DE2239892A1 - MEANS FOR CONTROL OF PLANT PATHOGENIC ORGANISMS - Google Patents

Description

Eli Lilly and Company »Indianapolis, Indiana, V.St.A. Agents for combating phytopathogenic organisms

The invention relates to means for combating phytopathogenic organisms and new s-triazolo- (4, 3-a) quinoline compounds of those defined below Formula II.

The agents according to the invention contain at least one s-triazolo (4,3-a) quinoline compound of the formula as active ingredient

or

3 0 9 8 0 9/1162

223S392

or their phytologically acceptable mineral acid addition salts, wherein

R is in each case a hydrogen atom, a halogen atom, a lower C -C alkyl radical, a lower C -C alkoxy group, a formyl radical, a cyano group, a trifluoromethyl radical or a substituted methyl radical of the formula -CH ₃ Y in which Y is Amino group, a lower C.-C-alkylamino group, a cyano group, a hydroxyl group, a halogen atom or a lower C.-C ₃ -alkoxy group,

2
R is a hydrogen atom, a lower C ^ Cg -alkyl radical, a vinyl radical, a C ₃ -Cg -cycloalkyl radical, a hydroxy group, a lower C.-C ₃ -alkoxy group, a mercapto group, a lower C.-C ₃ -alkylthio group, a benzylthio group, a halogen atom, an amino group, a C.-C ₃ lower alkylamino group, a di-C.-Cg lower alkylamino group, a carbamoyl group, a thiocyanate group, an acetamido group, a trifluoromethyl radical, a radical of the formula

Il

-COR ⁴ ,

in which R is sodium, potassium or a lower C ^ -C.-alkyl radical i «t, or a radical of the formula -CH ₃ -Y *, in which Y 'is an amino group, a lower C.-C.-alkylamino group, a Cyano group, a halogenatoB, a lower Cj-Cj -alkoxy group, a lower Cj-Cj -alkoxymethyl group or a haloethyl group, and

R in each case denotes a hydrogen atom, a lower C ₁ -C ₃ -alkyl radical or a halogen atom, with the proviso that no more than two radicals R are halogen atoms or lower alkyl radicals are, furthermore (1) in formula I not more than three radicals

1 2

R and R are substituents other than hydrogen.

3098Q & / 1162

12 3 (2) in formula II no more than three radicals R, R and R others Substituents as hydrogen atoms are and (3) in the two

2 formulas I and II represent at least one of the radicals R and R in the 9-position hydrogen atoms.

The compounds defined above are useful as fungi control agents.

The term "halogen" used above denotes fluorine , chlorine, bromine and iodine. The radicals referred to above as lower alkyl radicals or as part of the above-mentioned lower alkylamino groups, lower alkylthio groups and lower alkoxy groups can be branched or straight-chain. If R denotes a lower di-C 1 -C 4 -alkylamino group, the lower alkyl radicals can be identical to one another or different from one another. In the case of the salts, the term "phytologically acceptable" is used to denote acids which are non-phytotoxic in salt form. In other respects the choice of acid is not critical, although a certain anion can in some cases provide particular advantages, for example good solubility, easy crystallizability and the like. Representative and suitable acids are, for example, hydrochloric acid , hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid. s ~ · * ™ -

The compounds suitable for the purposes according to the invention can be prepared by various synthetic methods. Some of these methods are generally applicable.

A first method generally used for making the invention connections used is suitable? is the condensation of a 2-hydrazinoquinoline

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NH-NH,

or 3,4-dihydro-2-hydrazinoquinoline

NH-NH,

with an acid of the formula R ₃ -COOH or a suitable ester thereof. The reaction is necessary for the production of connec-

2
fertilize suitable, in which R is hydrogen, lower alkyl radicals, cycloalkyl radicals, the trifluoromethyl radical, a radical -CH-Y ', where Y ¹ · a lower C -C_ -alkoxy group or a lower C.-CL-alkoxymethyl group, or a radical

-COR ⁴ ,

in which R is a lower C.sub.1 -C.sub.6 -alkyl radical. if

2 years

R has a different meaning, other synthetic routes, which will be explained later, are preferred. This synthesis route is generally advantageous regardless of the meaning R has, but other synthetic routes may be preferred be when R has certain meanings. Such other ways will be discussed later.

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To carry out this condensation reaction, the Reactants united with one another. In the reaction, the reactants are under in equimolar amounts Formation of the desired compound and water consumed as a by-product. An inert solvent can be used however, the reacting acid is usually one Liquid, and it is more convenient to have an excess of it apply. The reaction takes place over a wide temperature range, but better yields are achieved more quickly. when the reaction is carried out at the reflux temperature of the reaction mixture. The separation and if desired, the cleaning can be carried out by customary methods.

A second synthesis method that is generally applicable for the preparation of the compounds used in the invention is the implementation of the same 2-Hydrazinochinolins or 3,4-dihydro-2-hydrazinochinolins

H-NH,

NH-NH,

as before with a. Orthoester of the formula R -C (O-alkyl) -,

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This synthetic route is advantageous for the preparation of compounds in which R is hydrogen, lower alkyl radicals or cycloalkyl radicals. As with the first synthesis method, the meaning of the radicals R is not critical.

In the reaction, the reactants are in equimolar Amounts consumed to form the desired compound and the corresponding alkanol as a by-product. An inert liquid is expediently used as the reaction medium. The implementation takes place in a wide temperature range instead, however, better yields are obtained more quickly if the reaction is carried out at the reflux temperature of the reaction mixture is made. The separation and, if desired, the Cleaning is carried out according to the usual methods.

With any of the methods described above, the implementation in some cases will provide a 2- {2-acylhydrazino) quinoline or 2- (2-acylhydrazino) 3,4-dihydroquinoline in place of the desired triazolo product. In such cases a ring closure can occur of the desired product can be achieved by immersing the intermediate product in a suitable solvent, for example phenol, is heated to reflux.

Other synthetic methods are required for such compounds.

2 2

borrowed, in which R has certain meanings. When R -OH or -SH means, the compounds are prepared by reacting the same 2-hydrazino compounds as previously indicated as starting materials with a phenyl isocyanate or phenyl isothiocyanate. In some cases the 1-OH and 1-SH compounds in equilibrium with the «S and «O-forms before, i.e.

HO- C

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Subsequent alkylation gives the initially obtained

2 products in compounds converted in which R AIkoxygrunnen lower, lower Alkylthiogrutroen or benzylthio

2 group means. Compounds in which R is an aminogruope means are obtained by reacting the same 2-hydrazinoquinoline or 3,4-dihydro-2-hydrazinoquinoline with cyanogen bromide manufactured.

Further compounds suitable for the purposes of the invention are obtained from the condensation product of dimethyl oxalate and a the 2-hydrazino compounds previously mentioned as starting materials

.1

(Lower alkyl) OOC

or

(Lower alkyl) OO

obtained by means of usual reactions. Such reactions include hydrolysis of the ester to the sodium or potassium salt

0
(R ² = -CO-sodium or -potassium)

and the aminolysis of the ester to the amide (R = carbamoyl). Acylation of the 1-NH ₂ compound yields the acetamido group

300800 / 11.0

(R «acetamido) or other amide groups, and a reduction

2 of the amides give substituted amino groups (R - (Cj-Cj amino or di-Cj-C ^ alkylamino)).

