR spectrum. After a second recrystallization from ethanol, the following values are obtained in the elemental analysis:

Analysis:

calc .: C53.17; H4.18; N 11.73. Found: C, 53.29; H 4.19; N 11.71.

Example 9 3- (Trifluoromethyl) -s-triazolo [3,4-b] benzthiazole

2.5 g of 1- (2-benzthiazolyl) -2- (trifluoroacetyl) hydrazine are slurried with 75 ml of polyphosphoric acid and heated to 160 ° C. for 4 hours. The reaction mixture is then poured onto ice, whereby the desired 3- (trifluoromethyl) -s-triazolo [3,4-b] benzothiazole precipitates, which is filtered off and dissolved in chloroform. The solution is filtered through activated charcoal. The chloroform is removed by evaporation under reduced pressure and a purified product is obtained which, after recrystallization from ethanol, melts ^{at 139 to 141 ° C}

Example 10 3,5-Dimethyl-s-triazoIo [3,4-b] benzthiazole

A solution of 6.1 g of 2-hydrazino-4-methylbenzthiazole (0.034 mol) and 6.4 g of triethyl orthoacetate (0.04 MoI) in 200 ml of xylene is heated to its reflux temperature within 5 hours and then heated to 96 Heated to reflux for hours. The reaction mixture is then reduced to a quarter of its original Concentrated in volume and allowed to cool to room temperature. The obtained 3,5-dimethyl-s-triazoIo [3,4-b] benzothiazole is filtered off and 4 g of substance with a temperature of 196-8 ° C. are obtained.

Example 7
3-chloro-s-triazolo [3,4-b] benzthiazoI-9,9-dioxide

50

10.5 g of 3-chloro-s-tria7o! O [3,4-b] benzth! Azo! are dissolved in 100 ml of methylene chloride and ^{cooled to 0} ° C. 10.2 g of m-chloroperbenzoic acid in 125 ml of methylene chloride are added in portions with stirring. The reaction mixture is heated then for 1 hour at the boil under reflux, with a further 10.2 mg of m-chloroperbenzoic acid in 125 ml of methylene chloride and again for 1 hour to boiling under reflux Then the reaction mixture to dryness under vacuum ^M The residue evaporated is heated to a Abandoned silica gel column and eluted first with benzene and then with graded mixtures of benzene and ethyl acetate and finally with ethyl acetate The first fraction collected turns out to be the desired 3-chloro-striazoIo on the basis of its IR and NMR spectrum, elemental analysis and mass spectroscopy [3 , 4-b] benzthiazoI-95-dioxide of M.p. = 218-20 ° G

Analysis: C 59.09; H 4.46; N 20.67. ber .: C 59.10; H 4.47; N 20.73. found:

Example 11 5,6-Dimethyl-s-triazoIo [3,4-b] benzthiazole

A solution of 12 ml of formic acid (97 to 100 percent) and 3.5 g of 2-hydrazino-4,5-dimethylbenzthiazole is heated to reflux for 24 hours with stirring. The reaction mixture is then increased Cooled to room temperature and poured into water. The 5,6-dimethyl-s-triazolo [3,4-b] benzthiazole precipitates and is filtered off. 2.6 g of substance with a melting point of 226-8 ° G are obtained

Analysis: C 59.09; H 4.46; N 20.67. ber .: C 58.88; H 4.17; N 2039. found:

Example 12

3- (Dimethylaminomethyl) -s-triazolo [3,4-b] benzthiazole hydrochloride

A mixture of 7.5 g (0.042 mol) of s-triazolo [3,4-bjbenzthiazole, 2.52 g paraformaldehyde, 4.48 g dimethylamine hydrochloride and 15.5 ml isoamyl alcohol is 7 Heated to reflux for hours. The reaction mixture is allowed to cool overnight. The desired 3- (dimethylaminomethyl) s-triazolo [3,4-b] benzthiazole hydrochloride precipitates and is filtered off. It is then washed with ether and recrystallized from ethanol / ether. Melting point up to 246X.

D c i S μ i c ι c

I J UIS HO

Further exemplary compounds that are based on those described above and demonstrated by examples Methods prepared using analogous starting materials are as follows:

3-amino-s-triazolo [3,4-b] benzoxazole hydrochloride, F. = 220 ° C (dec.).

s-triazolo [3,4-b] benzoxazole, mp = 162-163 ⁰ C. 15) 3-ethylthio-s-triazolo [3,4-b] benzothiazole, mp = 105-107 ⁰ C.

3- (2-Propynylthio) -s-triazolo [3,4-b] benzthiazole, mp = 165-166 ° C.

3- (Propylthio) -s-triazolo [3,4-b] benzthiazole,

F. = 81-83 ⁰ C.

3-ethyl-s-triazolo [3,4-b] benzothiazole, mp = 115-116 ⁰ C.

3-methyl-s-triazolo [3,4-b] benzothiazole,

F. = 146-148 ° C.
20) 3-methyl-s-triazolo [3,4-b] benzoxazole, mp = 175-178 ⁰ C.

3-Dimethylaminomethyl-s-triazolo [3,4-b] benzthiazole hydrochloride, m.p. = 245 - 246 ° C.

3,5,6-trimethyl-s-triazolo [3,4-b] benthiazole.

F. = 246-248 ° C.

3,6,7-Tnmethy! -S-triazo! O [3,4-b] benzthiazo !,

F. = 243-245 ° C.

3-chloro-5-methyl-s-triazolo [3,4-b] benzthiazoI,

M.p. = 170-172 ° C (dec.).
25) 3-Undecyl-s-triazo! O [3,4-b] benzthiazole,

F. = 68-70 ° C.

3-methyl-5-fluoro-s-triazolo [3,4-b] benzthiazole,

F. = 141-142 ° C.

5-fluoro-s-triazolo [3,4-b] benzthiazole, F. == 172-173 ⁰ C.

5-ethyl-s-triazolo (3.4-b1-benzothiazole,

F. = 152-153 ⁰ C. '

5,7-dichloro-s-triazolo [3,4-b] benzthiazole,

F. = 246-248 ° C.
30) 3-Amino-5-chloro-s-triazolo [3,4-b] benzthiazole hydrobromide, m.p. = 240 - 242 ° C.

3-Chloromethyl-s-triazo! O [3,4-b] benzthiazoI, m.p. 177-179 ° C.

