DE2250077A1 - PROCESS FOR PRODUCING BENZOXAZOLE AND BENZTHIAZOLE COMPOUNDS AND THEIR USE FOR PLANT PROTECTION - Google Patents

Description

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

Process for the production of benzoxazole and benzothiazole compounds and their use for crop protection

The invention relates to new processes for the preparation of triazolobenzoxazole and triazolobenzothiazole compounds.

The invention relates to a process for the preparation of a compound of the formula

R ^la

wherein the radicals R ^a , which can be identical or different from one another, are hydrogen, halogen, a lower alkyl group having 1 to 3 carbon atoms, a lower one

309816/1168 omOWAi. INSPECTED

Alkoxy group having 1 to 3 carbon atoms or a lower alkylthioqrunne with 1 to 3 carbon atoms, Z

4th
Oxygen or sulfur and R is hydrogen, an alkali having 1 to 11 carbon atoms, a cyclonronyl green, a trifluoromethyl group or a group of the formula

Il

-C-O- lower alkyl of 1 to 3 carbon atoms

mean with the proviso that at least two of the radicals R ^a or

at least one of the radicals R ^a and the radical R are hydrogen

4 la

and that if both the radical R and the radical R in the 5-position are groups other than hydrogen, these Groups do not contain more than 6 carbon atoms together, characterized in that a corresponding 2- (acylhydrazino) -benzoxazole or -benzthiazole of the formula

NH-NH-C-R

at a temperature of 0 to 250 C with polyphosphoric acid implements.

Einiqe this Verbindunqen zeiqen a very strong systemic activity and are claimed as new Verbindunaen. These compounds are 3-chloro-s-triazolo (3,4-b) benzthiazole,

309816/1168

5-chloro-s-triazolo (3,4-b) benzothiazole, 5-fluoro-s-triazolo- (3,4-b) benzthiazole and 5-methyl-s-triazolo (3,4-b) benzothiazole.

The invention also relates to new methods and means for the control of oraanisms pathogenic for plants, whereby the agents triazolobenzoxazole and triazolobenzothiazole compounds the formula

or phytologically acceptable acid addition salts of these compounds. In the above and in the following Mean formulas

-S-, -S- or

0 O -S-,

the individual radicals R, which can be identical to or different from one another, are hydrogen, halogen, a lower alkyl groups of 1 to 3 carbon atoms, one lower alkoxy groups with 1 to 3 carbon atoms or a lower alkylthio group with 1 to 3 carbon atoms,

R is hydrogen, an alkyl group with 1 to 11 carbon atoms, a cyclopropyl group, a HydroxvcTrunne, a

3 0 9 8 16/1168

lower alkoxy group having 1 to 3 carbon atoms, a mercapto group, a lower alkylthio group having 1 to Carbon atoms, an allylthio group, a propynylthio group, a benzylthio group, halogen, an amino group, a C.-C ^ - Alkylamino group, a di-C.-CU-alkylamino group Carbamoyl group, a thiocyanate group, an acetamido group, a trifluoromethyl group, a group of the formula

Il

-COR ³ ,

in the R sodium, potassium, a lower alkyl group with 1 to 3 carbon atoms, a halomethyl group or a mono- or di-C-C-j-alkylaminomethyl group,

with the proviso that at least two of the radicals R or

1 2
at least one radical R and R are hydrogen

2 1

and that when both the radical R and the radical R

in the 5-position mean groups other than hydrogen atoms , these groups together do not contain more than 6 carbon atoms.

The compounds defined above are suitable for controlling organisms pathogenic for plants. That's why the invention relates to methods of applying these compounds and to means of making these compounds contain to combat these organisms.

The invention therefore also relates to compositions which have a surface-active dispersant, an inert one finely divided solid and an active ingredient of the formula

309B 16/1168

or a nhytologically acceptable acid addition salt of which contain, where the individual symbols in the formula have the following meanings

t X the group -0-, -S-, -S-

0 0 or -S-,

each of the radicals R, which can be identical to or different from one another, is hydrogen, halogen, a lower alkyl group of 1 to 3 carbon atoms, one lower alkoxy groups of 1 to 3 carbon atoms or a lower alkylthio group with 1 to 3 carbon atoms,

R is hydrogen, an alkyl group with 1 to 11 carbon atoms, a cyclonropyl, hydroxy, C -C - alkoxy, mercapto, C.-C.j-alkylthlo-, allylthio-, propynylthio-, Benzylthio- or aminogroup, halogen, a C -C_ -alkylamino, Di-C -CU-alkylamino, carbamoyl, thiocyanate, Acetamido or trifluoromethyl group or a group of the formula

-C-O-R "

309816/1168

wherein R is sodium, potassium or a lower alkyl source

■ if

1 to 3 carbon atoms, a Haloenmethylqrunne or is a mono- or di- (C.-C, -alkyl) -aminoqrunne,

with the proviso (1) that at least two of the radicals R

1 2 or at least one radical R and R is hydrogen

and (2) that if both the radical R and the R in the 5-position denotes groups other than hydrogen, these greens together not more than 6 carbon atoms contain.

There is also a method of killing plants for plants nathoqenen Orqanisms described, with reference to places where such orqanisms occur or occur, a cause of failure sufficient amount of an active ingredient is applied which is a compound of the formula

or a pharmaceutically acceptable acid addition salt thereof can be, where in this formula mean

X the green -0-, -S-, -S- or

0 O

309816/1 168

each of the radicals R, which may be mutually the same or different, is hydrogen, halogen, a C ₁ ^- C ₃ "

Alkyl, alkoxy or alkylthio group,

ο
R is hydrogen, a 0.-C ₁ -alkyl-, cyclopropyl-, hydroxy-, C ₁ -C ₃ -AIkOXy-, mercapto-, C ₁ -C ₃ -AIlCy lthio-, ally lthio-, propynylthio, benzylthio- or amino group, halogen, C ₁ -C ₃ -alkylamino-, Dl-C -.- C. ^ - alkylamino-, CarbamoyX-, thiocyanate, acetamido or trifluoromethyl group or a group of the formula

Il

-COR ³ ,

where R is sodium, potassium, a Cj-C-j-alkyl, halomethyl, or mono- or di- (Cj-C - ^ - alkyl) amino group,

with the proviso (1) that at least two of the radicals R or

1 2

at least one of the radicals R and the radical R water

2 1

mean substance, and (2), if both R and the radical R in the 5-position mean groups other than hydrogen, se groups together do not contain more than 6 carbon atoms.

The term "halogen" refers to fluorine, chlorine, bromine and iodine. Those groups that are called lower alkyl groups and alkyl (alone or as part of a composite name) and lower alkoxy groups

2 branched or straight chain alkyl groups. If R denotes a di (C ₁ -C 3 -alkyl) amino group, then the lower alkyl groups can be identical to one another or different from one another. In the case of salts, the term "phytologically acceptable" is used to denote acids which, in the form of their salts, are not phytotoxic. Otherwise, the choice of acid is not critical, though

309 8 16/1168

_ Q -

in some cases a particular anion for particular benefits can lead, for example, easier solubility or good crystallization. Examples of suitable Acids include hydrochloric acid, hydrobronic acid, Hydriodic acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, trifluoroacetic acid, acrylic acid, o-aminobenzenesulfonic acid, bromoacetic acid, citric acid, cyclohexane-1,1-dicarboxylic acid, Formic acid, maleic acid »malonic acid, oxalic acid, p-toluenesulfonic acid and methanesulfonic acid.

The compounds to be used in the context of the invention can be prepared by several synthetic methods will. Some of these methods are generally applicable.

A first method used for making these connections is generally applicable, consists in the cyclization of a 2- (2-acylhydrazino) benzoxazole or 2- (2-acylhydrazino) benzthlazole

Il

NH-MH-C -R

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 hydrogen, an alkylorunoe as defined, a Cyclonrooylgrunoe, a TrIfluornethvlarunfte or • the green _

··
-COR ³

309816/1168

means in which R is a lower alkyl group with 1 to

2 is 3 carbon atoms. In cases where R is a has other meanings, various other synthesis methods explained below are preferred. In general is this synthesis method is independent of the meaning of R qanqbar.

The desired cyclization can easily be achieved by refluxing des 2- (2-acylhydrazino) benzoxazole or ' Achieve 2- (2-acylhydrazino) benzthiazoles in phenol. the Cyclization provides the desired product and water as a by-product. The separation and, if necessary, cleaning takes place according to conventional working methods.

The manufacturing process improved according to the invention is a process for the preparation of a compound of the formula

which is characterized in that a corresponding 2- (2-acylhydrazino) benzoxazole or benzothiazole formula

la

la

la

la

NH-NH-C-R

3098 16/1168

is reacted with polyphosphoric acid at a temperature of 0 to 250 ^{° C.} In the formulas above and below, the individual symbols have the following meanings:

la

each of the radicals R, which are identical to one another or to one another can be different, hydrogen, halogen or

a C -C ~ alkyl, alkoxy or alkylthio group, Z

4th
Oxygen or sulfur and R is hydrogen, an alkyl group with 1 to 11 carbon atoms, a cyclopropyl or trifluoromethyl group or a group of the formula

-COC ₁ -C ₃ -alkyl,

with the proviso (1) that at least two of the radicals R ^a or at least one of the radicals R ^a and

4th
the radical R is hydrogen, and (2) that if

both R and the radical R ^a in the 5-position denote groups other than hydrogen, these groups together do not contain more than 6 carbon atoms.