The compounds with R ^β halogen are made from compounds with

2
R = H and the thiocyanate derivatives from these halogen compounds

2 gen received. To do this, the connections with ReH are made with a Halogenating agents, for example N-halosuccinimide, implemented. Other halogen derivatives that are not readily available can be prepared by reaction with N-halosuccinimide, by halogen exchange reactions, for example the Finkelstein reaction. The thiocyanate group is introduced in a conventional manner, for example by reaction a 1-halogen compound with an alkali metal thiocyanate. the 1-Halogen compounds can also be used as precursors for the 1-substituted Amino compounds serve. To carry out these numerous reactions to generate the desired substituents

2
tuenten R is based on 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).

2 To prepare the compounds with R ^s -CHjY ¹ , in which Y ¹ denotes an amino group, a lower alkylamino group, a cyano group, a halogen atom or a lower alkoxy group, the corresponding methyl-substituted compounds are reacted with N-bromosuccinimide in the presence of a small catalytic amount of benzoyl peroxide . This reaction gives the corresponding bromomethyl compound. The bromine atom of the bromomethyl substituent can then be exchanged for other radicals to produce the other substituted methyl groups. The same bromomethyl-substituted compound can also be prepared by another method. As stated above, the compounds with R ■ -CH ₂ -Y ¹ , wherein Y 'is a lower alkoxy group, can be prepared according to the first general rule described above

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2239592

Synthesis method can be produced directly. These connections, with a lower 1-alkoxymethyl substituent can then into the corresponding 1-bromomethyl compounds by known methods being transformed.

2
The compounds with R = -CH ₂ -Y ¹ , in which Y ^{1 is} a lower alkoxymethyl group, are also obtained directly by the first synthesis method described above. The compounds can then be converted into the

corresponding compounds with R = -CH ₂ -Y ¹ , in which Y ^{1 is} a halomethyl radical, are converted. Subsequent

'2

Dehydrohalogenation gives the compounds with R = vinyl.

The previously described methods are practically independent of the nature of the substituents R and R are suitable for the preparation of products of the formulas I and II. Generally will it is preferred if the desired substituents are already in the 2-hydrazinoquinoline or 3,4-dihydro-2-hydrazinoquinoline compound used are present. However, sometimes it is preferred to use the methods described with a Carry out hydrazino compound, which is a different than has the substituent ultimately desired, and then the substituent on the resulting triazoloquinoline to convert into the desired substituent. There can also be compounds with a further substituent, especially a carboxyl group, can be used, and the carboxyl group can then be removed by decarboxylation will. Such conversions are carried out according to well known methods. For example, such Compounds in which R denotes a substituted methyl radical from the corresponding methyl-substituted one Connection established as it was above for making

2 of compounds has been described in which R is a substituted methyl radical means. As mentioned above, halogenation of the 1-position can also take place, if this is unsubstituted. Mixtures can by customary methods, especially by column chromatography, be separated.

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If R is a formyl radical, such compounds can easily be prepared by oxidation of corresponding compounds with -CH ₂ OH. If R denotes a cyano group, the corresponding compounds can be obtained by further oxidation to compounds with -COOH, amidation to compounds with -CONH- and subsequent dehydration. For further synthetic methods that can be used for this and are known to the person skilled in the art, reference is made to Synthetic Organic Chemistry, supra, and Advanced Organic Chemistry, supra.

In addition to the synthesis methods described above, some compounds of the formula II, especially those in which R is a hydroxyl group, are expediently prepared by selective reduction of the 4,5-position in the corresponding compounds of the formula I. For this purpose, the compound of the formula I, expediently in a suitable liquid as the reaction medium, is hydrogenated in the presence of a catalyst, usually a noble metal and preferably palladium or platinum. Liquids suitable as reaction medium are, for example, the lower alkenols, ethyl acetate and the lower alkane acids. The catalyst can be used on its own or, especially in the case of palladium, on a support such as carbon or an alkaline earth metal salt. A Parr hydrogenation device or another pressure apparatus is expediently used to take up the reaction mixture during the hydrogenation, if this is carried out at elevated pressure. The hydrogenation can be carried out at temperatures from 20 to 100 ^° C., but acceptably good results are normally achieved at room temperature. In the reaction, the reactants are consumed in amounts which correspond to 1 mole of hydrogen per mole of the compound of the formula I, and the reaction is preferably terminated after this amount of hydrogen has been taken up in order to carry out a further non-selective reduction

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2239692

to restrict. The desired product is obtained from the reaction mixture and separated from other hydrogenation products using established methods. Usually the reaction mixture filtered to remove any remaining catalyst, and then the solvent is evaporated, leaving the product is obtained as a residue. This residue can be purified, usually by recrystallization.

Form the compounds defined by Formula I and II acid addition salts with mineral acids. These salts are by customary methods by reacting the compound of Formula I or II prepared as a free base in a suitable solvent with the desired acid »The separation and, if desired, cleaning will be carried out according to usual Methods carried out. Generally these are salts Monosalts. Some compounds of formula I and II, viz

12 3

those in which R, R or R @ 1b © or substituted amino groups Is or contains an amino group? however, form salts with two molecules of acid per molecule - the compound of Formula I or II. Such disalts are also within the scope of the invention. In the case of dibasic or polybasic Acids are also salts with two or more molecules of a compound of the formula I or II per molecule of acid. Such di- or poly-salts are also within the scope of the invention. So that the salts for the purposes of the invention are suitable, phytologically acceptable salts are preferred.

The following examples illustrate the preparation of the compounds according to the invention »

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Example 1 1-methyl-s-triazolo (4,3-a) quinoline

A 250 ml three-necked flask equipped with a mechanical stirrer and a reflux condenser is charged with 5.0 g of 2-hydrazinoquinoline. 100 ml of acetic acid are added to the flask. The reaction mixture is refluxed for 12 hours and then allowed to cool. Acetic acid is removed by evaporation. The solid residue consists of pure l-methyl-s-triazolo (4,3-a) quinoline. The product is recrystallized from ethanol; Melting point 166 to 167 ⁰ C.

Example 2 1-propyl-s-trlazolo (4 _f 3-a) chinoline

A 250 ml three-necked flask equipped with a mechanical stirrer and a reflux condenser is charged with 5.0 g of 2-hydrazinoquinoline. 100 ml of n-butanoic acid are added to the flask. The reaction mixture is kept at reflux temperature overnight. In the morning the reaction mixture is cooled and then made alkaline by adding sodium hydroxide. The desired 1-propyl-s-triazolo (4,3-a) quinoline is extracted from this solution with methylene chloride, and then the methylene chloride is evaporated. The product is recrystallized from ethanol; Melting point 158.5 to 159.5 ⁰ C.

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■ ■ - 13 -

223989?

Example 3 s ~ Triazolo (4 _f 3-a) quinolin '* l'-ol

In a 250 ml three-necked flask fitted with a reflux condenser is equipped, 15.9 g (0.1 mol) of 2-hydrazinoquinoline given together with 70 ϊηΐ diphenyl ethers. Then 11.9 g (0.1 mol) phenyl isocyanate added. This reaction mixture is refluxed for three hours, cooled and poured over Left to stand overnight at room temperature. In the morning the precipitate from the desired s-triazolo (4,3-a) quinolinl-ol filtered off and recrystallized from water; Melting point 133.5-134.5 ° C.

Example 4 l-Methylthio-s-triazolo (4,3-a) quinoln

By reacting phenyl isothiocyanate and 2-hydrazinoquinoline according to the procedure described in the previous example s-triazolo (4,3-a) quinoline-1-thiol is produced.