3-chloro-s-triazolo [3,4-b] benzthiazoI, mp = 149-151 ⁰ C 5-methoxy-s-triazolo [3,4-b] benzothiazole, m.p. = 178-180 ° G

5-chloro-s-triazolo [3,4-b] benzothiazole,

M.p. = 186-187.5 ° C
35) 6,7-Dimethyl] -s-triazolo [3,4-b] benzthiazole, m.p. = 272-274 ° C.

3,5-dichloro-s-triazolo [3,4-b] benzthiazole, m.p. = 178-182 ° C.

7-methoxy-s-triazolo [3,4-b] benzthiazole,

M.p. = 178-181.5 ° C.

3-acetamido-s-triazolo [3,4-b] benzthiazole,

F. = 270-272 ° C.
5-methyl-s-triazolo [3,4-b] benthiazole,

M.p. = 184-185 ° C.
40) 3-methoxy-s-triazolo [3,4-b] benzthiazole,

M.p. = 155-156 ° C.

7-ethoxy-s-triazolo [3,4-b] benzthiazole,
F. = 162-163 ⁰ C.

s-triazolo [3,4-b] benzthiazol-3-yl-thiocyanate,

M.p. = 209-210 ° C.

s-triazolo [3,4-b] benzthiazole-3-carboxamide,

F. = 262-265 ° C.
3- Penty ls-triazolof 3,4-b] benzthiazole,

F. = 95-96 ° C.
45) 3-isopropyl-s-triazolo [3,4-b] benzthiazole,

F = 78-80 ° C.

3-propyl-s-triazolo [3,4-b] benzthiazole,

M.p. = 129-131 ° C.

3-methyl-s-triazolo [3,4-b] benzthiazole hydro-

chloride, F. = 239-240 ° C.

3-methyl-s-iriazolo [3,4-b] benzthiazole

hemisulfate, F. = 210-212 ° C.

B) application

It has been found that compounds of the formula I for combating organisms pathogenic for plants, for example fungi and bacteria are suitable. So can the Triazolobenzoxazol- and Triazolobenzthiazolverbindungen to combat organisms such as crown gall, rice blight, bean scab, powdery mildew and anthracnose can be used. They are particularly good at combating fungal organisms and give particularly good results in combating rice blight.

The compounds can be used to good effect in several different embodiments will. In the predominantly applied practice, the active ingredients on the foliage of the opposite To apply to plants sensitive to attack, the compounds against are pathogenic for plants Organisms effective. In addition, the Triazolbenzoxazol- and Triazolbenzthiazolverbindungen can Seeds are applied to him and the resulting plants against the attack of protect pathogenic organisms. The compounds can also be used to combat pathogens Organisms are distributed in the soil. It has been shown that many of the compounds occur through the plants be transported, so that in this embodiment not only a fight against the foliage attacking organisms, but also a fight against the organisms is achieved, which other parts of the plant infested.

The method according to the invention for controlling organisms pathogenic for plants exists entirely generally therein, an effective amount of one or more of the triazolobenzoxazole and triazolobenzothiazole compounds to apply to the place of occurrence of the pathogenic organisms. The connections can be used alone. Within the scope of the invention, however, is the use of liquid, powdery or dusty agents containing one or more of the triazolobenzoxazole or triazolobenzothiazole compounds contain. Such agents are suitable for use on living plants without

Harm to plants. In making such agents, the triazolobenzoxazole and triazolobenzothiazole compounds be modified with one or more of a number of different additives, for example with organic solvents, petroleum distillates, water or other liquid carriers, surface-active dispersants and finely divided inert solids. In such means, the Triazolobenzoxazole or triazolbenzothiazole compounds in concentrations of about 2 to 98 Be present in percent by weight. Depending on the concentration of the triazolobenzoxazole or triazolobenzothiazole compound in the agent, these agents are suitable for combating the undesired, pathogenic for plants Organisms as such, or after dilution with other inert carriers for the production of the ready-to-use means. Preferred agents are those which are both a finely divided solid and a contain surfactant.

The exact concentration of the triazolobenzoxazole or triazolobenzothiazole compounds contained in the Means for application to the pathogenic organisms and / or the places where they occur applied may vary provided that effective amounts are applied to the organism or its Environment to apply. The amount with which the desired effect is achieved depends on the Part of the sensitivity of each organism pathogenic to plants and the activity of each connection used. In general, good results are obtained with liquid preparations, the approximately 0.001 to 0.1 percent by weight of the triazolobenzoxazole or triazolobenzothiazole compound or contain more. In the case of dusting powders, good results are usually obtained with preparations containing 0.5 to 5 percent by weight of the triazolobenzoxazole or triazolobenzothiazole compound or more. Expressed in amounts per hectare will give good results in combating pathogenic organisms for Plants get when the compounds are on the acreage of growing plants with a Dosages of about 0.55 to 5.6 kg / ha or more can be used.

The triazolobenzoxazole and triazolobenzothiazole compounds can be used to produce dusts mixed with any finely divided solids, for example pyrophyllite, talc, lime or gypsum will. For this purpose, the finely divided carrier with the triazolobenzoxazole or triazolobenzothiazole compound ground or mixed, or with a solution of the latter in a volatile organic solvent beiicizi. in eiiisprcchciidef way can the dusts containing these compounds with various solid surface-active dispersants, for example fuller's earth, bentonite, attapulgite or other clays are combined. Depending on The proportions of the constituents can be used by these dusts to combat the pathogens for plants Organisms or as concentrates are applied, which then with further solid surface-active Dispersants or can be diluted with pyrophyllite, lime, talc or gypsum to get the To achieve the desired amount of active ingredient in a means that is suitable for use for fighting suitable for pathogenic organisms Such dusts can also be used as concentrates, be dispersed in water to form spray mixtures with or without the aid of dispersants.