To carry out the reaction, the 2- (2 ^ acylhydrazino) benzoxazole or benzothiazole used as starting material is combined with the polyphosphoric acid. An inert liquid can be used as the reaction medium, but since the polyphosphoric acid itself is a liquid, it is preferred to use only polyphosphoric acid in excess. The condensation of the compound of formula I is carried out at a reaction temperature from 0 to 250 ⁰ C. Preferably catfish are the 2- (2-acylhydrazino) benzoxazole or benzothiazole and mixed polyphosphoric acid and the mixture is heated to a higher temperature in the specified range, for example, 100 to 200 C heated.

3 0 9 8 16/1168

A part of the desired product becomes immediately after mixing the reactants are formed in the given temperature range, but higher yields are obtained, when the mixture is allowed to react for a period of time, a few minutes to a few hours.

The product can easily be separated off by pouring the reaction mixture into water and filtering it off effect or extract. If necessary, other conventional methods for the separation and the Cleaning can be applied.

A second method for the manufacture of the erfindungsqemäß compounds to be used is generally applicable, is the implementation of a 2-hydrazinobenzoxazole or 2-hydrazinobenzothiazoles

NH-NH,

with an orthoester of the formula

R-C (OAlkyl)

This synthetic route is suitable for the production of such Compounds of the formula I in which X is oxygen or sulfur and R is hydrogen, a methyl group, an ether or mean a cyclonronyl green. As in the case of the first

309816/1168

Syntheseweqs the meaning of the Grunoen R is not important. During the reaction, the reactants are ■ consumed in equimolecular amounts and the desired compound and the corresponding alkanol are formed as by-products. It is advisable to use an inert liquid as the reaction medium. The reaction lHuft in a wide temperature range from, beisnielsweise between 25 and 200 ⁰ C, but better yields are achieved in a shorter time when the reaction is carried out at the Rückflußtemoeratur the reaction mixture. The separation and, if necessary, purification is carried out by conventional methods.

A third method that is generally used for manufacturing According to the invention suitable compounds to be used, consists in the condensation of a 2-hydrazinobenzothiazole or benzoxazole

.NH.

with an acid of the formula R -COOH. This reaction eianet for the preparation of such compounds of the formula I,

2 wherein X is oxygen or sulfur and R is hydrogen, an alkyl green as defined, a cyclonronyl or trifluoro

3 0 9 8 16/1168

methylarunne or the group

Il

-COR ^:

means where R is an alkyl group with 1 to 3 carbon

2
Is atoms of matter. If R has another meaning, then other synthesis methods are preferred. In general, this synthetic route is suitable regardless of the meaning of R.

To carry out this condensation reaction, the reactants are mixed with one another. In the The reactants are converted in equimolar amounts Quantities consumed and the desired compound and water formed as a by-product. It can be an inert solvent can be used, but the acidic reactant in the Reael is a liquid, which is why it is more convenient to use an excess thereof. The reaction takes place over a wide temperature range ab, but better yields are achieved in less time when they are at the reflux temperature of the reaction mixture is carried out. Separation and, if necessary, cleaning are carried out using conventional methods,

For the preparation of compounds, in the formula of which R certain grunts will mean various others

2 synthetic methods applied. When R represents the group -OH, the compounds become one through conversion 2-hydrazinobenzoxazole or -benzthiazole

H-NH-

309816/1188

made with urea. Be in a corresponding manner the connections when R * "means the green -SH through Implementation of the same starting materials with potassium hydroxide and Carbon disulfide produced. In both cases it will initially obtained product by subsequent alkylation

converted into such compounds, in their formulas

2
R is a lower alkoxy, lower alkylthio, allylthio, proninylthio or benzylthioaruone. Links,

2
in the formulas R denotes an Aminoarunpe, are prepared by reacting the same 2-IIydrazinobenzoxazole or 2-hydrazinobenzothiazole with Bromcvan.

Still others of the compounds to be used according to the invention are derived from a cyclization product

Lower Alkyiooc

obtained by conventional reactions. To such reactions include the hydrolysis of the ester

to the sodium or potassium salt O II

2
(R s -CO- sodium or -potassium) and the aminolysis of the

Ester to amide (R = carbamoyl). The acylation of the

3-, NH _? -Compound provides the Acetamidogrunne (R = Acetamido) or other amides and the reduction of such amides

309816/1168

2 leads to substituted amino groups (R = C ₁ -CU amino or di (C ₁ -C_-alkyl) amino).

ο
Compounds in whose formula R is halogen or a thio

means cyanate group, are derived from the corresponding

bond of the formula I, in which R is hydrogen, obtained. The latter compound is made with a halogenating agent for example an N-halosuccinimide implemented. Other halogen derivatives that are not readily prepared by reaction with N-halosuccinimide can, according to known halogen exchange reactions, for example according to the Finkelstein reaction can be obtained. The. 3-halogen compounds can also be used as intermediates for the 3-substituted amino, 3-Nlederalkoxy-, and other 3-substituted compounds of the formula I can be used. So you can use the 3-halogen compound react with NaSCN to introduce the 3-thiocyanate group. Those compounds in whose formula R is Represents halomethyl group can easily be converted by reacting the corresponding compounds, in their form

2
mel R denotes a methyl group, prepare with a halogenating agent and optionally according to the above for the

Preparation of the compounds in whose formula R is halogen means to convert the mentioned Finkelstein reaction. The-

2 nigen compounds in whose formula R is a mono- or Di- (C -Cg -alkyDaminomethylgruppe means are from the unsubstituted compound produced by a Mannich reaction. With regard to the implementation of this

different reactions for the formation of the substituents R is referred to Synthetic Organic Chemistry, Wagner and Zook (John Wiley and Sons, Inc., New York, 1956) and Advanced Organic Chemistry, Fieser and Fieser (Reinhold Publishing Co., New York, 1961).

309816/1168

The methods described above are essentially suitable for the preparation of the compounds of the formula I regardless of the meaning of the radicals R. In general, it is preferred that substituents have those specified Meaning are already present in the source material. In some cases, however, it is preferable to use the above methods described to carry out with a starting material that has a different substituent than the final desired carries, and then the substituent of the resulting triazolobenzoxazole or triazolobenzothiazole to convert into the desired substituent. Also compounds that contain additional substituents, for example Carboxyl groups, can be used as the carboxyl groups are subsequently decarboxylated can be removed. Also in this context will reference is made to the literature references mentioned above, Synthetic Organic Chemistry and Advanced Organic Chemistry.

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

0 0 0 -S-, or -S-

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

The compounds of the formula I form acid addition salts with acids. The salts are prepared by conventional methods, namely by reacting a compound of the formula I as the free base with the desired acid in a suitable solvent. Separation and if necessary, cleaning is carried out in the usual way, In general, such salts are one-to-one salts. Some of the compounds of the formula I - those whose radicals R or

309 8 16/1168

ο
R containing an amino or substituted amino group form salts with two or more acid molecules per molecule of the compound of the formula I. In the case of dibasic or polybasic acids, salts can be formed from two or more molecules of the compound of the formula I per molecule of acid. Such di- or poly-salts are also within the scope of the invention. In order for the salts to be useful for the purposes of the invention, phytologically acceptable salts are preferred.

The invention is illustrated in more detail by the following examples.

Example 1 s-Triazolo (3,4-b) benzthiazole

125 g (0.76 mol) of 2-hydrazinobenzothiazole, 112.4 g (0.76 mol) of ethyl orthoformate and 2 liters of xylene are heated ^{to 105 ° C. with stirring in a 5 liter three-necked flask with a 20 cm column and a condenser.} 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 separates out, which is filtered off and triturated with diethyl ether. The resulting s-triazolo (3,4-b) benzothiazole is recrystallized from chloroform and melts at 174.5 to 7 ⁰ C.

Example 2 3-Trifluoromethyl-s-triazolo (3,4-b) benzthiazole

17.8 g of 2- (2- (trifluoroacetyl) hydrazino) benzthiazole are with 44.5 g of phenol mixed and heated to reflux for 24 hours. The reaction mixture then becomes one

309316/1168

Subjected to steam distillation to remove the phenol and the remaining oil is extracted with chloroform / water. After removal of the chloroform the residual substance behind, the desired 3-Trlfluormethyl-striazolo (3,4-b) benzothiazole is recrystallized from ethyl acetate, melting at 140-141 ⁰ C.

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 refluxed in 5500 ml of ethanol for 60 hours. Shortly after the reflux has started, a light yellow solid substance begins to precipitate. This substance is filtered off and dissolved in water to which 1500 ml of 0.5 η hydrochloric acid had been added. The mixture thickens. The formed s-triazolo (3,4-b) benzothiazole 3-thlol is filtered off and melts at 242 ⁰ 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 occasionally with stirring 174 g (1.64 mol) of cyanogen bromide were added. After all of the cyanogen bromide has been added, the reaction mixture thickens and the temperature begins to rise. The reaction mixture is cooled in an ice bath and half the contents of the flask

309 3 16/1168

is transferred to another flask. 1 l of methanol is added to each of the two portions and the mixture is heated to reflux while stirring. A clear red solution forms at the reflux temperature and soon afterwards a light brown precipitate begins to separate out. The reflux is continued for 5 hours. The reaction mixture is then cooled and freed from most of the solvent on a steam bath. After further cooling, diethyl ether is added, whereby a yellow precipitate, the desired 3-amino-striazolo (3,4-b) benzothiazole hydrobromide, is obtained, which is filtered off and washed with petroleum ether. The product is purified by dissolving it in as little boiling water as possible and filtering off the insolubles. When the filtrate cools, the product precipitates again. After ümkristallieren from methanol / diethyl ether and then from methanol alone, the product melts at 260-262 ⁰ C.