Then 10.0 g of the s-triazolo (4,3'-a) quinoline-1-thiol along with an equimolar amount of methyl iodide and one Pour excess sodium ethoxide in 100 ml of ethanol into a 250 ml flask. The reaction mixture is 4 hours refluxed and then allowed to cool.

Water is added to decompose the sodium ethoxide and the solvent is removed by evaporation. The solid residue obtained is then washed with water and recrystallized from ethanol, whereby the desired 1-methylthio-s-triazolo (4,3-a) quinoline is obtained; Melting point 115 to 116 ⁰ C.

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Example 5 s-Triazolo (4,3-a) quinoln-1-carboxylic acid sodium salt

By reacting diethyloxalate with 2-hydrazinoquinoline according to the procedure described in Examples 1 and 2, ethyl s-triazolo (4,3-a) quinoline-1-carboxylate is prepared.

1.0 g of the ethyl-s-triazolo-4 _# 3-a-quinoline-1-carboxylate are added to 25 ml of anhydrous ethanol. The reaction is carried out in a 100 ml three-necked flask equipped with a reflux condenser. The flask is heated to dissolve the starting material in the ethanol. This solution is mixed with 20 ml of a saturated solution of sodium hydroxide in ethanol. The reaction mixture is stirred for one hour at room temperature. The precipitate is then filtered off from the desired sodium salt of s-triazolo (4,3-a) quinoline-1-carboxylic acid. The product is boiled in ethanol to remove any starting material. The product thus obtained consists of pure white crystals with a melting point of 261 to 263 ^° C.

Example 6 1-Amino-s-triazolo (4,3-a) chlorine hydrobromide

In a 3 Hter three-necked flask with reflux condenser, the Containing 1500 ml of methanol, 25.0 g of 2-hydrazinoquinoline are added. Then 17 g of cyanogen bromide are added. The reaction mixture is heated to reflux temperature for 6 hours, then cooled and evaporated to about 200 ml. This solution is then poured into 1 liter of absolute ether. The resulting Precipitate from the desired 1-amino-s-triazolo (4,3-a) -quinoline hydrobromide is filtered off and washed with an aliphatic naphtha solvent.

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Example 7 1-Amino-s-triazolo (4.3 "a) quinoline

The l-amino-s-triazolo (4,3-a) quinoline hydrobromia _f obtained as described in the previous example is dissolved in water. To break down the salt, a mixture of sodium acetate and sodium hydroxide is added. The product is then deposited as a free base with a melting point of 250 to 253 ^{° C.}

Example 8

4,5-dihydro-s-triaz ©! ® {4,5-a) quinoline

A mixture of 6.6 g (0.04 mol) 3 "4 - dihydr © thioearbostyril and 20 ml anhydrous hydrazine becomes 0 _? Stirred for 5 hours at room temperature. The excess hydrazine is removed by evaporation. It remains a yellow oil surüek? which consists of the desired hydrazino derivative as determined by IR and NMR spectroscopy. Thin-layer chromatography (TLC) shows that the material is free from impurities. The yellow oil is used directly in the next stage without purification.

The yellow oil is dissolved in 50 ml of 98 percent strength formic acid and the solution is heated to reflux temperature for 2 hours while stirring. The excess formic acid is removed by evaporation. The solid brown residue is dissolved in water and an impurity, formylhydrazide, is crystallized and then removed. The water-soluble material is isolated by evaporating the water and recrystallizing the residue from chloroform. The desired 4,5-dihydro-s-triazolo (4,3-a) quinoline is obtained in a yield of 2.2 g; Melting point 164 to 165 ⁰ C.

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Example 1-methyl-8-triazolo (4,3-a) quinoline

15.9 g (0.1 mol) of 2-hydrazinoquinoline in 70 ml of xylene 13.0 g (0.11 mol) of methyl orthoacetate were added. The solution is kept at reflux temperature for 4 hours with stirring. During this time, methanol distills off from the reaction. The reaction mixture is cooled overnight and then for the separation of the desired l-methyl-s-triazolo (4,3-a) -quinoline filtered. Recrystallization from 1-butanol provides 9.0 g of product with a melting point of 166 to 167 C.

Example 10 1-chloro-s-triazolo (4,3-a) quinoln

3.8 l of carbon tetrachloride in a 5 liter three-necked flask are mixed with 10.0 g (0.0592 mol) of s-triazolo (4,3-a) quinoline and 15.75 g (0.1184 mol) of N-chlorosuccinimide were added. A trace of dibenzoyl peroxide is then added to the flask. the The reaction mixture is refluxed for 4 hours and during this time it is irradiated with a UV sunlight lamp. After the 4 hours have elapsed, the reaction mixture is allowed to cool. Then the solid material is filtered off and that Evaporated filtrate.

The residue from the filtrate is poured into ethanol which is saturated with hydrogen chloride. The material dissolves, but the 1-chloro-s-triazolo (4,3-a) quinoline forms an insoluble HCl salt which precipitates. This salt is then added to water to which sodium bicarbonate is added, thereby obtaining the free base as a white crystalline substance of melting point 162.5 to 163.5 ⁰ C.

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Example 11 5-Chloro-s-triazolo (4,3-a) chlnoline

1.0 mol of 2,4-dichloroquinoline is combined with 1 mol of anhydrous hydrazine in 4 liters of dioxane. The reaction mixture is heated to reflux temperature for 12 hours. It is then allowed to cool and the dioxane is evaporated. The solid obtained is refluxed for 12 hours in formic acid. The reaction mixture is then cooled and the formic acid evaporated. The 5-chloro-s-triazoloi4,3-a) quinoline is isolated and purified by column chromatography. A silica gel column with a solution of 5% methanol and 95% ethyl acetate is used as the eluent for this. The purified product melts at 242 to 243.5 ⁰ C.

Example 12 1-Trifluoromethyl-s-triazolo (4,3-a) quinoline

25.0 g of 2-hydrazinoquinoline, 50 ml of trifluoroacetic acid and 250 ml of xylene are refluxed overnight in a 500 ml three-necked flask equipped with a reflux condenser. In the morning the reaction mixture is allowed to cool and the solvent evaporated to give 10 g of a compound identified as 2- (2- (trifluoroacetyl) hydrazino) quinoline. The substance is poured into 40 ml of phenol and heated to reflux for 20 hours. Then, the reaction mixture is subjected to steam distillation to remove the phenol, whereby the desired 1-trifluoromethyl-s-triazolo (4,3-a) quinoline is obtained. After recrystallization from ethanol the melting point is 133.5 to 134.5 ⁰ C.

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Example 13 4,5-dihydro-s-triazolo (4,3-a) quinolin-1-ol

2.0 g of s-triazolo (4,3-a) quinolin-1-ol are mixed with 125 ml of ethanol, and 1.0 g of 5% palladium-on-carbon is added. The mixture obtained is hydrogenated at a hydrogen pressure of 3.5 atmospheres (50 psi) and a temperature of 50 ^° C. for 6 hours. Then, the mixture is filtered to remove the catalyst and the filtrate was evaporated, thereby obtaining the desired 4,5-dihydro-s-triazolo (4,3-a) quinoline-1-ol of melting point 181 to 182.5 ⁰ C. Its identity is confirmed by NMR spectroscopy and microanalysis.

