FI88920C - New triazolylquinoline derivatives, process for their preparation and phagocidal compositions containing them - Google Patents

Description

Novel triazolylquinoline derivatives, process for their preparation and fungicidal compositions containing them 1 88920

The invention relates to novel triazolylquinoline compounds of the formula r 2 in which R x is hydrogen, methyl, trihalomethyl or carboxy, R 2 is hydrogen, halogen, C 1 -C 4 alkyl, hydroxy, C 1-4 alkoxy, amino, acetamino, C 1-4 dialkylamino, acetyl, carboxy, ethoxycarbonyl, nitro or trihalomethyl, R 3 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, R 4 is hydrogen, methyl or ethyl and X is a valence bond or -S -, provided that R 4 is not methyl, when R x, R 2 and R 3 simultaneously represent hydrogen; and their acid addition salts. These compounds have a fungicidal effect.

The invention also relates to a process for the preparation of compounds of the formula I: fungicidal compositions and to a process for controlling fungal diseases.

The compounds of the formula I and their acid addition salts are prepared according to the invention as a halogenquinoline derivative of the formula. 30

Cl: 35 2 88920 or CD (lii) 5 R3 wherein Rx, R2 and R3 are as defined above, is reacted with 1,2,4-triazole of formula 10

HN-M

[oi (IV) 15 or HN-N, loi m 20 where R <is as defined above, in the presence or absence of a solvent and in the presence or absence of an acid or a base, at a temperature of 0-200 ° C, and if desired the product obtained isolated in the form of the free base or acid addition salt.

For the preparation of compounds of the formula 30, the 4-chloroquinoline derivative of the general formula (II) is reacted with the 1,2,4-tri- with azole (wherein R1, R2, R3 and R4 are as defined above).

To prepare compounds of formula, a 4-chloroquinoline derivative of general formula (II) is reacted with a 3-mercapto-1,2,4-triazole of general formula (V) (wherein R 1, R 2, R 3 and R4 denote as above).

To prepare compounds of formula 20, 2-chloroquinoline of general formula (III) is reacted with 1,2,4-triazole of general formula (IV) (wherein R 1, R 2, R 3 and R 4 are as defined above). To prepare compounds of formula 35 4 88920 [30 - .. (¾ R3 ™ * 4 10, a 2-chloroquinoline derivative of general formula (III) is reacted with 3-mercapto-1,2 of general formula (V), With 4-triazole (wherein R1, R2, R3 and R4 are as defined above).

The starting materials used in the process of the present invention are known compounds. The starting material references in the prior art are as follows:

4-Chloroquinolines of general formula (II): "The Chemistry of Heterocyclic Compounds" vol. 32 Quinolines, Part I, pp. 391-398; References in this patent application: Hungarian patent applications serial numbers 3869/82 and 4003/82.

2-Chloroquinolines of general formula (III): "The Chemistry of Heterocyclic Compounds" vol. 32 Quinolines, Part I, pp. 387-390; J. Chem. Soc. P.I. 1981 1 (5) 25 1537-1543.

1H-1,2,4-triazoles of general formula (IV): Hungarian Patent Application Serial No. 4370/83, DOS No. 2,802,491; Chem. Ber. 1968 101 (6) 2033-2036.

3 (5) -Mercapto-1,2,4-tri-30 azoles of general formula (V): Liebigs Ann. Chem. 637, 133, 135-165 (1960).

It has been found that the reaction which takes place between 4- and 2-chloroquinoline derivatives of general formula (II) or of formula (III) having electron-only push-through substituents (e.g. methyl-35 or methoxy groups) and general formula (V) or 5,88920 between 1H-1,2,4-triazoles of formula (V) or 3 (5) -mercapto-1H-1,2,4-triazoles, respectively, is autocatalytic such that the hydrochloric acid formed during the reaction acts as a catalyst. Other acids, especially strong mineral acids or organic acids or acid salts (e.g. sulfuric acid, trifluoroacetic acid or ammonium chloride) also catalyze the reaction. The reaction is preferably carried out in the presence of said acidic compounds, in particular hydrochloric acid, the application rate of which varies from catalytic to stoichiometric.