Example 5

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

100 g of 2-hydrazinobenzothiazole and 100 g of urea are ^{fused together on an oil bath at about 180 °} C. for about 1 hour. After this time, the melt has solidified and the development of ammonia has ceased. The solid substance thus obtained the desired s-triazolo (3,4-b) benzthiazole-3-ol is recrystallized twice from methanol and melts at 235 ⁰ C.

3 0 9 8 16/1168

Examples 3-methylthio-s-trlazolo (3,4-b) benzthiazole

238 g (1.14 mol) of s-triazolo (3,4-b) benzthiazol-3-thlol, 50 g (1.25 mol) sodium hydroxide and 325 g (2.30 mol) 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) benzthiazole 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 yield of the desired product crystallizes out of the aqueous solution. The combined proportions melt at 129 to 130 ^° C.

Example 7 3-Bromo-s-trlazolo (3,4-b) benzthiazole

6.4 g (0.0366 mol) of s-triazolo (3, 4-) 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 present on a

3 0 9 S 1 6/1 1 6 8

column filled with silica gel is chromatographed by elution with ethyl acetate. The second portion is through Elemental analysis and NMR spectrum checked and thus proves to be the expected 3-bromo-s-triazolo (3,4-b) benzthiazole from m.p. = 166-7 ° C.

Example 8 3-Chloro-s-triazolo (3,4-b) benzthiazole-9,9-dioxide

10.5 g of 3-chloro-s-triazolo (3,4-b) benzothiazole are dissolved in 100 ml of methylene chloride and cooled to 0 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 then heated to boiling under reflux for 1 hour, a further 10.2 g of m-chloroperbenzoic acid in 125 ml of methylene chloride are added and the mixture is again heated to boiling under reflux for 1 hour. The reaction mixture is then evaporated to dryness in vacuo. The residue is applied to a 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-s-trlazolo (3,4-b) -benzthiazole-9,9-dioxide with a melting point of 218 on the basis of its IR and NMR spectrum, elemental analysis and mass spectroscopy -20 ⁰ C.

Example 9 3-Methyl-s-triazolo (3,4-b) benzthiazole-p-toluenesulfonate

2 g of 3-methyl-s-triazolo (3,4-b) benzthlazole are dissolved in 50 ml of ethanol and treated with 2 g of p-toluenesulfonic acid while stirring. After thorough mixing, the reaction mixture is ^{heated to 90 °} C. and at this temperature for 1 hour

3 0 9 Π 1 6/1 1 6 8

held. 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 calculated: C 53.17; II 4.18; N 11.73. Found: C, 53.29; H 4.19; N 11.71.

Example 10 3- (Trifluoromethyl) -s-triazolo (3,4-b) benzthlazole

2.5 g of l- (2-benzthiazolyl) -2- (trifluoroacetyl) hydrazine are slurried with 75 ml polyphosphoric acid and heated for 4 hours at 160 ⁰ C. The reaction mixture is then poured onto ice, whereby the desired 3- (trifluoromethyl) -striazolo (3,4-b) benzthiazole 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 11 3,5-Dimethyl-s-triazolo (3,4-b) benzthiazole

A solution of 6.1 g of 2-Hyclrazino-4-methylbenzthiazole (0.034 mol) and 6.4 g of triethyl orthoacetate (0.04 mol) in 200 ml of xylene is brought to its reflux temperature within 5 hours heated and then refluxed for 96 hours heated. The reaction mixture is then concentrated to a quarter of its original volume and poured on

Ί 0 f) ^: I 6 / M 6 8

let temperature cool down. The 3,5-dimethyl-trlazolo (3, 4-b) benzothiazole is filtered off and 4 g of substance with a temperature of 196 ° -8 ° C. are obtained.

Analysis calculated: C 59.09; H 4.46; N 20.67. Found: C 59.10; H 4.47; N 20.73.

Example 12 5,6-Dimethyl-s-triazolo (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 with stirring for 24 hours. The reaction mixture is then cooled to room temperature and poured into water. The 5,6-dimethyl-s-triazolo (3,4-b) benzothiazole precipitates and is filtered off. This gives 2.6 g of material melting at 226-8 ⁰ C. =

Analysis calculated: C 59.09; H 4.46; ISI 20.67. Found: C 58.88; H 4.17; N 20.39.

Example 13 3- (Dimethylaminomethyl) -s-triazolo (3,4-b) benzthiazole hydrochloride

A mixture of 7.5 g (0.042 mol) of s-triazolo (3,4-b) benzthiazole, 2.52 g of paraformaldehyde, 4.48 g of dimethylamine hydrochloride and 15.5 ml of isoamyl alcohol is refluxed for 7 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 245 to 246 ⁰ C.

3 0 9 ■■ '. 16/1168

221) 0077

Examples 14 to 49

Further exemplary compounds, according to the methods described above and demonstrated by examples below Using analogous starting materials are the following:

3-Amino-s-triazolo {3,4-b) benzoxazole hydrochloride, m.p. «220 ⁰ C (dec.)

s-triazolo (3,4-b) benzoxazole, mp = 162-163 ⁰ C. 3-ethylthio-s-triazolo (3,4-b) benzothiazole, mp = 105 - 1O7 ° C.

3- (2-Propynylthio) -s-trlazolo (3,4-b) benzthiazole, F. ■ 165 - 166 ⁰ C.

3- (Propylthio) -s-triazolo (3,4-b) benzthiazole, F. «81-83 ⁰ C. 3-Ethyl-s-triazolo (3,4-b) benzthiazole, F. 115-116 ⁰ C. 3-methyl-s-triazolo (3,4-b) benzothiazole, m.p. = 146-148 ⁰ C. 3-methyl-s-trlazolo (3,4-b) benzoxazole, F., "175-178 ⁰ C.

3-Dimethylaminomethyl-s-triazolo (3,4-b) benzthiazole hydrochloride, F. = 245 - 246 ⁰ C.

3,5,6-trimethyl-s-triazolo (3,4-b) benzthiazole, m.p. = 246-248 ° C. 3,6,7-trimethyl-s-triazolo (3,4-b) benzthlazol, F., "243-245 ⁰ C, 3-chloro-5-methyl-s-triazolo (3,4-b) benzthiazole. F.- 170 - 172 ⁰ C (decomp.)

3-undecyl-s-triazolo (3,4-b) benzothiazole, F. "68-70 ⁰ C.

3-Methyl-5-fluoro-s-triazolo (3,4-b) benzthiazole, F. = 141 - 142 ⁰ C.

5-Fluoro-s-triazolo (3,4-b) benzothiazole, F., "172-173 ⁰ C. 5-Ethyl-s-triazolo (3,4-b) benzothiazole, F.," 152-153 ⁰ C. 5,7-dichloro-s-triazolo (3,4-b) benzthiazole, F. = 246 - 248 ⁰ C.

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

F. = 240 - 242 ⁰ C.

3-chloromethyl-s-triazolo (3,4-b) benzthiazole, F. * 177-179 ⁰ C. 3-chloro-s-triazolo (3,4-b) benzthiazole, F. 149-151 ⁰ C. 5-methoxy-s-triazolo (3,4-b) benzothiazole, m.p. = 178-180 ⁰ C.

3 0 9 R 1 67 1 1 6 8

INSPECTED

225ÜÜ77

5-chloro-s-triazolo (3,4-b) benzothiazole, m.p. = 186 to 187.5 ⁰ C. 6,7-di: methyl-s-trlazolo (3,4-b) benzothiazole, F. = 272-274 ⁰ C. 3,5-dichloro-s-triazolo (3,4-b) benzothiazole, m.p. = 178-182 ⁰ C. 7-methoxy-s-triazolo (3,4-b) benzothiazole, F . = 178 - 181.5 ⁰ C 3-acetamido-s-triazolo (3,4-b) benzthiazole, F. = 270 - 272 ⁰ C. 5-methyl-s-triazolo (3,4-b) benzthiazole, F. = 184 - 185 ⁰ C. 3-Methoxy-s-triazolo (3,4-b) benzthiazole, F. = 155 - 156 ⁰ C. 7-Xthoxy-s-triazolo (3,4-b) benzthiazole, F. = 162 - 163 ⁰ C. s-Triazolo (3,4-b) benzthiazol-3-yl-thiocyanate, F. = 209 - 210 ⁰ C. s-Triazolo (3,4-b) benzthiazol-3- carboxamide, F. = 262 - 265 ⁰ C. 3-Pentyl-s-triazolo (3,4-b) benzthiazole, F. = 95 - 96 ⁰ C. 3-Isopropyl-s-triazolo (3,4-b) benzthlazol _f F. = 78 - 80 ⁰ C. 3-Propyl-s-triazolo (3,4-b) benzthiazole, F. = 129 - 131 ⁰ C.