The Triazolobenzoxazol- and Triazolobenzthiazolverbindungen or liquid or dust concentrates, the Containing these compounds can also be mixed with surface-active dispersants. For example, nonionic emulsifiers can be processed into sprays. Such means can easy to use for the control of pathogenic organisms, or you can get it by dispersing in produce diluted spray mixtures for liquid carriers, which contain the active ingredients in any desired amount. The choice of dispersant and the Amount of the same depends on their ability to disperse the concentrates in the liquid carrier to promote the desired spray.

The triazolobenzoxazole and triazolobenzothiazole compounds but can not do with water either miscible organic liquids and a surface-active dispersant to emulsifiable Concentrates are mixed that can be further diluted with water and oil and then spray mixes in the form of oil-water emulsions. In such means, the carrier consists of one aqueous emulsion, d. H. a mixture of a water-immiscible solvent, emulsifying agent and water. Preferred dispersants that can be used for these preparations are oil-soluble and among others the nonionic emulsifiers. z. B. Condensation products of alkylene oxides with inorganic acids, polyoxyethylene derivatives of sorbitan esters and complex ether alcohols. To the for Organic liquids that can be used in these preparations include petroleum grades and petroleum distillates. Toluene and synthetic organic oils. The surfactant dispersants are in liquid form Preparations, usually in amounts of 0.1 to 20.0 percent by weight, based on the total weight of the Dispersant and active ingredient used.

In working according to the invention, the triazolobenzoxazole and triazolobenzothiazole compounds are used or agents containing these compounds on the pathogenic organisms to be controlled or Sites of their occurrence applied in any way, for example with the help of hand dusting devices or spray devices. The application to the plant parts above the ground can be more expedient Manner with motor sprayers, boom sprayers, high pressure sprayers and spray atomizers. When used on a large scale, airborne dusts or aerosols can be applied will. When using the Triazolobenzoxazol- and Triazolobenzthiazoloverbindungen for Special methods can be used to combat rice blight be preferred for the application, which can be attributed to the special conditions of rice cultivation One of these special methods is the application to the surface of the water, the soaking treatment of plants to be transplanted, seed treatment and the like. Other methods are for readily apparent to those skilled in the art.

The following examples illustrate the beneficial results obtained in combating for Plant pathogenic organisms achieved with the triazolobenzoxazole and triazolobenzothiazole compounds and enable those skilled in the art to utilize these compounds to advantage.

Examples 49-71
A number of those to be used in accordance with the invention

13 14

Triazolobenzoxazole and triazolobenzothiazole-linked water were covered and the surface

fertilizers were made with regard to their effect when scraped off. The aqueous suspensions of 4

Control of Colletetrichum lagenarium (Anthra plates were filtered through a cheesecloth, on a

knose) for cucumbers and assessed. The tests brought volume of 50 ml and used for spraying

and ratings were performed as follows- 5 plants used in about 35 pots,

men. After inoculation, the plants became 48

For each individual test, a 10 cm pot was kept in a damp room at 18 ° C. for hours and

with sterilized soil with a vermiculite layer on then for about 9 days under normal vegetation

inseminated the surface with 4 cucumber seeds and left to stand under house conditions and finally to

allowed to stand under normal greenhouse conditions. Checked for the determination of the fight against anthracnose.

The shoots were reduced to two. About 15 Each test also included a comparative test,

Days after the insemination, the foliage was treated with an aqueous solution which

Sprayed solution of the respective compound, dry cyclohexanone and the mixture of surface-active

left and then with an aqueous suspension of ven agent in the same concentrations

Comidia of Colletotrichum lagenarium sprayed and contained 15, took place,

so inoculated. The results obtained are as follows

The individual triazolobenzoxazole and triazolo tables are listed, with the following disease

Benzothiazole compounds have been applied in conventional rating system: Formulated wisely. For the most part, the

respective compound in a certain amount 20 1 - difficult

Cyclohexanone dispersed, which is a small amount of a 2 - moderately heavy

Mixture of two nonionic surface-active 3 - moderately

Containing agents of the sulfonate type, and then with water 4 - weak

diluted so that a finished treatment mixture 5 - no disease was obtained, the 400 parts of the respective compound 25

per million parts (weight) of the finished agent in addition to In the control pots, there was always a severe infestation

the cyclohexanone in a concentration of 0.67% of the cucumber plants with anthracnose. In

and the mixture of surfactants in all cases is not or only partially phytotoxic

at a concentration of 0.0353%. exceptionally small in scope. One

The conidia suspension was prepared with the exception of those with 5-methyl-s-triazolc {3,4-

PiIz in Petrischaleri on orange juice agar 14 days with b] benzthiazole treated plants, since this involves

24 ° C was grown, the dishes then with distilled phytotoxicity could be observed.

Table I.

Combating Anthracnose

Link disease assessment

3-pentyl-s-triazolo (3,4-b) benzthiazole 4+

50) 3-trifluoromethyl-s-triazolo (3,4-b) benzthiazole 5

3-chloro-s-triazolo (3,4-b) benzthiazole-9,9-dioxide 4-

s-Triazolo (3,4-b) benzthiazole-3-thiol 4+

3-propyl-s-triazolo (3,4-b) benzthiazole 3 -

3,5-dichloro-s-triazolo (3,4-b) benzothiazole 4+

55) 3-Methylthio-s-triazolo (3,4-b) benzthiazole 5

s-Triazolo (3,4-b) benzthiazole 5

s-Triazolo (3,4-b) benzoxazole 4

3-Ätri> lthio-s-triazolo {3,4-b) bcnzthia2o! 5

3-propylthio-s-triazolo (3,4-b) benzthiazole 5

60) 3-ethyl-s-triazolo (3,4-b) benzthiazole 5

3-methyl-s-triazolo (3,4-b) ben2thiazole 4+

3-methyl-s-triazolo (3,4-b) benzoxazole 4+

3-chloro-s-triazolo (3,4-b) benzthiazole 4+

3-Bromo-s-triazolo (3,4-b) benzthiazole 4+

65) 5-methoxy-s-triazolo (3,4-b) benzthiazole 3

5-chloro-s-triazolo (3,4-b) benzothiazole 4+

6,7-Dimethyl-s-triazolo (3,4-b) benzthiazole 3+

7-methoxy-s-triazolo (3,4-b) benzthiazole 3

5-methyl-s-triazolo (3,4-b) benzthiazole 5

70) 3-methoxy-s-triazolo (3,4-b) benzthiazole 5

s-Triazolo (3,4-b) benzthiazol-3-yl-thiocyanate 3

Examples 72-79

Exemplary representatives of the triazolobenzoxazole and triazolobenzothiazole compounds have also been referred to evaluated for their effectiveness in combating the pathogenic organism that causes kxonengall disease (Agrobacterium tumefaciens) in tomato plants. The following procedure was used