Example 14 1- (2-Xthoxyethyl) -s-triazolo (4,3-a) quinoline

A mixture of 50.0 g (about 0.3 mol) of 2-hydrozinoquinoline and 100 g (about 0.85 mol) of 3-ethoxypropionic acid is refluxed for 8 hours. The reaction mixture is then allowed to cool and made alkaline with 50 percent sodium hydroxide solution. A precipitate forms from the desired 1- (2-XthoxyMthyl) -s-triazolo (4,3-a) -quinoline. The precipitate is filtered off and recrystallized from ethanol. Melting point 93 ^° C. The identity of the product is confirmed by NMR spectroscopy and by microanalysis.

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1-vinyl-s-triazolo (4,3-a) quinoline

s-Triazolo (4,3-a-) quinoline-l-ethanol hydrochloride salt, which is obtained by refluxing l- (2-ethoxyethyl) -s-triazolo- (4,3-a) quinoline in concentrated hydrochloric acid and then working up by customary methods is obtained is used for the preparation of 1-vinyl-s-triazolo (4,3-a) quinoline via l- (2-chloroethyl) -s-triazolo (4,3-a) quinoline as an intermediate. For this, 2.0 g of s-triazolo (4,3-a) quinoline-1-ethanol are mixed with 40 ml of phosphoryl chloride. The reaction mixture is refluxed for 3 hours , then allowed to cool and quenched by slowly pouring it into water. The mixture obtained is kept at a temperature of 40 to 50 ^° C. by adding ice. The reaction mixture is stirred during the quench. The reaction mixture is then made alkaline with 50 percent sodium hydroxide solution and extracted with methylene chloride. The desired 1-vinyl-striazolo (4,3-a) quinoline is obtained as a solid substance from the extract. After recrystallization from ethanol the melting point is 117 to 117.5 ⁰ C. The identity of the product is confirmed by NMR and IR spectroscopy and micro-analysis.

Examples 16-46

Other representative compounds according to the described Methods obtained using analog output stage are:

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5-methyl-s-triazolo (4,3-a) quinoline-l-thiol, mp. About 295 ⁰ C.

9-chloro-4,5-dihydro-s-triazolo (4,3-a) quinoline, m.p. 212-213 ⁰ C..

9-methyl-s-triazolo (4,3-a) quinoline, m.p. 193-194 ° C. s-triazolo (4,3-a) quinoline, m.p. 176-177 ⁰ C..

l, 5-dimethyl-s-triazolo (4,3-a) quinoline, m.p. 194-195 ⁰ C..

5-methyl-s-triazolo (4,3-a) quinoline-l-ol, mp. 280 to 280.5 ⁰ C.

7-Methoxy-s-triazolo (4,3-a) quinoline, m.p. 190.5 to 191.5 ⁰ C.

s-triazolo (4,3-a) quinoline-1-thiol, mp 256-258 ⁰ C. 9-Chloro-s-triazolo (4,3-a) quinoline, mp. 208-210 ⁰ C. s-. Triazolo (4,3-a) quinoline hydrochloride, m.p. 270 C. (dec.). 5-methyl-s-triazolo (4,3-a) quinoline, m.p. 222-223 ⁰ C..

1-ethyl-s-triazolo (4,3-a) quinoline, mp. 126-127 ⁰ C. 9-Fluoro-s-triazolo (4, 3-a) quinoline, m.p. 199-202 ⁰ C.. 9-ethyl-s-triazolo (4,3-a) quinoline, m.p. 198-199 ° C.

5-chloro-1,4-dimethyl-s-triazolo (4,3-a) quinoline, m.p. 224 to 225.5 ° C.

5-chloro-4-methyl-s-triazolo (4,3-a) quinoline, m.p. 252-254 ⁰ C..

1-isopropyl-s-triazolo (4,3-a) quinoline, 82 to 85 ⁰ C. mp.

s-triazolo (4,3-a) chinolinhydrojodid, mp. 235-240 ⁰ C. (dec.).

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l-methylthio-s-triazolo (4,3-a) chinolinhydrojodid, mp. 195-200 ⁰ C (dec.)

7-methoxy-l-methyl-s-triazolo (4,3-a) quinoline, m.p. * 146 to 147 ° C.

Ethyl-s-triazolo (4,3-a) quinoline-l-carboxylate _/ mp. 149 to 151. ⁰ C.

4,5-dihydro-l-methyl-s-triazolo (4,3-a) quinoline, m.p. 118-119 ⁰ C..

l-Cyclopropyl-s-triazolo (4,3-a) quinoline, 94 to 96 ⁰ C. mp.

1-acetamido-s-triazolo (4,3-a) quinoline, 151 to 153 ⁰ C. mp.

l-ethyl-5-methyl-s-triazolo (4,3-a) quinoline, mp. to 154 ⁰ C.

1-Butyl-s-triazolo (4,3-a) quinoline, 115 to 117 ⁰ C. mp.

9-methyl-4,5-dihydro-s-triazolo (4,3-a) quinoline 110 to 111 ⁰ C. mp.

5,7,9-trimethyl-s-triazolo (4,3-a) quinoline, mp. '260-262 ⁰ C.

5,8-dimethyl-s-triazolo (4,3-a) quinoline, m.p. 275-277 ⁰ C..

1-ethylthio-s-triazolo {4,3-a) quinoline, m.p. 121-122 ⁰ C..

s-Triazölo (4,3-a) quinoline-1-carboxamide, mp. 230-232 ⁰ C.

Other suitable for the purposes of the invention Connections are for example:

309-09 / 1 1

1-methylamino-s-triazolo (4,3-a) quinoline l-diethylamino-4,5-dihydro-s-triazolo (4,3-a) quinoline 4,5-dihydro-l-propylamino-s-triazolo ( 4,3-a) quinoline 1-diethylamino-s-triazolo (4,3-a) quinoline 1-amino-4,5-dihydro-s-triazolo (4,3-a) quinoline 4,5-dihydro-s -triazolo (4,3-a) quinoline-1-thiol 4,5-dihydro-1-methoxy-s-triazolo (4,3-a) quinoline 4,5-dihydro-1-methylthio-s-triazolo (4 , 3-a) quinoline l-benzylthio-4,5-dihydro-s-triazolo {4,3-a) quinoline 4, S-dihydro-l-thiocyanato-s-triazolo (4,3-a) quinoline 1- (Ethoxymethyl) -s-triazolo (4,3-a) quinoline potassium 4 _/ 5-dihydro-7-methyl-s-triazolo (4,3-a) quinoline-1-carboxylate 1-bromo-5-methyl- s-triazolo (4,3-a) quinoline 4,5-dihydro-l-fluoro-s-triazolo (4,3-a) quinoline l-iodine-5-methyl-s-triazolo (4,3-a) quinoline 4,5-dihydro-1,4,5-trichloro-s-triazolo (4,3-a) quinoline

Methyl s-triazolo (4,3-a) quinoline-1-carboxylate Butyl 4,5-dihydro-s-triazolo (4,3-a) quinoline-1-carboxylate