3-methyl-s-triazolo (3,4-b) benzthiazole hydrochloride, F. = 239 - 240 C.

3-methyl-s-triazolo (3, 4-b) benzthiazole hemisulfate, F. = 210 - 212 ⁰ C.

Examples 50 to

Further exemplary compounds of the formula I are obtained as described and explained above:

s-triazolo (3,4-b) benzthiazole-9-oxide 3-cyclopropyl-s-triazolo (3,4-b) benzthiazole 3-methyl-s-triazolo (3,4-b) benzthiazole acetate 3-methoxy -s-triazolo (3,4-b) benzoxazole s-triazolo (3 , 4-b) benzoxazole phosphate 3-methyl-s-triazolo (3,4-b) benzoxazole 3-ethoxy-s-triazolo (3, 4-b) benzthiazole 3-propoxy-s-triazolo (3,4-b) benzoxazole hydrobromide s-triazole (3,4-b) benzthiazole sulfate 3-allylthio-s-triazolo (3,4-b) benzthiazole 3- (1-Propynylthio) -s-triazolo (3,4-b) benzoxazole

.. /.30 9 8 16/1168

3 ~ benzylthio-s-triazolo (3,4-b) benzthiazole / ZbUl) II 3-fluoro-5-methyl-s-triazolo (3,4-b) benzoxazole 3-methylamlno-s-triazolo (3,4- b) benzthiazole 3-diethylamino-s-triazolo (3,4-b) benzoxazole 3-propylamino-s-triazolo (3,4-b) benzthiazole ethyl-s-trlazolo (3,4-b) benzthiazole-3-carboxylate Sodium-s-triazolo (3,4-b) benzoxazole-3-carboxylate 3,8-dimethyl-s-triazolo (3,4-b) benzothiazole 5,6,8-trichloro-s-triazolo (3,4- b) benzthiazole 3-chloromethyl-s-triazolo (3,4-b) benzoxazole potassium 3-triazolo (3,4-b) benzthiazole-3-carboxylate a-triazolo (3,4-b) benzoxazole phosphate
3-ethylaminomethyl-s-triazolo (3,4-b) benzoxazole 5-methylthio-s-triazolo (3,4Ha) benzthiazole 5-ethylthio-s-triazolo (3,4-b) benzoxazole

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

309816/1168

The compounds can be used in several different embodiments to good effect. In _: the predominantly applied practice of applying the active ingredients to the foliage of plants sensitive to attack, the compounds are effective against organisms pathogenic to plants. In addition, the triazole benzoxazole and triazole benzothiazole compounds can be applied to seeds to protect them and the resulting plants against attack by pathogenic organisms. The compounds can also be distributed to control the pathogenic organisms in the soil. It has been shown that many of the compounds are transported through the plants, so that in this embodiment not only control of the organisms attacking the foliage, but also control of the Organisms is achieved that attack other parts of the plant.

The inventive method for combating for Plant pathogenic organisms generally consists in adding an effective amount of one or more of the triazolobenzoxazole and To apply trlazolobenzothiazole compounds to the place of occurrence of pathogenic organisms. the Connections can be applied to four den alone. In the context 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 means are suitable for use on living plants without harm to the plants. In the production of such agents, the Triazolobenzoxazol- and triazolobenzothiazole compounds modified with one or more of a number of different additives become surface-active, for example with organic solvents, petroleum distillates, water or other liquid carriers Dispersants and finely divided inert

30 9: 16/1 1 G8

Solids. In such agents, the triazolobenzoxazole or triazolobenzothiazole compounds can be used in concentrations from about 2 to 98 percent by weight be present. Depending on the concentration of the triazolobenzoxazole or triazolobenzoxazole 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 ready-to-use Middle. Preferred agents are those which are both a finely divided solid and a surfactant Funds included.

The exact concentration of the triazolobenzoxazole or triazolobenzothiazole compounds, those in the means for application to the pathogenic organisms and / or the places their occurrence may vary provided that effective amounts are applied to the organism or its Environment to apply. The amount at which the desired effect is achieved depends in part on the sensitivity the respective organism pathogenic for plants and the activity of the compound used in each case. In general, good results have been obtained with liquid formulations that are about 0.001 to 0.1 percent by weight the triazolobenzoxazole or triazolobenzothiazole compound or more. In the case of dusting powders, they are good Results usually obtained with formulations containing 0.5 to 5 percent by weight of the triazolobenzoxazole or triazolobenzothiazole compound or more. When expressed in terms of quantities per hectare, it gives good results in control from pathogenic organisms to plants obtained when the compounds are applied to the acreage of growing plants at a dosage of about 0.55 to 5.6 kg / ha (0.5 to 5.0 pounds per acre) or more.

For the production of dusts, the Trlazolobenzoxazol- and Triazolobenzthiazolverbindungen can be used with any finely divided Solids, for example pyrophyllite, talc, lime or plaster of paris. For this purpose, the finely divided

309M6 / 1 16.8

Carrier with the triazolobenzoxazole or triazolobenzothlazole compound ground or mixed or with a solution of the latter in a volatile organic solvent wetted. Correspondingly, the dusts containing these compounds can be mixed with various solid surface-active dispersants, for example fuller's earth, bentonite / attapulgite or other clays combined will. Depending on the proportions of the constituents, these dusts can be used to control plants pathogenic organisms or as concentrates are used, which are then mixed with other solid surface-active dispersants or diluted with pyrophyllite, lime, talc or gypsum to get the desired amount of active ingredient in one To achieve means that are suitable for use in combating the pathogenic organisms. Such dusts can also be in the form of concentrates, with or without the aid of dispersants in water can be dispersed into spray mixtures.

The Triazolobenzoxazol- and Triazolobenzthlazolverbindungen or liquid or dust concentrates containing these compounds may also contain mixtures with surface-active dispersants, for example nonionic emulsifiers can be processed into sprays. Such agents can easily be used to combat pathogenic organisms, or it can be used to prepare diluted spray mixtures which contain the active ingredients by dispersing them in liquid carriers Contained in any desired quantity. The choice of dispersant and the amount of the same depends according to their ability to disperse the concentrates in the liquid carrier into the desired spray agent support financially.

309816/1188

The trlazolobenzoxazole and triazolobenzothiazole compounds but can also with water-immiscible organic liquids and a surface-active dispersant be mixed to emulsifiable concentrates, which can be further diluted with water and oil and then result in spray mixtures in the form of oil-water emulsions. at For such agents, the carrier consists of more aqueous media Emulsion, i.e. 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, e.g. condensation products of alkylene oxides with inorganic acids, polyoxyethylene derivatives of sorbitan esters and complex ether alcohols. Among the organic that can be used for these preparations Liquids include petroleum types and petroleum distillates, toluene and synthetic organic oils. the Surface-active dispersants are used in liquid preparations, usually in amounts of 0.1 to 20.0 percent by weight, based on the total weight of the dispersant and the active ingredient used.

In working in accordance with the invention, the triazolobenzoxazole and triazolobenzothiazole compounds or agents which contain them Contain compounds on the pathogenic organisms to be controlled or sites of their occurrence in any Wise applied, for example with the help of hand dusting devices or spray devices. The application to the Plant parts above the earth can be used in a practical manner. with motor sprayers, boom sprayers, high pressure sprayers and spray atomizers. When used on a large scale, dust or spray can be used can be applied from aircraft. When using the triazolobenzoxazole and triazolobenzothiazolo compounds for the control of rice blight, special methods for the application may be preferred, depending on the

0 B 3 1 6/1 1 6 8

special conditions in rice cultivation is reduced. Such special methods include the application to the water surface, the watering treatment of plants to be transplanted, the treatment of seeds and the like. Further
Methods are readily apparent to those skilled in the art.

The following examples illustrate the beneficial results obtained in the control of plant pathogenic, Organisms with the triazolobenzoxazole and triazolobenzothiazole compounds can be achieved, and enable the person skilled in the art to utilize these compounds to advantage.

Examples 76-98

A number of the triazolobenzoxazole and Triazolobenzothiazole compounds have been recognized for their effect in controlling Colletotrichum lagenariUm (Änthraknose) "tested and evaluated on cucumbers. The tests and evaluations were made as follows.

A 10 cm pot was used for each individual test
sterilized soil with a vermiculite layer on the surface inseminated with 4 cucumber seeds and under normal. Allowed greenhouse conditions to stand. The saplings
were reduced to two. About 15 days after insemination, the foliage was sprayed with a solution of the compound in question, allowed to dry and then with a
aqueous suspension of Conidles from Colletotrichum
lagenarium sprayed and so inoculated.

309816/4

The individual triazolobenzoxazole and triazolobenzothiazole compounds were formulated in a conventional manner. In most cases the particular connection was in a certain amount of cyclohexanone dispersed, which is a small amount of a mixture of two nonionic sulfonate-type surfactants, and then diluted with water so that a finished treatment mixture was obtained comprising 400 parts of each Compound per million parts (weight) of the finished product in addition to the cyclohexanone in a concentration of 0.67% and the surfactant mixture at a concentration of 0.0353%.