3 tomato seeds were placed in sand in 10 cm plastic pots and later reduced to 2 plants, ι ο An inoculum of Agrobacterium tumefaciens was grown in the meantime on self-prepared potato dextrose agar in test tubes. Sterile water was then added to the cultures to provide the required amount of bacterial suspension which was used to inoculate the tomato plants about 4 weeks after the seeds were planted. Inoculation was done by dipping a small insect attachment needle into the bacterial suspension and then stabbing it through the stem of each tomato plant. The plants were then removed from the sand and the roots of each individual plant were placed in an aqueous solution in a large test tube containing the compound to be tested at a concentration of 40 ppm, 0.067% cyclohexanone and 0.00353% surfactant and sodium chloride in one Concentration of 0.85%. The plants were kept for about 10 days under normal greenhouse conditions with daily aeration. Each plant was then examined for symptoms of kroria bile egg disease

For comparison, 2 inoculieite plants were placed in a solution in separate test tubes which contained all components with the exception of the compound to be tested. Otherwise they were in treated in every way exactly as the test tubes with the treated plants.

The results of this test are compiled in the following table, using the same rating scale as in the previous examples. All control plants showed severe symptoms of crown gall disease. The phytotoxicity was either completely absent or only minor in all cases with the exception of the plants treated with 5-methoxy-s-triazolo [3,4-b] benzthiazole, in which considerable phytotoxicity was found.

Table II

Combating the crown gall

link

Disease assessment

3-methylthio-s-triazolo (3,4-b) benzthiazole s-triazolo (3,4-b) benzthiazole
3- (propylthio) -s-triazolo (3,4-b) benzthiazole 75) 5-methoxy-s-triazolo (3,4-b) benzthiazole 7-methoxy-s-triazolo (3,4-b) benzthiazole 3 -Methoxy-s-triazolo (3,4-b) benzthiazole 7-ethoxy-s-triazolo (3,4-b) benzthiazole s-triazolo (3,4-b) benzthiazole-3-carboxamide

3-

3-

3-

3-

Examples 80-85

A number of the triazolobenzoxazole and triazolobenzothiazole compounds were tested and evaluated for their effectiveness in combating powdery mildew (Erysiphe polyconi) on beans. the Tests were carried out as follows:

4 bean seeds were placed in 10 cm pots with soil, which were later reduced to 2 plants. On the tenth day after the seeds were planted, the compound to be tested was applied to the young plants in Applied in the form of a preparation corresponding to those described in Examples 76-98. The treated Plants were then placed near and under other plants that were in large measure of Powdery mildew were infested, so that the treated plants also due to the usual draft of air were infested. In this position, the plants were kept under normal greenhouse conditions for about 7 to 10 days and then examined to see if they had symptoms of powdery mildew disease. A blank test was carried out with each test. The blank test consisted of one group of 4 plants grown with a solution of solvent and emulsifier without a compound to be tested were treated, as was also described in Examples 49 to 71. The results are in the The table below is compiled using the same rating scale as in the previous examples was applied. The bean plants in the blind samples all showed severe powdery mildew infestation. In all cases no or only very little phytotoxicity was observed.

17th Powdery mildew 22nd 50 077 18th Table III from the Combat

Connection of disease

valuation

80) s-Triazolo (3,4-b) benzthiazole-3-thiol 3-

3-ethylthio-s-triazolo (3,4-b) benzthiazole 3

6,7-dimethyl-s-triazolo (3,4-b) benzthiazole 5

s-Triazolo (3,4-b) benzthiazole-3-carboxamide 3

3-propyl-s-triazolo (3,4-b) benzthiazole 3

85) 3,5-dichloro-s-triazolo (3,4-b) benzthiazole 5

Examples 86-122 Suspension of the conidia of the rice brandy organism

A number of Triazolobenzoxazol- and Triazolo- were inoculated. In every single case it contained the

was benzthiazole compounds with respect to their WIR 20 treatment solution 400 parts of compound per million

kung to combat rice blight (Piricularia parts of the finished solution, based on weight. The

oryzae) checked and assessed. For this purpose, the following pots were kept in a damp room for 48 hours

Working method used: let stand by mixing the same 18 ° C and then again under for 6 days

Parts of building sand and crushed earth crust were kept under the greenhouse conditions. Then followed

Material made that is placed in 10 cm pots 25 the rating, using the same rating scale as

and was sown vigorously with rice seeds. The inseminated in the previous examples was applied.

Pots were then placed under vegetation for about 2 weeks.

House conditions, according to which each led: pots of rice saplings were with a

Pot found a dense vegetation of rice saplings. aqueous solution of cyclohexanone and the like

In addition, an aqueous suspension of 30 mixture of two nonionic surface-active

Produced conidia of the rice brandy fungus. The fungus means of the sulfonate type, but without active ingredient

was sprayed on rice husk agar at 28 ° C in Petri dishes. Otherwise the pots turned out just like that

bred. After 8 days, the dishes were treated with the remainder.

20 ml of distilled water are added, and the surface The evaluation results are as follows

The culture was compiled with a rubber flag to separate the J5 table. The ratings were

scraped off the conidia. not all done at the same time. In all exams

In each individual case, however, the untreated control pots were treated

solution, as described in Examples 49 to 71, strong symptoms of rice blight. In general it was

and no phytotoxicity was observed on the leaf surfaces of the rice plant. Only at

zen in the individual pots and sprayed dry w few pots lay low phytotoxicity

left, whereupon the foliage with the watery front.