4,5-dihydro-1-trifluoromethyl-s-triazolo (4,3-a) quinoline 1-acetamido-4,5-dihydro-s-triazolo (4,3-a) quinoline 4,5-dihydro-s-triazolo (4,3-a) quinoline-1-carboxamide 1-isopropoxy-s-triazolo (4,3-a) quinoline 1-butyl-4,5-dihydro-s-triazolo (4,3-a) quinoline 1-Cyclopentyl-4,5-dihydro-s-triazolo (4,3-a) quinoline 1-Benzylthio-s-triazolo (4,3-a) quinoline 1-thiocyanato-s-triazolo (4,3-a) quinoline 4,5-dichloro-4,5-dihydro-s-triazolo (4,3-a) quinoline 4,5-dihydro-7-methoxy-s-triazolo (4,3-a) quinoline 7-bromo-4,5-dihydro-s-triazolo (4,3-a) quinoline 9- (methoxymethyl) -4,5-dihydro-s-triazolo (4,3-a) quinoline 4, S-dihydro-5-ethyl-s-triazolo (4,3-a) quinoline 4,5-dihydro-9- (ethoxymethyl) -s-triazolo (4,3-a) quinoline 4,5-dihydro-5,9-dimethyl-s-triazolo (4,3-a) quinoline 1- (aminomethyl) -s-triazolo (4,3-a) quinoline 1 - ((Xthylamino) methyl) -s-triazolo (4,3-a) quinoline 1- (cyanomethyl) -s-triazolo (4,3-a) quinoline 1- (Bromomethyl) -s-triazolo (4,3-a) quinoline 1- (ethoxymethyl) -9-methyl-s-triazolo (4,3-a) quinoline

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The compounds of the formulas I and II (hereinafter referred to as "triazoloquinoline compounds") are used for combating numerous phytopathogenic organisms, including fungi and bacteria. So can the triazoloquinoline compounds for combating such organisms as the pathogens of the crown galls, rice brandy, powdery meltau, anthracnose and the like can be used. The connections are special advantageous for combating fungal organisms. Particularly good results are obtained in combating rice blight achieved. The compounds can be used successfully in numerous forms. With the predominant type of application the compounds are effective against phytopathogenic organisms when they act on the foliage of Plants are applied that are exposed to an infestation. In addition, the triazoloquinoline compounds are applied to seeds to protect the seeds and the resulting plants against attack by plant pathogens Protect organisms. The connections can also be used to Control of phytopathogenic organisms distributed in the soil will. It has been found that many of the compounds are transported by the plants, so that in such Felling both organisms that attack the foliage and organisms that attack other parts of the plant, be fought.

The method according to the invention exists very generally to combat phytopathogenic organisms in it, at a point where the organisms occur, a to apply effective amount of one or more of the triazoloquinoline compounds. The triazoloquinoline compounds can be used alone. The invention also includes the use of a liquid, a Powder or dust containing one or more

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Contain triazoloquinoline compounds. Such agents are not essential for application to living plants Suitable for damage to plants. The triazoloquinoline compounds can be used to produce such agents with one or more of a large number of excipients modified, including organic solvents, petroleum distillates, water or other liquids Carriers, surface-active dispersants and finely divided inert solids. In such compositions the triazoloquinoline compound can be contained in a concentration of about 2 to 98% by weight. Depending on the concentration the triazoloquinoline compound in the composition can be such preparations to combat undesirable phytopathogenic organisms are used or serve as concentrates, which later with further inert Carriers to be diluted to the finished treatment agents. Preference is given to those preparations which have both a finely divided solid as well as a surfactant.

The exact concentration of the triazoloquinoline compound used in the agent for use on phytopathogenic Organisms and / or the sites where they occur may vary, provided that it is guaranteed that an effective amount thereof can be applied to either the organisms or the sites of their occurrence. The effective The amount depends in part on the sensitivity of the phytopathogenic organism in question and on the Activity of the connection used. In general, liquid formulations that are about 0.001 to 0.1 percent by weight triazoloquinoline compound or more, has given good results. With dusts good results are usually obtained with formulations containing 0.5 to 5.0 percent by weight triazoloquinoline compound or more. Related to the field order

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will be a good control of phytopathogenic organisms achieved when the triazoloquinoline compounds on areas with growing plants in amounts of 0.57 to 5.65 kg per hectare (0.5 to 5.0 pounds per acre) or more can be applied.

Triazoloquinoline compounds can be used to produce dusts be compounded with finely divided solids such as pyrophyllite, talc, chalk, gypsum and the like. For this purpose, the finely divided carrier with the triazoloquinoline compound ground or mixed, or with a solution of the compound in a volatile organic solvent moisturizes. Dusts containing such compounds can also be used with various surfactants Dispersants, for example fuller's earth, bentonite, attapulgite and other clays, can be compounded According to the properties of the constituents, these dusts can be used to combat phytopathogenic organisms can be used or serve as concentrates and later with another solid surfactant dispersant and diluted with pyrophyllite, chalk, talc, plaster of paris and the like, so that an agent with the desired amount of active ingredient is obtained, which is used for combating phytopathogenic organisms can be. When such dusts are used as concentrates, they can also be used in water with or without help dispersed by dispersants to create spray mixtures.

The triazoloquinoline compounds or liquid or dust concentrates containing such compounds, can also be combined with surface-active dispersants, for example nonionic emulsifiers to produce sprays. Let such means

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can be used to combat phytopathogenic organisms or can be dispersed in liquid carriers to produce diluted sprays containing the active ingredients in any desired amount. the Choice of dispersants and their amounts are determined by the ability of the agents to disperse the Concentrate in the liquid carrier to facilitate the creation of the desired spray.

Likewise, the triazoloquinoline compounds can be mixed with a suitable water-immiscible organic liquid and a surface-active dispersant Emulsifiable concentrates can be prepared, which are further mixed with water and oil in the form of spray mixtures Oil-water emulsions can be diluted. In such compositions the carrier consists of an aqueous emulsion, i. a mixture of water-immiscible solvent, emulsifier and water. Used in such media Dispersants are preferably oil-soluble and belong to the group of nonionic emulsifiers, for example condensation products of alkylene oxides with inorganic acids, polyoxyethylene derivatives of sorbitan esters, complexes Ethereal alcohols and the like. Suitable organic liquids to be used in the agents are, for example, petroleum and petroleum distillates, toluene and synthetic organic oils. The surface-active Dispersants are usually used in liquid preparations in amounts of 0.1 to 20.0 percent by weight, based on the total weight of the dispersant and active compound.

In the practice of the invention, the pathogenic organisms to be controlled or the sites their occurrence with the triazoloquinoline compounds or preparations containing these compounds, be treated in any convenient way, for example

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with the help of hand dusters or sprayers. The order a can expediently with motor-driven piling devices, boom sprayers, High pressure sprayers and spray dusters succeed ». To treat large areas, dust or Low volume sprays can be applied from aircraft. When using the triazoloshinoline compounds to combat rice blight can be due to the particular kulfurbedisagungen under which rice is grown, special application methods are preferred. Such special methods include application to the water surface, the watering of plants, the to be offset, the treatment of the seeds and the like. The application of other methods lies in the Framework of skill.

The following examples explain the suitability of the triazοlochinoline compounds for combating phytopathogenic organisms.

Examples 47-61

Various triazoloquinoline compounds have been tested for effectiveness in combating Colletotrichum lagenarium (anthracnose) tested on cucumber. These tests were carried out as follows.

For each test a 10 cm (4 ") pot of sterilized Soil with a vermiculite layer on the surface, planted with 4 cucumber seeds and kept under normal greenhouse conditions. The seedlings were diluted to two plants. About 15 days after planting

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the foliage was sprayed with a solution of the relevant triazoloquinoline compound, allowed to dry and then infected by spraying with an aqueous suspension of conidia of Colletotrichum lagenarium.

Each triazoloquinoline was prepared in the usual manner. The compound was dispersed in a certain amount of cyclohexanone, which is a small amount of a mixture comprised of two surfactants (sulfonate and nonionic) and then mixed with water to make one Treatment agent diluted that except for 400 parts of the compound in question per million parts by weight of the agent the cyclohexanone in a concentration of 0.67% and the mixture of surface-active agents in a concentration of 0.0353%.