The conidia suspension was prepared by placing the fungus in Petri dishes on orange juice agar for 14 days at 24 ° C was grown, the dishes were then covered with distilled water and the surface was scraped off. the aqueous suspensions of 4 plates were filtered off through a cheesecloth, brought to a volume of 50 ml and poured Used for spraying plants in about 35 pots.

After inoculation, the plants were kept in a damp room at 18 ^° C. for 48 hours and then left to stand for about 9 days under normal greenhouse conditions, and finally to determine how to combat the anthracnose

checked.

Each test also included a comparative test in which treatment with an aqueous solution containing cyclohexanone and the surfactants were mixed in the same concentrations.

3 0 9 ΙΠ 6/1 1 6 8

The results obtained are shown in the table below, using the following disease rating system was applied:

1 —— difficult

2 moderately difficult

3 moderate

4 weak

5 no disease

In the control pots, the cucumber plants were always severely infected with anthracnose. In all In some cases, phytotoxicity cannot be determined or only to an extremely low extent. An exception formed the plants treated with 5-methyl-s-triazolo (3,4-b) benzthiaezole, as this caused considerable phytotoxicity was observed.

3 0 9 8 16/1168

* ■ 34 -

T a b e 1 le

Combating Anthracnose

link

Disease assessment

3-pentyl-s-triazolo (3,4-b) benzothiazole

3-trifluoromethyl-s-triazolo (3,4-b) benzothiazole 3-chloro-s-triazolo (3,4-b) benzthiazole-9 _f 9-dioxld

a-Triazolo (3,4-b) benzothiazole-3-thiol 3-propyl-s-triazolo (3,4-b) benzthiazole

3-methylthio-s-triazolo (3,4-b) benzthiazole s-triazolo (3,4-b) benzthiazole s-triazolo (3,4-b) benzoxazole 3-Xthylthio-s-triazolo (3 _r 4-b ) benzthiazole 3-propylthio-s-triazolo (3,4-b) benzthiazole 1-ethyl-a-triazolo (3,4-b) benzthiazole 3-methyl-s-triazolo (3,4-b) benzthiazole 3-methyl -s-trlazolo (3,4-b) benzoxazole 3-chloro-s-triazolo (3,4-b) benzthiazole 3-bromo-s-triazolo (3,4-b) benzthiazole 5-methoxy-3-triazolo ( 3,4-b) benzthiazole 5-chloro-s-triazolo (3,4-b) benzthiazole 6,7-dimethyl-s-triazolo (3,4-b) benzthiazole 7-methoxy-s-triazolo (3,4 -b) benzthiazole 5-methyl-3-triazolo (3,4-b) benzthiazole 3-methoxy-s-trlazolo (3,4-b) benzthiazole 3-triazolo (3,4-b) benzthiazol-3-yl- thiocyanate

4+

4-

4+

3-

4-f

4+

4+

4+

4+

4+

3+

309B 16/1168

Examples 99-106

Exemplary representatives of the triazolobenzoxazole and triazolobenzothiazole compounds have also been referred to its effectiveness in combating the pathogenic organism that causes crown gall disease (Agrobacterium tumefaclens) in tomato plants. The following procedure was used.

3 tomato seeds were placed in sand in 10 cm plastic pots introduced and then reduced to 2 plants. An inoculum of Agrobacterium tumefaciens was found in the Meanwhile on homemade potato dextrose agar grown in test tubes. The cultures were then treated with sterile water, so that the required Amount of bacterial suspension obtained necessary for inocullerening the tomato plants about 4 weeks after was used when the seeds were planted. The inoculation was done in such a way that a small insect attachment needle Submerged in the bacterial suspension and then stabbed through the stem of each tomato plant. The plants were then taken out of the sand and the roots of each individual plant in an aqueous solution in one placed in a large test tube containing the compound to be tested at a concentration of 40 ppm, 0.067% cyclohexanone and contained 0.00353% surfactant and sodium chloride at a concentration of 0.85%. the Plants were kept for about 10 days under normal greenhouse conditions with daily aeration. After that it was each plant examined for symptoms of crown gall disease.

For comparison, 2 inoculated plants were used separately Reacrensgl'isern placed in a solution containing all components with the exception of the compound to be tested.

309816/11 Qβ

Otherwise, they were treated in exactly the same way in all respects, like the test tubes with the treated plants.

The results of this test are in the table below compiled using the same rating scale as in the previous examples is applied. All comparison plants showed severe symptoms of crown gall disease. The phytotoxicity was either in all cases completely absent or only slightly with the exception of the plants containing 5-methoxy-s-triazolo (3,4-b) benzthiazole had been treated with significant phytotoxicity.

Table II Combating the crown gall

Link disease assessment

3-methylthio-s-trlazolo (3,4-b) benzthiazole 5

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

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

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

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

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

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

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

3 0 f ⁵ · B 1 6/1 16 8

Examples 107-112

A number of the triazolobenzoxazole and triazolobenzothiazole compounds have been regarding their effect. combating powdery mildew (Erysiphe polyconi) tested and assessed 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 onset of the. Seed, the compound to be tested was applied to the young plants in the form of a preparation which corresponded to those described in Examples 76-98. The treated plants were then placed near and under others. Plants placed which were heavily infested with powdery mildew, so that the treated plants were also infested due to the usual draft of air. In this position, the plants were kept under normal greenhouse conditions for about 7 to 10 days and then examined to see if they showed symptoms of powdery mildew disease. A blank test was carried out with each test. The blank sample consisted of a group of 4 plants which were treated with a solution of solvent and emulsifier without a compound to be tested, as was also described in Examples 76 to 98. The results are compiled in the following table, using the same rating scale as in the previous examples. The bean plants of the blind samples all showed severe powdery mildew infestation. In all cases no or only very little phytotoxicity was observed.

309816/1168

Table III

Combating powdery mildew

link

Disease assessment

s-Triazolo (3,4-b) benzothiazole-3-thiol 3-ethylthio-s-triazolo (3,4-b) benzthiazole 6,7-dimethyl-s-triazolo (3,4-b) benzthiazole s-Triazolo (3,4-b) benzthiazole-3-carboxamide 3-propyl-s-triazolo (3,4-b) benzthiazole 3,5-dichloro-s-triazolo (3,4-b) benzthiazole

Examples

113-149

A series of triazolobenzoxazole and triazolobenzothiazole compounds was tested for its effectiveness in combating rice blight (Piricularia oryzae) and rated. The following procedure was used for this purpose: By mixing the same parts of building sand and Crushed earth crust, the material was made, which was placed in 10 cm pots and vigorously with rice seeds was sown. The inseminated pots were then left to stand for about 2 weeks under greenhouse conditions, after which in each pot a dense vegetation of rice pods found.

In addition, an aqueous suspension of rice brandy fungus conidia was prepared. The fungus was in Petri dishes grown on rice husk agar at 28 ° C. After 8 days, the dishes were each distilled with 20 ml Water was added and the surface culture was

3 0 9 Π 1 6/1 1 6 8

'£ 250077

scraped off with a rubber flag to separate the conidia.

In each individual case, a treatment solution was prepared as described in Examples 76 to 98 and sprayed onto the leaf surfaces of the rice plants in the individual pots and allowed to dry, whereupon the foliage was inoculated with the aqueous suspension of the conidia of the rice blight organism. In each individual case, the treatment solution contained 400 parts of the compound per million parts by weight of the final solution. The pots were left to stand in a damp room at 18 ^° C. for 48 hours and then again kept under greenhouse conditions for 6 days. Evaluation was then carried out using the same evaluation scale as in the previous examples. The comparative experiments were carried out as follows: Pots with rice saplings were sprayed with an aqueous solution of cyclohexanone and the same mixture of two nonionic surfactants of the sulfonate type, but without any active ingredient. Otherwise the pots were treated the same as the rest.

The evaluation results are in the following table compiled. The assessments were not all carried out at the same time. In all tests, however, the untreated comparison substances, strong symptoms of rice blight. In general, no phytotoxicity was observed. Only a few pots showed low phytotoxicity.

3 0 9JM 6/1 1 G 8

Tabel

IV

Fighting rice blight

link

Disease assessment

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

s-Trlazolo (3,4-b) benzthiazol-3-thlol 4 3-Amino-s-trlazolo (3,4-b) benzthiazole hydrobroniid 4

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

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

s-Trlazolo (3 _r 4-b) benzthiazole 4+

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

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

3-Ethylthlo-s-triazolo (3,4-b) benzthiazole 3 3- (2-propynylthio) -s-triazolo (3,4-b) benzthiaiol '3+

3- (Propylthio) -s-trlazolo (3,4-b) benzthlazole 3+

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

3-methyl-s-trlazolo (3,4-b) benzoxazole 5

3-chloro-s-trlazolo (3,4-b) benzthlazole 5

3-Broni-s-tri azolo (3,4-b) benzthlazole 4+

5-methoxy-s-trlazolo (3,4-b) benzthlazole 4+

5-chloro-s-trlazolo (3,4-b) benzthlazole 5

6,7-dimethyl-s-trlazolo (3,4-b) benzthlazole 4+

7-methoxy-s-triazolo (3,4-B) benzthiazole 3+

3-acetamido-s-triazolo (3 _f 4-b) benzthiazole 4

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

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

7-ethoxy-s-trlazolo (3 _f 4-b) benzthlazole .3

s-TrlazoloO ^ -bJbenzthiazol-S-yl-thlocyanate 3 s-Trlazolo (3,4-b) benzthiazole-3-carboxamide. 3-3-chloro-s-trlazolo (3,4-b) benzthiazole-9,9-dloxide 4+

309816/1168

Table IV (cont.)