Table IV

Fighting rice blight

Link disease assessment

3-trifluoromethyl-s-triazolo (3,4-b) benzthiazole 4

s-Triazolo (3,4-b) benzthiazole-3-thiol 4

3-Amino-s-triazolo (3,4-b) benzthiazole hydrobromide 4

s-Triazolo (3,4-b) benzthiazol-3-ol 5

90) 3-Methylthio-s-triazolo (3,4-b) benzthiazole 4+

s-Triazolo (3,4-b) benzthiazole 4+

3-Amino-s-triazolo (3,4-b) benzthiazole 3

s-Triazolo (3,4-b) benzoxazole 4+

3-ethylthio-s-triazolo (3,4-b) benzthiazole 3

95) 3- (2-Propynylthio) -s-triazolo (3,4-b) benzthiazole 3+

3- (Propylthio) -s-triazolo (3,4-b) benzthiazole 3+

3-methyl-s-triazolo (3,4-b) benzthiazole 4+

ä 3-Methy! -s-triazolo (3,4-b) benzoxazole 5

t ^5. (- chloro-s-triazolo (3,4-b) benzthiazole 5

continuation

link

20th

Disease assessment

100) 3-Bromo-s-triazolo (3,4-b) benzthiazole 4+

5-methoxy-s-triazolo (3,4-b) benzthiazole 4+

5-chloro-s-triazolo (3,4-b) benzothiazole 5

6,7-Dimethyl-s-triazolo (3,4-b) benzthiazole 4+

7-methoxy-s-triazolo (3,4-b) benzothiazole 3+

105) 3-Acetamido-s-triazolo (3,4-b) benzthiazole 4

5-methyl-s-triazolo (3,4-b) beiizthiazole 5

3-methoxy-s-triazolo (3,4-b) benzthiazole 3+

7-ethoxy-s-triazolo <3,4-b) benzthiazole 3

s-Triazolo (3,4-b) benzthiazol-3-yl-thiocyanate 3

110) s-Triazolo (3,4-b) benzthiazole-3-carboxainide 3-

3-chloro-s-triazolo (3,4-b) ben2thiazole-9,9-dioxide 4+

3-propyl-s-triazolo (3,4-b) benzthiazole 4

3,5-dichloro-s-triazolo (3,4-b) benzthiazoI 3

3-pentyl-s-triazolo (3,4-b) benzthiazole 4+

115) 3-Chloro-5-methyl-s-triazolo (3,4-b) benzthiazole 4+

3-methyl-5-fluoro-s-triazolo (3,4-b) benzthiazole 3+

5-fluoro-s-triazolo (3,4-b) benzthiazole 4

5-ethyl-s-triazolo (3,4-b) benzothiazole 4

5,7-dichloro-s-triazolo (3,4-b) benzthiazole 3

120) S-Amino-S-chloro-s-triazoloO ^ -bJbenzthiazol-hydrobromid 3

S-dimethylaminumethyl-s-triazoloO ^ -bJbenzthiazole hydrochloride 4-

3-chloromethyl-s-triazolo (3,4-b) benzthiazole 3 -

Examples 123-126

A number of additional evaluations for each compound were made within the scope of the invention

using compounds was carried out with reference to 40, with the concentration of the respective

Effectiveness in combating rice blight tested compound was 250,500 or 1,000 parts per million,

and rated. The evaluations were made according to the results are the same in the following table Procedures as set out in Examples 86 to. were reported with the following differences: With

Table V

Fighting rice blight

link

Concentration of
Treatment solution Disease
valuation (ppm.) 1000
500
250 5
4+
5 1000
500
250 5
5
5 1000
500
250 3
3-
4+ 1000
500
250 5
5
2

123) 3-Methyl-s-triazolo (3,4-b) benzthiazole-p-toluenesulfonate

124) 3-methyl-s-triazolo (3,4-b) benzthiazole hemisulfate

125) 3-Undecyl-s-triazolo (3,4-b) benzthiazole

126) 3-Methyl-s-triazolo (3,4-b) benzthiazole hydrochloride

Examples 127-132

A number of the triazolobenzoxazo and triazolobenzothiazole compounds to be used in the context of the invention were nxh on their effect in combating rice blight when applied The soil was checked and assessed before planting. For this purpose, a certain amount of the respective Compound dissolved in ethanol and the solution was blown up in a drum with a DeVilbiss sprayer sprayed rotating soil and the so treated soil was in round 10 cm pots without drainage holes brought in It was worked in such a way that there was a certain amount in kg per ha, namely 28, 14, 7, 5.6, 2.8 and 1.4 kg / ha, respectively. Then the pots were sown with rice seeds (variety Nato) and under for 2 weeks Maintained greenhouse conditions, whereupon the rice

Shoots inoculated with conidia of Piricularia oryzae became; the preparation of the conidia suspension and the inoculation were as in the preceding Examples carried out The pots were then carried out for 48 hours in a damp room at 18 ° C. and finally kept under greenhouse conditions for a further 5 days. The results of the examination of the Disease severity is assessed using the rating scale given in the previous examples reproduced below.

Three repetitions and a blind test were carried out for each test, in which Soil was used, which was treated only with an aqueous solution of ethanol in the same concentration had been. Strong symptoms of rice blight appeared in the comparison pots.

Table VI

Combat rice blight by introducing the active ingredient into the soil before planting

link

127) s-Triazolo (3,4-b) benzothiazole

128) 3-methyl-s-triazolo (3,4-b) benzthiazole

129) 3-methyl-s-triazolo (3,4-b) benzoxazole

130) 3-Chloro-s-triazolo (3,4-b) benzthiazole

131) 5-chloro-s-triazolo (3,4-b) benzthiazole

132) 5-methyls-triazolo (3,4-b) benzthiazole

Amount of connections Disease in kg per ha valuation 28 4th 14th 3 + 7th 2+ 28 3+ 14th 4+ 7th 2+ 28 4+ 14th 3 7th 3- 28 5 14th - 7th - 28 5 14th 5 7th 4+ 5.6 5 2.8 4+ 1.4 3 28 5 14th 4+ 7th 4+ 5.6 4+ 2.8 3

Examples 133-136

A number of the triazolobenzoxazole and triazolobenzothiazole compounds to be used according to the invention was tested for its effect on combating rice blight (Piricularia oryzae) when it was applied to the Surface of with. Water of saturated soil in which the rice grew.

Rice (variety NATO) was sown in round 10 cm pots without drainage holes. The earth became during the entire experiment carried out in the greenhouse kept in a saturated state with water.