The fungus was used to produce the conidia suspension cultured in Petri dishes on orange juice agar for 14 days at 22 ° C. Then the bowls were filled with distilled water covered and the surface was scraped off. The aqueous suspension obtained from 4 dishes was passed through cheesecloth filtered, brought to a volume of 50 ml and used for spraying the plants in about 35 pots.

After the plants were infected, they were placed in a humid room at 18 ^° C. for 48 hours, then kept under normal greenhouse conditions for about 9 days and then tested for control of anthracnose.

For each test, a control test was carried out in which the plants were only treated with an aqueous control solution treated the cyclohexanone and the surfactant mixture in the same concentrations contained.

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2239832

The test results were evaluated according to the following system and are given in the table below:

1 - severe illness

2 moderately severe illness

3 moderate illness

4 minor illness

5— · —no disease

The control pots uniformly showed severe anthracnose infestation on the cucumber plants. Phytotoxicity has been in all cases not or only to a minor extent. When more than one test is performed on the same compound a mean value is given in the table.

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Tabel

Combating Anthracnose

link

valuation

9-chloro-4,5-dihydro-s-triazolo (4,3-a) quinoline

9-methyl-s-triazolo (4,3-a) quinoline 1,5-dimethyl-s-triazolo (4,3-a) quinoline 5-methyl-s-triazolo (4,3-a) quinolin-1-ol 4,5-dihydro-s-triazolo (4,3-a) quinoline 5-methyl-s-triazolo (4,3-a) quinoline s-triazolo (4,3-a) quinolin-1-ol 1-methyl-s-triazolo (4,3-a) quinoline 1-ethyl-s-triazolo (4,3-a) quinoline 1-trifluoromethyl-s-triazolo (4,3-a) quinoline Ethyl s-triazolo (4,3-a) quinoline-1-carboxylate 4,5-dihydro-1-methyl-s-triazolo (4,3-a) quinoline 1-chlorotriazolo (4,3-a) quinoline 5-chloro-s-triazolo (4,3-a) quinoline 1-vinyl-s-triazolo (4,3-a) quinoline

4+

4+

3-

4+

3-

4+

3+

4+

4+

3-

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Examples ■ 62 ■; 74

Representative triazoloquinoline compounds were also tested for their effectiveness in combating the pathogen. Crown gall disease (Agrobacterium tumefaciens) on tomato plants tested. The tests were carried out as follows

Three tomato seeds were potted in 10 cm (4 ") plastic pots planted in sand and later diluted to 2 plants. Meanwhile an inoculum of Agrobacterium tumefaciens grown in test tubes on homemade potato dextrose agar. The cultures were then using covered with sterile water to create the required amount of bacterial suspension. With this suspension the tomato saplings were infected about 4 weeks after planting. A small insect attachment pin was used for this purpose dipped in the bacterial suspension and then stabbed through the stem of each tomato plant. Then were the plants are taken out of the sand and placed with the roots in an aqueous solution in a large test tube, which the test compound in a concentration of 40 ppm, 0.067% cyclohexanone and 0.00353% surfactants and sodium chloride in one concentration of 0.85% contained. The plants were grown for about 10 days with daily aeration under normal greenhouse conditions held. Each plant was then examined for symptoms of crown gall disease. ·

A control test was also carried out in which two infected plants were placed in a solution in a separate test tube containing all ingredients except the test compound. This test tube was in everyone Treated in the same way as the test tubes with the treated plants.

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The test results obtained using the same rating scale as in the previous examples are given in the following table. All control plants showed severe symptoms of crown gall disease. Phytotoxicity was not found in all cases, or only to a minor extent, only with 1-ethyl-striazolo (4,3-a) quinoline; Moderate phytotoxicity was observed for l-methylthio-s-triazolo (4,3-a) -quinoline and l-propyl-s-triazolo (4 _{r 3-a) -quinoline.}

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Table II

Combating crown gall
Connection rating

Sodium s-triazolo (4,3-a) quinoline-1-carboxylate 3

1-methylthio-s-triazolo (4,3-a) quinoline 5

9-methyl-s-triazolo (4,3-a) quinoline 5

s-triazolo (4,3-a) quinoline 5

1,5-dimethyl-s-triazolo (4,3-a) quinoline 3

7-methoxy-s-triazolo (4,3-a) quinoline 5

s-Triaz.olo (4,3-a) quinolin-1-ol 5

1-Methy1-s-triazolo (4,3-a) quinoline 5

1-ethyl-s-triazolo (4 "3-a) quinoline 5

7-methoxy-1-methyl-s-triazolo (4,3-a) quinoline 3

1-propyl-s-triazolo (4,3-a) quinoline 5

l-trifluoromethyl-s-triazolo ( A, 3-a) quinoline 5

Ethyl s-triazolo (4,3-a) quinoline-1-carboxylate 5

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Examples 75-77

Several triazoloquinoline compounds have been tested for effectiveness in combating powdery meltau (Erysiphe polygon!) Tested on beans. The tests were carried out as follows.

Four bean seeds were planted in 4 "(10 cm) pots of soil and later thinned to two seedlings for 10 days after planting, the test compounds were applied to the young plants in the form of one as in the examples 47 to 61 prepared agent applied containing 400 parts by weight of test compound per million parts by weight of the agent contained. Then the treated plants were placed near and under other plants that were heavily infested with powdery meltau to the treated plants by natural air movements infect. The plants were kept under normal greenhouse conditions for about 7 to 10 days. then the plants were examined for symptoms of powdery meltau. Each test was a control test carried out. For this purpose, a group of 4 plants was prepared with one also as in Examples 47 to 61 Solution treated with solvent and emulsifier which did not contain any test compound. The test results, obtained using the same rating scale as in the previous examples indicated in the table below. In the control tests, the bean plants showed uniformly strong results Infestation with powdery meltau. No phytotoxicity was observed in any of the plant groups.

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Table III Control of Powdery Meltau Compound Rating

1-methylthio-s-triazolo (4,3-a) quinoline 3

l-propyl-s-tria2olo (4 _/ 3-a) chlnolin 3-

1-chlorotriazolo (4,3-a) quinoline 3-

Examples 78-116

A number of triazoloquinolines have been tested for effectiveness in combating rice blight (Piricularia oryzae) checked. The tests were carried out as follows. By mixing equal parts of building sand and A potting soil was prepared from crushed humus soil. The soil was placed in 10 cm (4 ") pots and densely sown with rice seeds. The planted pots were then under typical greenhouse conditions for about 2 weeks held. After that, each pot showed a dense population of rice saplings.

An aqueous conidia suspension of the rice blot was also prepared. For this purpose, the mushroom was placed in Petri dishes grown on rice bran agar at 28 ° C. After 8 days, each dish was filled with 20 ml of distilled water covered and with a rubber plume, conidia were scraped from the surface of the culture.

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In each case, a treating solution prepared as in Examples 47 to 61 was applied to the sheet surfaces of the rice stock sprayed in a saucepan and allowed to dry. Then the foliage with the aqueous conidia suspension of rice blight infected. In each case the treatment solution contained 400 parts by weight of the compound per million parts by weight of solution. The pots were in one for 40 hours placed in a humid room at 18 C, then returned to the greenhouse and there for 6 days under typical greenhouse conditions held. Then the results were rated on the same scale as in the previous examples. The control test was carried out as follows. Pots of rice saplings were made with a watery Solution of cyclohexanone and the same mixture of two surfactants sprayed, but none Test compound contained. Otherwise the pots were in the treated the same way.