Fighting rice blight

Link disease assessment

3-Propy1-s-triazolo (3,4-b) benzthlazole 4

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

3-Pentyl-s-trlazolo (3,4-b) benzthiazole 4+

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

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

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

5-ethyl-s-trlazolo (3,4-b) benzthiazole 4

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

3-amino-5-chloro-s-triazolo (3 _f 4-b) benzthiazole

hydrobromide 3

3-Dlmethylaminomethy1-s-triazolo (3/4-b) benz-

thlazole hydrochloride 4-

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

Example 150-153

A number of further compounds to be used in the context of the invention have been investigated with regard to their effect in combating tested and assessed by Reisbrand. The evaluations were made according to the same procedures as in the Examples 113-149 were reported, with the following differences: Multiple ratings were given with each compound performed, the concentration of each compound being 250, 500 and 1000 parts per million, respectively fraud. The results are compiled in the following table.

309816/1 168

link lie V 2250077 T a b e 3-methyl-s-triazolo (3,4-b) -
benzthiazole-p-toluenesulfonate of rice brandy Combat concentration
d.Treatment
solution (ppm.) 3-methyl-s-triazolo (3,4-b) -
benzthiazole hemisulphate 1000
500 Disease
valuation 250 5
4+ 3-undecyl-s-triazolo (3,4-b) -
benzthiazole 1000
500 5 3-methyl-s-triazolo (3,4-b) -
benzthiazole hydrochloride 250 5
5 1000
500
250 5 1000
500 3
■ j || lv
4+ 250 5
5 2

Examples

154-159

A number of the triazolobenzoxazole and triazolobenzothiazole compounds to be used in the context of the invention have also been assessed for their effect in controlling rice blight when applied to the ground prior to planting checked and assessed. For this purpose, a certain amount of the respective compound was dissolved in ethanol and the Solution was sprayed with a DeVllbiss atomizer onto soil rotating in a drum and the treated in this way

309816/1 1 88

Soil was placed in round 10 cm pots without drainage holes. It was worked in such a way that a certain amount was available in kg per ha, namely 23, 14, 7, 5.6, 2.8 or 1.4 kg / ha (25, 12.5, 6.25, 5.0 2.5 or 1.25 pounds per acre). The pots were then sown with rice seeds (Nato variety) and kept under greenhouse conditions for 2 weeks, after which the rice saplings were inoculated with conidia of Piricularia oryzae; the preparation of the conidia suspension and the inoculation were carried out as in the previous examples. The pots were then kept in a damp room at 18 ^° C. for 48 hours and finally under greenhouse conditions for a further 5 days. The results of the disease severity test are presented below using the rating scale given in the previous examples.

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

309816/11 $ 8

Table VI

Combating rice fringes by introducing the active ingredient in the ground before planting

link

s-triazolo (3,4-b) benzothiazole

3-methyl-s-triazolo (3,4-b) benzothiazole

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

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

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

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

Amount of ver
binding in
kg per ha , 6 i , 6 Disease
valuation 28 ,8th ,8th 4th 14th , 4 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 5 2 4+ 1 3 28 5 14th 4+ 7th 4+ 5 4+ 2 3

30 9 8 16/1108

Examples 160-163

A number of the triazolobenzoxazole to be used according to the invention and triazolobenzothiazole compounds have been tested for their effect in combating rice blight (Piricularia oryzae) when applied to the surface of water-saturated soil in which the rice grew became.

Rice (variety Nato) was placed in round 10 cm pots without Sown drainage holes. The soil was saturated with water throughout the experiment carried out in the greenhouse Condition kept.

The shoots were treated about 14 days after sowing. For this purpose, a treatment solution, which had been prepared as described in Examples 154 to 159, was poured onto the surface of the earth in each pot. On the third day after treatment, the plant suspension of the pathogenic organisms have been described with a prepared, as in Examples 113-149 inoculated and placed for 48 hours in a humid chamber at 18 ⁰ C. The plants were then kept for 5 days under customary greenhouse conditions and then examined for the presence of symptoms of rice blight and, in the positive case, 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 evaluations are as follows Table compiled. The comparison pots uniformly showed very strong symptoms of rice blight.

309816/116 8

Table VII

Combating rice blight by using the active ingredient

on the surface of the earth

link

applied amount

the connection disease

in kg per hectare rating

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

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

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

s-Triazolo (3,4-b) benzthiazole 28

14th
7th

28

14th
7th

5.6
2.8
1.4

28

14th
7th

5.6
2.8
1.4

28

14th

4+

4+ 3+

5+

4+

4+

4-

4+

4-

3-

4+ 4-3-

3 0 9 8 16/1168

Examples 164-167

A number of the triazolobenzothiazole compounds have been tested for effectiveness in combating rice blight, when applied to rice seeds by watering the seed.

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

20 ml of each solution was placed in a 125 ml Erlenmeyer flask brought and mixed with 20 ml (about 12.5 g) rice seeds (variety Nato). Each flask was sealed and shaken for 43 hours, after which the rice was drained and rinsed with tap water.

The treated seed was planted in 10 cm square pots and kept under greenhouse conditions. As soon as the rice shoots reached a height of three to four inches (about 14 days after sowing), they became with a fungi suspension of Piricularia oryzae prepared as described in Examples 113 to 149 (Rice brandy) inoculated. The plants were then incubated in a humid room at 18 ° C. for 48 hours, for another 5 days kept in the greenhouse and then using the rating system described in the previous examples rated for the severity of the disease.

3 0 9 8 16/1168

For each test, three tests and two comparative tests were carried out: (1) with water with 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.

309816/1168

Table VIII

Reviews after soaking the seed link

Concentration of the compound in the hand.

solution

Amount of sick

Connection

in g per application

45.3 kg of semen

3-methyl-striazolo- (3,4-b) -benzthiazole

3-chloro-striazolo- (3,4-b) -benzthiazole

5-chloro-striazolo- (3,4-b) -benzthiazole

5-methyl-striazolo- (3,4-b) -benzthiazole

1000 500 250

1000 500 250

1000 500 250 175 100

1000 500 250 175

45.4 4th 22.7 3 11.4 2 45.4 5 22.7 4+ 11.4 3 45.4 5 22.7 5 11.4 4+ 7.8 3+ 4.5 3 45.4 5 22.7 4+ 11.4 4th 7.8 3-

in ppm based on the weight of the seed

309816/1168

The invention relates not only to the use of the triazolobenzoxazole and triazolobenzothiazole compounds in each case alone or in combinations with one another, but also the use of these compounds in combination with other known fungicides, herbicides or other crop protection agents.

Such combination therapy is used in the following Examples illustrated:

Examples 168-177

5-Chloro-s-triazolo (3,4-b) benzthiazole has been used along with numerous other substances on the effect in combating rice blight, helminthosporium and dry rot in young Rice plants (variety NATO), Penrod barley and tomatoes (Variety Bonny Best) tested. Each compound or combination of compounds was made by spraying a conventional Preparation applied to the foliage. After the foliage had dried, the plants were covered with Piricularia oryzae, Helminthosporium sativum or Phytophthora infestans and inoculated for 48 hours at 18 ° C incubated in a humid room. The plants were then kept under greenhouse conditions and finally for 5 days examined for the development of the disease after spraying. The results of two attempts per treatment are compiled in the following table.

3 0 9 816/1168

- 51 -

Table IX

Dosages Medium Disease assessment Dry rot (ppm active ingredient) Rice brandy Helminth. 1 25th 4+ 2+ 2+ 5 3+ 2+ 2- 25 + 600 4+ 3 1+ 5 + 200 4- 3- 1+ 600 1 2+ 2+ 200 1+ 2 3+ 25 + 400 4+ 3- 3+ 5 + 100 3+ 2+ 4+ 400 2+ 4- 4th 100 1+ 3- 4+ 25 + 400 5 4+ 4th 5 + 100 4th 4- 4+ 400 3- 4th 4+ 100 2 3 4- 25 + 400 5 4+ 4- 5 + 100 4th 3- 3- 400 3 4+ 3 100 3- 4- 3+ 25 + 400 4+ 4+ 4+ 5 + 100 4- 3+

309816/1168

- 52 -

225-077

Table IX (continued)

Dosages Medium Disease assessment Dry rot (ppm active ingredient) Rice brandy Helminth. 3+ 400 2 4+ 4+ 100 2+ 4+ 3+ 25 + 400 4+ ■ ^ _ 3 5 + 100 4- 3- 4+ 400 2 3 2+ 100 1 - 1+ 1 25 + 50 5 2- 1+ 5 + 10 3 3 1+ 50 1+ 3- 2- 10 1 2+ 1 25 + 25 5 2+ 2- 5 + 5 4+ 2- 2+ 25th "ί— 1 1+ 5 1+ 2- 2+ 25 + 25 4+ 1+ 3 5 + 5 4- 2- 3- 25th 2 1 2 5 1 1 2- 25 + 200 4+ 4+ 1 5 + 50 4+ It is about ■

3098 16/1168

Table IX (continued)