About 14 days after sowing, the saplings became treated. For this purpose, a treatment solution was poured onto the surface of the earth in each pot, which as in Examples 154 to 159 described. On the third day after the treatment the plants were treated with a suspension prepared as described in Examples 86 to 122 pathogenic organisms inoculated and placed in a humid room at 18 ° C for 48 hours. Afterward the plants were kept under normal greenhouse conditions for 5 days and then checked for presence tested for symptoms of rice burn and, if positive, for its severity.

For each test three repetitions and a comparative test were carried out, one aqueous Solution with an ethanol content of 0.5% was applied. The results of these assessments are in the compiled in the following table. The comparison pots uniformly showed very strong symptoms of the Rice blight.

23 24

Table VH

Fighting rice blight by applying the active ingredient to the surface of the earth

link

applied amount of disease

Compound in kg per hectare rating

133) 3-chloro-s-triazo! O (3,4-b) benzothiazole

134) 5-chloro-s-triazolo (3,4-b) benzthiazole

135) 5-methyl-s-triazolo (3,4-b) benzthiazole

136) s-Triazolo (3,4-b) benzthiazole 28
14th

28

14th
7th

5.6
2.8
1.4

28

14th
7th

5.6
2.8
1.4

28

14th
7th

4+ 4+ 3+

5 +

4+

4+

4-

4+

4-

3-

4+

4-

3-

Examples 137-140

30th

A number of the triazolobenzothiazole compounds have been tested for effectiveness in combating Rice brandy tested when applied to rice seeds by soaking the seed.

The respective compound to be tested was dissolved in ethanol and diluted with water, the 0.1% Containing polyoxyethylene sorbitan monolaurate, whereby a treatment solution was obtained which the compound concerned at a concentration of 250 parts per million parts of total solution. All solutions contained 0.5% ethanol and about 0.1% of the polyoxyethylene sorbitan monolaurate.

20 ml of each solution was placed in a 125 mm Erlenmeyer flask, and 20 ml (about 12.5 g) rice seeds (variety NATO) added. Each flask was capped and shaken for 48 hours, after which the rice was drained and rinsed with tap water.

The treated seed was planted in 10 cm square pots and under greenhouse conditions held. As soon as the rice shoots reached a height of three to four inches (about 14 days after the Sowing), they were with a fungi suspension prepared as described in Examples 86 to 122 of Piricularia oryzae (rice brandy) inoculated. The plants were then kept in a humid room at 18 ° C. for 48 hours incubated, kept in the greenhouse for about 5 days and then using the one in the preceding Evaluation system described in the examples with regard to the severity of the disease.

For each test, three tests and two comparison tests were carried out: (1) with water mil 0.5% ethanol and 0.1% polyoxyethylene sorbitan monolaurate and (2) with water alone.

The results of these tests are summarized in the following table

Table VIII

Reviews after soaking the seed

link

Concentration of the compound in the treatment solution ¹ )

Amount of Compound in grams per 45.3 kg of seeds

Disease assessment

137) 3-methyl-s-triazolo (3,4-b) benzthiazole

138) 3-chloro-s-triazolo (3,4-b) benzothiazole

139) 5-chloro-s-triazolo (3,4-b) benzthiazole

1000 45.4 4th 500 22.7 3 250 11.4 2 1000 45.4 5 500 22.7 4+ 250 11.4 3 1000 45.4 5 500 22.7 5 250 11.4 4+ 175 7.8 3+ 100 4.5 3

25th

l-'orlsct / uni!

26th

link

Concentration of
Connection in the
Treatment solution ')

Amount of
Connection in g
per 45.3 kg of seeds

Disease assessment

140) 5-methyl-s-triazolo (3,4-b) benzthiazole

¹ I In ppm, based on the weight of the seed.

The compounds according to the invention can not only be used alone or in combinations with one another, but can also be used in combination with other known fungicides, such as the following Examples show.

Example 141

5-Chloro-s-triazolo [3,4-b] benzothiazole was used along with numerous other substances on the Effect in combating rice blight, Helminthosporium and dry rot in young rice plants (Varietal Nato), Penrod barley and tomatoes (Varietal

1000 45.4 5 500 22.7 4 + 250 11.4 4th 175 7.8 3 -

Bonny Best). Each compound or combination of compounds was applied to the foliage by spraying a conventional preparation. After drying of the foliage plants with Piricularia oryzae, Helminthosporium sativum or Phytophthora infestans was inoculated and incubated hours at 18 ⁰ C in a humidified chamber. The plants were then kept under greenhouse conditions and finally examined for the development of the disease 5 days after spraying. The results of two tests per treatment are compiled in the table below.

Table IX

dosage
(ppm active ingredient)

Mean disease score
Rice Brand Helminth.

Dry rot

A. + B 25th + 600 5 + 200 A. 25th 5 B. t-C 600 + 400 200 + 100 A. 25th 5 Q + D 400 + 400 100 + 100 A. 25th 5 D. + E 400 + 400 100 + 100 A. 25th 5 E. + F 400 + 400 iöö + 100 A. 25th 5 F. + G 400 + 400 100 + 100 A. 25th 5 G + H 400 + 50 100 + 10 A. 25th 5 H + 1 50 + 25 10 + 5 A. 25th 5

2+
2+

3
3-

2+
2

3-

2+

A.
t "

3-4 +
A-

4th
3

4+
A-

4+
3+

4+
4+
3-3-

3
+

2-3

3-2 +

2+
2-

2+

2-1 +

1 + 2+

3+

3+ 4+ 4

4+ 4

4+ 4+

A-

4-

T _

3+ 4+

3+ 4+

3+ 3

4+ 2+ 1

1 + 1 + 2-1
2-

28

dosage
(ppm active ingredient) Mean disease rating of rice blight Helminth.

Troekenluule

1 25th 5 A + J 25 +25 5+ 5 J 25th 5 A + K 25 + 200 5 + 50 K 200 50 control 0 0 0

3-1 +

4+

4-

4+

4+

2+

1 1 1 2-

+ 2-

1
1

4+ 3-

3-

2
1

2 +

1 +

2 + 3

3-

2-

2-

2+

2 1 1

A = S-chloro-s-triazoloCS ^ -bJbenzthiazole.