The test results are shown in the table below. Not all of these tests were done at the same time carried out. In all tests, however, the untreated control pots showed severe rice burn symptoms. in the In general, no phytotoxicity was found, but some treated pots showed low phytotoxicity observed.

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Tabel

IV

Fighting rice blight link

valuation

Sodium s-triazolo (4,3-a) quinoline-1-carboxylate 1-methylthio-s-triazolo (4,3-a) quinoline 9-chloro-4,5-dihydro-s-triazolo (4,3-a) quinoline 9-methyl-s-triazolo (4,3-a) quinoline s-triazolo (4,3-a) quinoline 1,5-dimethyl-s-triazolo (4,3-a) quinoline 5-methyl-s-triazolo (4,3-a) quinolin-1-ol 7-methoxy-s-triazolo (4,3-a) quinoline 4,5-dihydro-s-triazolo (4/3-a) quinoline s-triazolo (4,3-a) quinoline-1-thiol 5-methyl-s-triazolo (4,3-a) quinoline s-triazolo (4,3-a) quinolin-1-ol 1-methyl-s-triazolo (4,3-a) quinoline 1-ethyl-s-triazolo (4,3-a) quinoline s-triazolo (4,3-a) quinoline hydroiodide 7-methoxy-1-methyl-s-triazolo (4,3-a) quinoline 1-propyl-s-triazolo (4,3-a) quinoline 1-trifluoromethyl-s-triazole (4,3-a) quinoline Ethyl s-triazolo (4,3-a) quinoline-1-carboxylate 4,5-dihydro-1-methyl-s-triazolo (4,3-a) quinoline l-amino-s-triazolo (4,3-a) quinoline 1-Cyclopropyl-s-triazolo (4,3-a) quinoline 1-butyl-s-triazolo (4,3-a) quinoline 4,5-dihydro-9-methyl-s-triazolo (4,3-a) quinoline 5,7,9-trimethyl-s-triazolo (4,3-a) quinoline 5-chloro-s-triazolo (4,3-a) quinoline 1- (2-Ethoxyethyl) -s-triazolo (4,3-a) quinoline

3-

4+

4+

4-

3+

4+

4-

4-

3-

4+

4+

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Table IV (cont.) Compound Rating

1-chloro-s-triazolo (4,3-a) quinoline 5

1- (ethoxymethyl) -s-triazolo (4,3-a) quinoline 3

1-vinyl-s-triazolo (4,3-a) quinoline 3+

s-triazolo (4,3-a) quinoline hydrochloride 3-

9-fluoro-s-triazolo (4,3-a) quinoline 4+

9-ethyl-s-triazolo (4,3-a) quinoline 4-

5-chloro-1,4-dimethyl-s-triazolo (4,3-a) quinoline 3+

4-chloro-5-methyl-s-triazolo (4,3-a) quinoline 5

1-isopropyl-s-triazolo (4,3-a) quinoline 3

1-ethylthio-s-triazolo (4,3-a) quinoline 4-

1-ethyl-5-methyl-s-triazolo (4,3-a) quinoline 4

9-chloro-s-triazolo (4,3-a) quinoline 5

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Examples 117-12O

Some of the triazoloquinoline compounds suitable for the purposes of the invention were also tested for their effectiveness in combating rice blight when applied to the ground before planting = for these tests, the compound in question was dissolved in ethanol, which was opened in a DeVilbiss atomizer Drum circulated earth was sprayed and the soil was treated in this way. placed in round 10 cm (4 ") pots without drainage holes" The triazoloquinoline compounds were in certain M®ng @ n " namely in amounts of 28.25 kg and 14.13 kg per hectare (25 and 12.5 pounds per acre) When “Daa” wui? d © is planted with rice (Nato variety) and kept for 2 weeks with typical greenhouse conditions. Then the rice shoots were adorned with conidia of Piricularia orysae irafi · = which were applied as received in the previous examples were, and 48 stood kept in a humid room at 18 ⁰ C. Then the pots further 5 days were kept under Gewächshausbedingungexi. It was then tested for disease symptoms "di © f © st @ R§ © fcmisss ©, di @ using the same B © Werttaag @ slsaia previous examples were given in the table.

Each test was done three times

a control test carried out, b®i dem. Earth uses vrar.de, die'nur with an aqueous solution with the same ethanol concentration dealt with was »In the! control pots were severe rice burn symptoms found »

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Table V

Fighting rice blight

Soil treated before planting

Order quantity,

Compound kg / ha (pounds rating

per acre)

4,5-dihydro-s-triazolo (4,3-a) - 28 _r 25 (25) 4

quinoline 14.13 (12.5) 3

9-chloro-s-triazolo (4,3-a) - 28.25 (25) 4+

quinoline 14.13 (12.5) 3+

1-methyl-s-triazolo (4,3-a) - 28.25 (25) 4+

quinoline 14.13 (12.5) 3-

9-chloro-4,5-dihydro-s-triazolo-28.25 (25) 5 (4,3-a) -quinoline 14.13 (12.5) 4+

Examples 121-125

Various triazoloquinoline compounds have been tested for effectiveness in combating rice blight (Piricularia oryzae) when applied to the surface of water-saturated soil in which the rice was grown.

Rice was placed in round 10 cm (4 ") pots with no drainage holes (Variety Nato) planted. The earth became during the test,

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carried out under greenhouse conditions, kept in a water-saturated state.

The shoots were treated 14 days after planting. For this purpose, a treatment solution prepared as in Examples 1.17 to 120 was poured onto the surface of the earth in each pot. On the third day after the treatment, the plants were infected with a suspension prepared as in Examples 78 to 116 and placed in a humid room at 18 ^° C. for 48 hours. The plants were then returned to the greenhouse and kept under normal greenhouse conditions for 5 days . The plants were then examined for the presence and, if present, for the extent of rice burn symptoms.

Each test was carried out three times. Furthermore, a Control attempt made for each test. For the control experiment, an aqueous solution was used which contained only 0.5% ethanol. The test results are given in the table below. The control pots showed consistently strong rice burn symptoms.

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Table VI Fighting rice blight Order to the earth

link

Application quantity, kg / ha (pounds per acre)

valuation

4,5-dihydro-s-triazolo (4,3-a) ~ 28.25 (25)

quinoline 14.13 (12.5)

7.06 (6.25)

4+

4 4—

9-chloro-s-triazolo (4,3-a) -quinoline

28.25 (25) 4-14.13 (12.5) 4-7.06 (6.25) 3+

1-trifluoromethyl-s-triazolo-28.25 (25) 4+ * (4,3-a) quinoline 14.13 (12.5) 2

^, 5-dihydro-s-triazolo- 28.25 (25)

(4,3-a) quinoline 14.13 (12.5)

7.06 (6.25)

5.65 (5)

2.83 (2.5)

1.41 (1.25)

1)

4+

4+

4-

3-

l-chloro-s-triazolo (4,3-a) -quinoline

28.25 (25) 4+ 14.13 (12.5) 4-7.06 (6.25) 3-

considerable phytotoxicity observed.

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Examples 126-130

Various triazoloquinoline compounds were tested for their effectiveness in combating rice blight when applied to the rice seeds. For this purpose, the relevant triazoloquinoline compound was dissolved in ethanol and the solution was with water, the 0.1. % Polyoxyethylene sorbitan monolaurate contained i diluted to treatment solutions which contained the compound in question in various concentrations. 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 ml Erlenmeyer flask and then 20 ecm (about 12.5 g) rice seeds (variety Nato) were augesetat. Every flask was sealed and shaken for 48 hours. Then irarde the rice drained and rinsed with tap water.