Dosages Medium Disease assessment Dry rot (ppm active ingredient) Rice brandy Helminth. 2- 200 1 3- 2+ 50 2+ 2 2 Lie O 1 2 1 0 1 1 1 0 1 1

A = 5-chloro-s-triazolo (3,4-b) benzthiazole B = tribasic copper sulfate

C = mixture of aramoniates 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-4-cyclohexene-1,2-dicarboximide

H = O-ethyl-S, S-diphenyldithiophosphate I = pentachloromandelonitrile

J = 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester

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

309816/1168

Examples 178-179

5-chloro-s-triazolo (3,4-b) benthiazole was also tested and evaluated for its effect in combating rice blight when it was applied to the water surface together with known fungicides. Rice plants were in with
Pulled water-covered pots. The compound or compounds were prepared in a conventional manner and applied to the surface of the water when the plants were 10 days old. Two experiments were carried out with each compound or combination of compounds. Three days
then all plants were inoculated with Piricularia oryzae and incubated for 48 hours in a humid room at 18 ° C. 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:

309816/1 168

Table X

Dosage kg / ha

1.13
3.39

1.13 + 5.6 3.39 + 11.2

5.6
11.2

1.13 + 5.6 3.39 + 11.2

5.6
11.2

ng 5
IO Rice brandy
valuation (pounds / acre) 5
10 3+
4+ 1
3 4+
5 1 +
3 + 3 5
10 4+
4+ 1 +
3 + 2+
2 5
IO

solvent
for control

A = 5-chloro-s-triazolo (3,4-b) benzthiazole B = methyl 1- (butylcarbamoy1) -2-benzimidazole carbamate C = 0,0-diisopropyl-S-benzyl-phosphorothiolate

3 0 9 8 16/1168

Examples 180-182

5-chloro-s-triazolo (3,4-b) benzothiazole was also used along with other substances for combating rice blight
checked and assessed by seed treatment.

Rice seeds were first treated with 5-chloro-s-triazolo (3,4-b) -benzthiazole and then with a second substance. These seeds were planted in pots with sterile and non-sterile soil. Once the rice shoots are 7 1/2 to
10 cm high, they were inoculated with Piricularia oryzae and incubated as described in the previous examples. They were then 5 days in the greenhouse
held and then evaluated in terms of combating the disease. The results are compiled in the following table:

309816/1168

Tabel

XI

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

Methy1-Mercury- Active ingredient Seeds 0 e ^x) RB sterile RB Earth RB E. 0 non-sterile soil 10g / 100kg RB 30q / 10Okg 4th RB silver cyanogen ml or g / 10 1+ 1Og / 100kg 5 5 1, E. 4+ E. 9 5 diamid 100kg ί ml 10 1+ E. 4+ 30g / 100kg • 5 9 67 RB 6.67 4+ 8.67 5 O
co Bis (dimethy1- 0 ml 10 1 10 4+ E. 5 9, 1 10 5 8.33 5 co dithiocarbamoyl) - 1.57 10 2- 10 5 9 5 6, 33 1 10 4+ 8th 4+ OT disulfide 3 _r 15 G 10 1+ 9 5 8th 4+ 10 33 1 1.33 5 8.33 5 N-trichloromethyl 0 G 10 1 10 5 8th 5 10 1 9.67 5 9 5 CD thio-4-cyclohexene 124.6 10 1 9 4+ 9 5 4th 1 9.67 4+ 8.33 5 1,2-dicarboximide 249.7 G 10 1 9 5 9 5 10 1 5.67 5 9.67 5 0 G 10 1 10 5 8th 5 10 1 10 4+ 5 124.6 10 9 1 10 249.7 10 9 1 9

= Rating of the emergence of the plants on a scale from 0-10, where
corresponds to 100 percent germination and emergence of the plants.

cn O CD

Examples 183-184

Any of the compounds 5-chloro-s-triazolo (3,4-b) benzthiazole and 3-methyl-s-triazolo (3,4-b) benzthiazole was on their Effectiveness tested in combating rice blight when used to water roots when transplanting.

Each of the compounds was used to prepare a series of aqueous suspensions at different concentrations the compound used, but the uniform 0.05% PoIyoxyäthylensorbitanmonolaurat and contained 1.0% ethanol. The roots of 21 day old rice plants became 5 minutes immersed in the suspensions, 36 plants per suspension. The rice plants were then placed in containers with transplanted earth covered with water. After the plants grew, they were covered with Piricularia oryzae inoculated using the measures described in the previous examples. 11 days later the plants examined for rice blight and damage. 3 tests were carried out for each concentration of active substance. In addition to the rice plants treated with one of the two compounds, a group of rice plants was also used Treated for 5 minutes in the same way with an aqueous solution containing 1.0% ethanol and 0.05% of the same polyoxyethylene sorbitan monolaurate and another group was treated with water alone, so that two comparative tests were carried out.

The results are compiled in the following table. The rice burn ratings were based on the same scale as used above. The plant damage was determined on the basis of a scale from O to IO rated, where mean:

0 = all plants healthy 10 = all plants dead

309816/1 1 68

Tabel

XII

Rice blight and plant damage assessment, application by soaking the roots when transplanting

link

5-chloro-striazolo- (3,4-b) -benzthiazole

3-methyl-striazolo- (3,4-b) -benzthiazole

concentration
the connection
in the potion
solution
in percent Rice-
fire-
apply
tion plants
damage 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

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

0.6

water

3093 16/1188

-6Or

Any of the compounds 5-chloro-s-triazolo (3,4-b) benzthiazole and 3-methyl-s-triazolo (3,4-b) benzthiazole were on their Effect tested in combating leaf rust (Puccinla recondita) of wheat by applying it to the seeds.

Certain amounts of wheat seeds (Monon variety) were used with liquid preparations of the respective compound coated. Specifically, there were two formulations of each compound applied, a 15 percent wettable powder ("15W") and a 25 percent wettable powder ("25W"). Each Powder was mixed with several small portions of water and about 3 percent by weight of the seed was mixed with each the respective preparation treated. A large number of treatment preparations thus resulted from each stock preparation produced, which vary in terms of the amount of applied to the seeds treated with the respective preparation Compound (expressed as g of compound per 100 kg of seeds). After the treatment, the seeds were planted. Other seeds that were not treated for comparison were also planted. All plantings were kept under the usual agricultural conditions, until the wheat saplings were around 7 1/2 inches high. Then all plants were inoculated with rust leaf spores (Puccinia recondita) and 48 hours incubated in a humid room at 18 C. Then the plants were grown for another 8 days under normal growth conditions and finally examined for damage to plants and the occurrence of leaf rust.

The results are compiled in the following table: Leaf rust was rated on a scale from 1 to 5, with mean: 1 = severe infestation by the disease and 5 = no symptoms of illness. The plant damage was not assessed numerically, but, if present, with respect to their kind specified.

0 9 8 16/1168

Table XIII

Assessment of leaf rust and plant damage, application to seeds

g compound / kg seed

link

3-methyl-s-triazolo- (3,4-b) benzothiazole

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

preparation 2 100 3
4th 200 4-
5 400 600 15W
25W 3 thin
growth 3 2 5 very low
inhibition 15W thin
growth inhibited low
inhibition -

25W

2-

inhibited no plants no plants

Comparative experiment

1+

Examples 187-138

Each of the compounds 3-methyl-s-triazolo (3 _f 4-b) benzthiazole and 3-chloro-s-triazolo (3,4-b) benzthiazole was tested for its effect in combating leaf spots on wheat (Helminthosporium sativum) . The compounds were applied using the seed coating technique. The tests were carried out exactly as described in Examples 185 to 186 with the exception that the inoculation was carried out with Helminthosporium sativum. The results are compiled in the following table:

Table XIV

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

400

3+

2 inhibition 4 inhibition

Preparation. G 100 link / link tion 3+ 200 3-methyl-s-triazolo- 15W 3 3+ 3+ (3,4-b) benzothiazole 25W 2- 3 3+ 3-chloro-s-triazolo- 15W 1 3+ 4+ (3,4-b) benzothiazole 25W 4- 2

Comparative experiment

3 0 9 8 1 6/1 1 6 8

Examples 189-190

Any of the compounds 5-chloro-s-triazolo (3,4-b) benzthiazole and 5-methyl-s-triazolo (3,4-b) benzthiazole has been shown to be effective in combating rice blight (Piricularia oryzae) when used on boxes with ■ young rice plants checked before transplant. Each 27Og more swollen Rice arrows were placed on clay in a box with the dimensions 28 χ 58.5 χ 3 cm sown, germinate and up to the stage of 4 to 5 leaves with a leaf length of 15 to 18 cm let grow. At this stage, each box with the plants to be treated was immersed in a treatment solution for 15 minutes. containing the respective compound, immersed. The connections were in the solutions in different concentrations. On average, about 1.2 liters of the treatment solution were taken up by each box. The plants treated in this way and control plants which remained untreated were on the same day transplanted into rice fields. About two months later, the plants were asked to fight rice blight, the Checked plant height and number of saplings per plant. The results are compiled in the following table.