B = tribasic copper sulfate.

C = mixture of ammoniates from ethylene bis (dithiocarbamate) zinc and ethylene bis (dithiocarbamic acid) bimolecular

and trimolecular cyclic anhydrosulfides and disulfides.

D = 2,4,5,6-tetrachloroisophthalonitrile.

E = 2,4-dichloro-6- (o-chloroanilino) -s-triazine.

F = mangano ethylene bisdithiocarbamate.

G = N-trichloromethylthio- ^ - cyclohexene-l ^ -dicarboximide.

H = O-ethyl-S.S-diphenyldithiophosphate.

I = pentachloromandelonitrile.

J = HButylcarbamoylJ ^ -benzimidazole-carbamic acid methyl ester.

K = alpha- (2,4-dichlorophenyl) -alpha-phenyl-5-pyrimidinomethanol.

example

5-Chloro-s-triazolo [3,4-b] benthiazole has also been shown to contribute to its effects in combating rice blight tested and evaluated its application together with known fungicides on the water surface. Rice plants were grown in pots covered with water. The connection or connections were made in Usually prepared and applied to the surface of the water as soon as the plants are 10 days old. With

Table X

Two experiments were carried out for each compound or combination of compounds. Three days later, all plants were inoculated with Piricularia oryzae and incubated in a humid room at 18 ° C. for 48 hours. The plants were then kept in the greenhouse for 5 days and finally evaluated with regard to the effect achieved. The results are shown in the following table:

Dosage kg / ha

(pounds / acre) rice burn rating

A + B

A + C

Control solvent

1.13 3.39

1.13+ 3.39 + 11.2

5.6 11.2

1.13+ 5.6 3.39 + 11.2

5.6 11.2

5 10

I + 3 + 5 10

3+ 4+ 4+ 5

3-3

4+ 4+

2+

A = S-chloro-s-triazolo (3,4-b) benzthiazole.

B = methyl-1-O-butylcarbanioylH-benzimidazole carbamaL

C = 0,0-diisopropyl-S-benzyl-phosphorothiolate

Example 143

5-Chloro-s-triazolo [3,4-b] benzothiazole was also used together tested with other substances for the control of rice blight through seed treatment and rated.

Rice seeds were initially made with 5-chloro-s-triazolo [3,4-b] benzthiazole and then treated with a second substance. These seeds were placed in sterile pots

Table XI

Evaluation of the emergence of the plants and the rice brandy 5-chloro-s-triazolo (3,4-b) benzthiazole

and planted in non-sterile soil. Once the rice shoots were 3 1/2 to 4 inches tall, they became inoculated with Piricularia oryzae and incubated as described in the previous examples. Afterward they were kept in the greenhouse for 5 days and thereafter for the control of the disease rated. The results are summarized in the following table:

Active ingredient sterile Earth 10 g / 100 kg
E RB 5
4+
4+ 30 g / 100 kg
E RB 5
5
5 non-sterile RB Earth 4+
4+
5 30 g / 100 kg
E RB 5
5
5 ml or
g / 10Okg
Seeds 0
pi) RB O O Ov 5
5
5 CTv OO OO 5
4+
5 0
E. 1
1
1 4+
5
5 4th
9
8.67 4+
5
5 Methyl mercury
dicyandiamide 0
1.57 ml
3.15 ml 10
10
10 + + 10
9
9 4+
5
5 Ov Ov OO 5
5
5 1.67
9
9.33 1
1
1 10 g / 100 kg
E RB 4+
5
4+ 8.33
8th
8.33 5
5
5 Bis (dimethyldithio-
carbamoyl) disulfide 0
124.6 g
249.7 g 10
10
10 2-
1 +
1 10
10
10 9
9
9 6.33
10
10 1
1
1 6.67
10
10 9
8.33
9.67 N-trichloromethylthio-
4-cyclohexene-1,2-di-
carboximide 0
124.6 g
249.7 g 10
10
ID 1
1
1 4th
10
10 1.33
9.67
9.67 5.67
10
10

') »Evaluation of the emergence of the plants on a scale of 0-10, with 10 being 100 percent germination and emergence corresponds to the plants.

Examples 144-145

Any of the compounds 5-chloro-s-tria;: olo [3,4-b] benzothiazole and 3-methyl-s-triazolo [3,4-b] ben; '. thiazo! was used on its effect in combating rice blight checked when used to water roots when transplanting.

Each of the compounds was used to prepare a series of aqueous suspensions with different Concentrations of the compound used, which, however, were uniformly 0.05% polyoxyethylene sorbitan monolaurate and contained 1.0% ethanol. The roots of 21 day old rice plants were immersed in the Submerged suspensions, 36 plants per suspension. The rice plants were then grown in Transplanted container with earth covered with water. After the plants grew, they became inoculated with Piricularia oryzae, taking the measures described in the previous examples were applied. 11 days later the plants were

Table XII

Rice blight and plant damage caused by soaking the roots when transplanting

link

144) 5-chloro-s-triazolo (3,4-b) benzthia.ral

145) 3-methyl-s-triazolo (3,4-b) benzthiazole

aqueous solution containing 1.0% ethanol and
0.05% polyoxyethylene sorbitan monolaurate water

examined for rice burn and damage. 3 experiments were carried out for each active ingredient concentration. In addition to the rice plants treated with one of the two compounds, a group of Rice plants treated for 5 minutes in the same way with an aqueous solution containing 1.0% ethanol and Containing 0.05% of the same polyoxyethylene sorbitan monolaurate, and another group was mixed with water treated alone, so that two comparative tests were carried out.