The treated seeds were then planted in 10 cm (4 ") square pots and maintained under typical growing conditions. After the sprouting rice shoots had reached a height of 7.5 to 10 cm (3 to 4") {about 14 days after the plant), they were treated with a as in examples 78-116 prepared fungal suspension of Pisrisularia oryzae (Re'isbrand) infected .. the plants were then _v they followed for 48 hours in a humid room at 18 ^Q C incubated in the greenhouse returned vnä were kept there for about 5 days. The plants were then examined for the extent of disease using the rating system given in the previous examples.

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Each test was repeated three times. In addition, two control experiments were carried out with (1) water containing 0.5% ethanol and 0.1% polyoxyethylene sorbitan monolaurate, and (2) performed with bare water. Severe rice blight symptoms were observed in the control plants.

The test results are given in the following table:

link

Tabel

VII

Treatment of the seeds

Concentration of
Connection in the
Treatment solution,

valuation

4,5-dihydro-s-triazolo (4,3-a) -quinoline

1000 500 250

3+

3-

4, S-dihydro-g-methyl-s-triazolo-1000 (4,3-a) quinoline 500

4+ 4-3-

9-chloro-s-triazolo (4,3-a) -quinoline

1000 500 250

4+ 4-3 +

9-chloro-4,5-dihydro-s-triazolo- (4,3-a) quinoline

4+ 4-3

1-chloro-s-triazolo (4,3-a) -quinoline

3
3-

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As previously described in detail, the Compounds of 2-hydrazinoquinolines used for purposes of the invention and 3,4-DihYdro-2-hydrazinoquinolines produced as starting materials. These connections correspond to the formulas given below, in which R and R have the meanings given above.

H-NH,

Lots of these 2-hydrazinoquinoline and S ^ Quinoline compounds are themselves made by known methods produced, for example by reacting 2-chloroquinoline with hydrazine. However, a preferred method for preparing the 3,4-dihydro-2-hydrazinoquinolines is hydrazine with a 2-thio-3,4-dihydrocarbostyril

implemented. The reaction is conveniently carried out in a liquid Reaction medium carried out. Suitable are water that

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lower alkanols and ethers. The reaction takes place over a wide range of temperatures, but is preferred carried out at room temperature. The hydrazine can be used as Hydrate or as a hydrazine salt can be added. In the reaction, the reactants are in equimolar Quantities consumed, but the reaction is expediently carried out with an excess of hydrazine. The separation and, if desired, cleaning is carried out in accordance with the usual methods Methods.

The 2-hydrazinoquinoline and 3,4-dihydro-2-hydrazinoquinoline compounds have always been previously indicated as compounds with only one structure, but it is assumed that the Compounds actually exist as tautomers as indicated below:

> N '

= N-NH,

-NH-NH ₂ __

Such tautomers are known for the synthesis of the compounds Formula I and II can be used.

309809 / i162

Claims (16)

Claims 1. means for combating plant pathogenic organisms, characterized in that there is at least one s-triazolo (4,3-a) quinoline compound of the formula as active ingredient or or phytologically acceptable mineral acid addition salts of which contains, in which R each represents a hydrogen atom, a halogen atom, a lower C ₁ -C ₃ -AIkVIrCSt, a lower CJ-C ₃ -alkoxy group, a formyl radical, a cyangruone, a trifluoromethyl radical or a substituted methyl radical of the formula -CH ₃ Y, in which Y is an amino group , is a lower C -C ^ alkylamino group, a cyangrunpe, a hydroxy group, a halogen atom or a lower C -Cj alkoxy group, 3 0 9 8 0 9/1182 ORIGINAL IMSPECTED R ^{2 represents} a hydrogen atom, a lower C 1 -C 6 alkyl radical, a vinyl radical ,. a Cj-Cg-cycloalkyl, a hydroxy group, a lower C ^ C ₃ -alkoxy group, a mercapto group, a lower C.-CU-alkylthio group, a benzylthio group, a halogen atom, an amino group, a lower C ^ -Cj -alkylamino group, a lower di-Cj-Cj-alkylamino group, a carbamoyl group, a thiocyanate group, an acetamido group, a trifluoromethyl radical, a radical of the formula It -COR ⁴ , 4th
in which R is sodium, potassium or a lower C.-C ^ -alkyl radical, or a radical of the formula -CH ₂ -Y ¹ / in which Y ^{1 is} an amino group, a lower C .- ^ - alkylamino group, a cyano group, a halogen atom, is a C.-C ₃ lower alkoxy group, a C.-Cj lower alkoxymethyl group or a halomethyl group, and R in each case denotes a hydrogen atom, a lower C -C alkyl radical or a halogen atom, with the proviso that not more than two groups R are halogen atoms or the lower alkyl radicals defined above, where (1) 1 ■ '■■''2' ■■■ '■■' ■ ''' mel I no more than three radicals R and R are substitutes other than Wasseratoffatoifte , (2) in formula II no more than three radicals R , R and R are other substituents al * wet hydrogen atoms and (3) In both formulas I and II at least one of the 1
Means hydrogen. 2 1 at least one of the radicals R and R in the 9-position 2. Agent according to claim 1, characterized in that it contains a surface-active dispersant and an inert, finely divided solid. 309809 / 11ß2 3 "Medium according to claim 2, characterized in that it contains I-methyl-s.-triazolo (4,3-a) ehinolin as active ingredient" 4. Composition according to claim 2, characterized in that it contains l-ehlor-s-triazolo (4 _/ 3-a) quinoline as the active ingredient. 5. means after; Claim Z, characterized in that it contains 9'-Ghlox.-a'-triazolQ (4:, 3-a) ghinolin as an active ingredient. 6. Means according to: Claim 2 :, characterized> that it contains g ^ ethyl-sHirlazolo ^ jS-ajchinolin as an active ingredient. 7. Means according to claim 2, characterized in that it as active ingredient 4> 5 .-- Dihydro-s - triaz.olo (: 4,; 3 - a) -chinoliii ·. contains. - 8 * Agent according to claim 2, characterized in that it contains 4,5-dihydro * -l-raethYl-s-triazolo (4 _< p3-a) quinoline as the ingredient. 9. Means according to claim 2, characterized in that e * ice active ingredient 9-chloro-4,5-dihydro-s-triazolo (4,3-a) quinoline contains. 10. Composition according to claim 2, characterized in that it contains 4, S-dihydro-g-methyl-s-triazolo (4,3-a) quinoline as active ingredient. 11. s-Triazolo (4,3-a) quinoline compounds of the formula II and their phytologically acceptable mineral acid addition salts, wherein R, R and R are as defined in claim 1. 12. The compound of claim 11 which is 4,5-dihydro-striazolo (4,3-a) quinoline. 13. The compound of claim 11 which is 4,5-dihydro-1-methyl-s-triazolo (4,3-a) quinoline. 14. Compound according to claim 11, namely 9-chloro-4,5 · dihydro-e-tria »olo (4,3-a) quinoline. 15. A compound according to claim 11 which is 4,5-dihydro-9-methyl-a-triazolo ( A, 3-a) quinoline. 16. A method for combating phytopathogenic organisms, characterized in that the sites of occurrence the organisms are treated with an effective amount of the agent according to any one of claims 1 to 10. 309809/1162