3 0 9 8 16/1168

Comparative experiment

EPJS Brandbe
fighting Plants-
height
- * number
the SchöB-
linge pro in% ^a) (cm) ^b) Plant ^b) 5-chloro-s-tria- 1000 zolo {3,4-b) benz- 4000 0 64 15.6 thiazole 22nd '66 14.2 5-methyl-s-tria- 1000 zolo (3,4-b) benz- 4000 15th 65 15.0 thiazole 51 67 13.7

65

14.5

(24)

a) The percentage of rice brandy (Piriculariä oryzae) on rice leaves was determined by determining the degree of infection and the type of injury on 100 plants determined per approach.

b) The average plant height and the number of shoots per plant were determined by examining 100 plants determined per approach.

c) Infection of the leaves of untreated plants in percent.

3098 16/1168

Examples 190-191

5-Methyl-s-triazolo (3,4-b) benzthiazole has been further proven to be effective in combating rice blight (Piricularia oryzae) checked. The treatment was carried out by two different methods, one by immersing the boxes with rice seeds, as described in the previous examples, and on the other hand the application in the form of a Watering the soil of the boxes with rice seeds, the boxes having the same dimensions as in the previous ones Examples. Each box was doused with 0.5 liters of treatment solution, increasing the concentration of the compound was set so that specific amounts in kg / ha were used. The plants were grown on rice fields transplanted. The observations made two months later gave the following results:

3098 16/1168

kg / ha Brandbe
fighting plants
height Number-
the lap
linge pro 5 in% ^a) (cmi ^b) Plant ^b) 10 20th 25th 77 15.5 Soak; 40 31 75 14.6 transplantation 80 21 79 15.9 13-14 hours ppm 68 79 16.2 thereafter 500 56 78 15.6 1000 Root impregnation 2000 19th 78 16.4 15 minutes; 4000 43 77 13.6 transplantation 8000 27 77 13.7 the same day 57 78 15.8 71 75 14.7

Comparative experiment

(16)

c)

78

16.4

a) The percentage of rice brandy (Piricularia oryzae) on rice leaves was determined by determining the degree of infection and the type of injury on 100 plants determined per approach.

b) The average plant height and the number of shoots per plant were determined by examining 100 plants determined per approach.

c) Infection of the leaves of untreated plants in

Percent.

309816/1

The 2- (2-acylhydrazino) benzoxazole to be used as starting materials and 2- (2-acyl hydrazine) benzothiazole compounds

> —NH-NH-C-R

τ /

are for their part according to the usual methods for the production made from hydrazides. The corresponding 2-hydrazine compounds are expedient

,1

Rl

2 "
with an acyl halide (R -C halogen),

O
Acyl anhydride (R ² -CO) ₂ ,

O
an acid (R ² -C-OH) or

0
an ester (R ² -CO-alkyl)

implemented. The reaction is carried out in the usual manner. The 2-hydrazinobenzoxazole and 2-hydrazinobenzothiazole compounds can be easily manufactured by known methods. In such a procedure, the appropriate

309816/1 168

2-amino compound diazotized and then introduced chlorine, which is then replaced by hydrazine. In another method, the mercapto group becomes the corresponding 2-mercapto compound displaced by hydrazine: J. Chem. Soc, 1949, 355. In another method, exchange lamination, the amino group of the corresponding 2-amino compound is replaced by a hydrazino group (J. Gen. Chem. U.S.S.R. (English translation) Vol. 29, P. 2036 (1959)). In an improvement of the latter process, the reaction is catalyzed by acid, and the reactants are applied in amounts a ratio of one mole of the 2-amino compound to 1 to 5 moles of hydrazine, preferably about 3 moles of hydrazine correspond.

In the case of 3-methyl-s-triazolo (3,4-b) -benzthiazole, one of the compounds to be used according to the invention, was found that they were under the conditions normally used for the preparation of pesticides are applied, forms a hydrate easily. If water is added to the compound, it forms initially a viscous liquid. By adding more water, the viscous liquid turns into a solution above. Drying the viscous liquid leads to a powder whose analysis values are accurate for the monohydrate voices. This monohydrate can be used as an active ingredient of any preparations within the scope of the invention, among others can also be used for seed treatment. Other compounds to be used in the context of the invention can also form hydrated forms which are also useful.

9 816/1168 ^

Claims (12)

Claims il. Method for producing a compound of formula Ria , la in which mean each of the radicals R ^a , which can be identical to or different from one another, hydrogen / halogen, C.-CU-alkyl radicals, C.-C ₃ -alkoxy radicals or C.-CU-alkylthio radicals, Z oxygen or sulfur and 4th
R is hydrogen, a C -C alkyl group, a cyclopropyl group, a trifluoromethyl group or a group the formula -C-O- or with the proviso (1) that at least two radicals R la 4
at least one radical R and R are hydrogen and (2) that when both R and the radical R are in the. 5-position represent groups other than hydrogen, these groups together do not contain more than 6 carbon atoms, characterized in that a corresponding 2- (2-acylhydrazino) benzoxazole or benzothiazole of the formula 3098 16/1168 , la H-NH-C-R Reacts at 0 to 250 C with polyphosphoric acid. 2. The method according to claim 1, characterized in that 3-chloro-s-triazolo (3,4-b) benzthiazole, 5-chloros-triazolo (3,4-b) benzthiazole, 5-fluoro-s-triazolo {3,4-b) -benzthiazole or 5-methyl-s-triazolo (3,4-b) benzthiazole. 3. 3-chloro-s-triazolo (3,4-b) benzothiazole. 4. 5-chloro-s-triazolo (3,4-b) benzothiazole 5-fluoro-s-triazolo (3,4-b) benzthiazole, 5-methyl-s-triazolo (3,4-b) benzothiazole, 7. Pesticides made from a surface-active dispersant, an inert, finely divided solid and an active ingredient, characterized in that it is a compound of the formula as active ingredient 30981 6/116 8 r2-C- or phytologically acceptable acid addition salts thereof contains, where in the formula mean 0 0 0 X -0-, -S-, -S-, or -S-, the radicals R, which can be the same or different from one another, hydrogen, halogen, a Cj - C - alkyl group, a C.-C ₃ -alkoxy group or a C.-Cg-alkylthio group, 2
R is hydrogen, a C ₁ -C ₁₁ -alkyl group, a cyclopropyl group, a hydroxyl group, a C.-C ^ -alkoxy group, a mercapto group, a Cj-G ₃ -alkylthio group, an allylthio group, a propynylthio group, a benzylthio group, halogen, a Amino group, a Cj-Cj-alkylamino group, a di- (Cj-Cj-alkyl) amino group, a carbamoyl group, a thiocyanate group, an acetamido group, a trifluoromethyl group, a group of the formula ■ I -COR ³ ,
wherein R is sodium, potassium, a C.-C ₃ alkyl group, a 309 3 16/1168 Halomethyl group or a mono- or di ~ (C | -C - alkyl) -amino group 1st, with the proviso (1) that at least two radicals R or 1 2 at least one radical R and the radical R is hydrogen 2 ■. ■ mean and (2) that if both R and the remainder 1 ■ ' R in the 5-position mean groups other than hydrogen, these groups together contain no more than 6 carbon atoms. 8. Composition according to claim 7, characterized in that it is the active ingredient 3-methyl-s-triazolo (3,4-b) benzthiazole, 3-methyl-s-triazolo (3,4-b) benzoxazole, 3-chloro-s-triazolo- (3,4-b) benzothiazole, Contains 5-chloro-s-triazolo (3,4-b) benzthiazole or 5-methyl-s-triazolo {3,4-b) benzthiazole. 9. Use of a compound of the formula ,1 in which mean -O-, -S-, -S-, or -S-, each of the radicals R, which can be the same or different from one another, hydrogen, halogen, a ^c i "" Cj -alkyl group, a C.-C ₃ -alkoxy group or a C.-C ^ -alkylthio group, 309816 / 11G8 R- hydrogen, a CL-C ₁ -alkyl group, a cyclopropyl group, a hydroxy group, a C, -C., - alkoxy group, a mercapto group, a Cj-CU-alkylthio group, an allylthio group, a propynylthio group, a benzylthio group, halogen, an amino group, a Cj-CU-alkylamino group, a di- (C 1-6 alkyl) -amino group, a carbamoyl group, a thiocyanate group, an acetamido group, a trifluoromethyl group, a group the formula Il -COR ³ , where R is sodium, potassium, a C.-C ^ alkyl group, halomethyl group or a mono- or di- (C, ~ C ₃ -alkyl) amino group, with the proviso (1) that at least two radicals R or 1 2
at least one radical R and R are hydrogen and (2), 2 1 that when both R and the radical R in the 5-position denote groups other than hydrogen, these groups together do not contain more than 6 carbon atoms, or a phytologically acceptable acid addition salt thereof, for controlling organisms pathogenic to plants by applying to the place of occurrence of these organisms. 10. Embodiment according to claim 9, characterized in that that the pest is a fungus. 11. Embodiment according to claim 10, characterized in that that the fungus is the rice bladder (Piricularia oryzae). 3098 16/1168 12. Embodiment according to claim 10, characterized in that 3-methyl-s-triazolo (3,4-b) benzothiazole _# 3-methyl-s ~ triazolo (3,4-b) benzoxazole, 3-chloro-s-triazolo - (3,4-b) benzthiazole, 5-chloro-s-triazolo (3,4-b) benzthiazole or 5-methyl-s-triazolo {3,4-b) benzthiazole is used. 3098 16/1168