The results are compiled in the table below. The rice burn assessments were made based on the same scale used above. The plant damage was rated on a scale from 0 to 10, where:

0 = all plants healthy
10 = all plants dead

Concentration of Rice brandy Plants- Connection in the valuation damage Soaking solution in percent 0.05 3+ 0 0.1 4+ 0.3 0.2 4+ 0 0.05 3- 0 0.1 4- 0.3 0.2 3- 1.3 - 1 0.6

Examples 146-147

I ede of the compounds 5-chloro-s-triazolo [3,4-b] benzthiazole and 3-methyl-s-triazo) o [3,4-b] benzthiazole have been tested for their effect in combating leaf rust (Puccinia recondita) of wheat tested by application to the seed

Certain amounts of wheat seeds (Monon variety) were mixed with liquid preparations of the respective Coated connection. Specifically, two formulations of each compound were used, a 15 percent wettable powder (»15 W«) and a 25 percent wettable powder (»25 W«). Each Powder was mixed with several small portions of water, and about 3 percent by weight of the seed was added to each preparation treated. A large number of treatment preparations were thus produced from each master preparation which, in terms of the amount of the on with the compound applied to the respective preparation treated seeds (expressed as g of compound per 100 kg of seeds). After the treatment, the seeds were planted. Other seeds that were not treated, for the sake of comparison, were also planted. All plantings were also planted were kept under the usual agricultural conditions until the wheat saplings were about 7 '/ 2 cm were high. Then all plants were inoculated with rust leaf spores (Puccinia recondita) and 48 hours

then incubated in a humid room at 18 ° C the plants were kept under normal growth conditions for a further 8 days and finally examined for damage to plants and the occurrence of blue rust The results are in the table below

Compiled: Leaf rust was rated on a scale from 1 to 5, where: 1 = severe infestation due to the disease and 5 = no symptoms of the disease. The plant damage did not become numerical assessed, but, if available, with regard to their type

specified.

Table XIII Assessment of leaf rust and plant damage, application to Sarn-n

link Preparation g compound / kg 3- 2- Seeds 400 600 tion 100 1 + 200 4- 146) 3-methyl-s-triazolo- 15W 2 thin 3 thin 3 (3,4-b) benzothiazole growth growth 5 5 very low 25W 4th inhibition 2 minor - 147) 5-chloro-s-triazolo- 15W 3 inhibited inhibition (3,4 ~ b) benzothiazole no plants no plants 25W 3 inhibited Comparative experiment

Examples 148-149

Any of the compounds 3-methyl-s-triazolo [3,4-b] benzothiazole and 3-chloro-s-triazolo [3,4-b] benzthiazole has been tested for its effect in combating wheat leaf spots (Helminthosporium sativum) checked. The compounds were applied after the seed coating technique. The exams were carried out exactly as described in Examples 185 to 186 with the exception that the Inoculating with Helminthosporium sativum was done. The results are in the following Table compiled:

Table XIV Assessment of leaf spots and damage to plants, application by seed coating

link

Preparation g compound / 100 kg seeds
200

400

600

148) 3-methyl-s-triazolo- 15W 3+ 3+ 3+ - (3,4-b) benzothiazole 25W 3 3 3+ 3+ 149) 3-chloro-s-triazolo- 15W Ί - 3+ 4+ - (3,4-b) benzothiazole 25W 1 4- 2 escapement 4 escapement Comparative experiment - 1

Examples 150-151

Each of the compounds 5-chloro-s-triazolo [3,4-b] benzthiazole and 5-methyl-s-triazolo [3,4-b] benzthiazole have been used for their effect in combating rice blight (Piricularia oryzae) checked for boxes of young rice plants just before transplanting. In each case 270 g of swollen rice seeds were sown on loam soil in a box with the dimensions 28 × 58.5 × 3 cm , germinated and allowed to grow up to the stage of 4 to 5 leaves with a leaf length of 15 to 18 cm. At this stage, each box of the treating plants was immersed in a treatment solution for 15 minutes. which contained the respective compound immersed. The compounds were present in the solution in various concentrations. On average, about 1.2 liters of each crate were used

33 34

Treatment solution added. The plants treated in this way with regard to combating rice blight, the

Plants as well as comparison plants, the untreated plant height and the number of shoots per

were plant tested in rice fields on the same day. The results are in the following

transplanted About two months later the table was compiled

ppm Fire fighting
in%') Plant height
(cm) ^b ) Number of lap
things per plant ^b ) 150) 5-chloro-s-triazolo (3,4-b) -
benzthiazole 1000
4000 0
22nd 64
66 15.6
14.2 151) 5-methyl-s-triazolo (3,4-b) -
benzthiazole 1000
4000 15th
51 65
67 15.0
13.7 Comparative experiment 0 0
(24) 0 65 14.5

") The percentage of rice blight (PiricularU oryzae) on rice leaves was determined by determining the degree of infection and the nature of the damage to 100 plants per batch was determined.

^b ) The average plant height and the number of shoots per plant were determined by testing 100 plants per batch.

^c ) Percentage of infection of the leaves of unchecked plants.

_R. . . ,. the soil of the boxes with rice seeds, the boxes ^e ' ^sp ' ^e 25 had the same dimensions as in the previous examples. Each box was doused with 0.5 liters for its effect in combating rice blight treatment solution, the concentration (Piricularia oryzae) being checked. The treatment of the compound was adjusted so that specific two different methods were used, once by amounts in kg / ha. The plants dipping the boxes with rice seeds, as in Figure 30, were transplanted onto rice fields. The examples described two months before, and observations made later, the following other application in the form of irrigation provided the results:

kg / ha Fire fighting Plant height Number of lap 5 in %") (cm)") plants per plant ¹ ") 10 Soak; transplantation 20th 25th 77 15.5 13-14 hours after that 40 31 75 14.6 80 21 79 15.9 ppm 68 79 16.2 500 56 78 15.6 1000 Root soak 15 minutes; 2000 19th 78 16.4 Transplant on the same day 4000 43 77 13.6 8000 27 77 13.7 0 57 78 15.8 71 75 14.7 Comparative experiment 0 78 16.4

") The percentage of rice blot (Piricularia oryzae) on rice leaves was determined by determining the degree of infection and

the type of injury to 1 OCi plants per approach was determined. ^b ) The average plant height and the number of shoots per plant were determined by testing 100 plants per batch

certainly. ') Infection of the leaves of untreated plants in percent.

Claims (1)

Patent claims: 1. Plant protection agent composed of a surface-active dispersant, an inert finely divided solid and an active ingredient, characterized in that it is an s-triazolo [3,4-b] benzoxazole or s-triazolo [3,4-bjbenzthiazole of the general formula I as active ingredient