When less basic quinolines with an electron-withdrawing group or groups (e.g., chlorine, trifluoromethyl) are used, no such catalysis is observed. In such a case, however, the reaction may be promoted by carrying it out in the presence of an organic or inorganic base (e.g., triethylamine, potassium carbonate or sodium hydroxide) having a stoichiometric or higher application rate. This also applies to the case where a 1H-1,2,4-triazole or 20 3 (5) mercapto-1H-1,2,4-triazole derivative is used in the form of an alkali salt (e.g. sodium salt).

In addition, it has been found that the mercapto group is more reactive than the -NH- group of the thiazole ring.

The reaction (preparation of compounds of general formulas (Ia), (Ib), (Ie) and (Id)) can be preferred! performed in the presence of a polar, organic solvent (e.g., ethanol, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc.). As the reaction medium, a non-polar, organic solvent (e.g.

30 benzene, toluene, chlorobenzene, dichlorobenzene) and can also be operated in the molten state without an organic solvent.

The reaction of the present invention can be carried out at a temperature of 0 to 200 ° C, preferably 20 to 150 ° C.

The reaction temperature is selected based on the properties of the reactants and the method used.

6 88920

It is sufficient to react the chloroquinoline component with a molar equivalent of 1H-1,2,4-triazole or 3 (5) -mercapto-1,2,4-triazole, but the reaction is generally more rapid and complete if the general formula 5 (IV) or ( V) 1-2 molar equivalents of starting material are used.

According to one embodiment of the process of the present invention, the reaction components are melted and the product formed is isolated after completion of the reaction. According to said embodiment of the process, the product is obtained in the form of the hydrochloride. The directly obtained reaction product is treated with a non-polar, organic solvent (e.g., ether, chloroform, benzene, hexane) or crystallized from a polar solvent (e.g., ethanol, methanol, acetonitrile, dimethyl, dimethylformamide) or solvents of polar and non-polar oxides.

The free base of general formula (I) can be isolated by cooling the reaction mixture, dissolving in water or a mixture of water and ethanol, preferably by adding a mineral acid or an organic acid, and precipitating the product by adding an organic or inorganic base. The crude product can be crystallized from a mixture of a polar, organic solvent and water or polar and non-polar organic solvents.

According to a further embodiment of the process of the present invention, the reactants are reacted in a non-polar organic solvent (e.g. benzene, toluene, xylene, hexane, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc.). Upon completion of the reaction, the product precipitated as the hydrochloride is isolated by filtration, crystallized if necessary, and converted to the free base form as described above.

According to a further embodiment of the process of the present invention, the reactants are reacted in a polar organic solvent (e.g. ethanol, ethylene glycol, acetonitrile, acetone, ethyl methyl ketone, dimethylformamide, dimethyl sulfoxide), dimethyl sulfoxide. Product 5 is isolated as the free base or as a salt with a mineral acid.

According to a preferred embodiment of the present invention, the reaction is carried out in a polar, organic solvent (e.g. ethanol, ethylene glycol, acetonitrile, acetone, methyl ethyl ketone, dimethylformamide), preferably in the presence of hydrochloric acid.

The acidic medium is obtained either by adding an acid (preferably hydrochloric acid) to the reaction mixture or by using a chloroquinoline component in the form of a salt (preferably the hydrochloride). The product obtained in the form of a salt can be isolated from the reaction mixture by any of the methods described above.

According to a further preferred embodiment of the process of the present invention, the reaction may be carried out in a polar organic solvent in the presence of a molar equivalent amount or more of a strong base (e.g. triethylamine, potassium carbonate, sodium carbonate, etc.).

The reaction described above can also be carried out using triazole or mercaptotriazole of general formula (IV) or formula (V), respectively, in the form of its alkali salt (e.g. sodium or potassium).

The structure of the novel compounds prepared by the method of the present invention has been characterized and verified by NMR, IR and MS spectra and the purity of the product has been determined by thin layer, gas and liquid chromatography.

The compounds of formula (I) have a remarkable activity against fungi and are effective against phytopathogenic fungal strains and diseases. The compounds of general formula (I) in particular produce cereal mildew. Table I shows the potency of some compounds of formula (I) against the strain Erysiphe graminis f. Sp. tritici.

The following test methods were used: 5 Greenhouse conditions: temperature 20 ° C, relative humidity 80%, illumination intensity 6000 lux. Test seedlings (autumn wheat MV-9) were grown in pots (diameter 20 cm) in a 1: 1 mixture of sand and perlite. Each pot contained an average of 180 doughs with a height of 6-7 cm.

The seedlings were sprayed with about 8 ml of an aqueous suspension of the test compound.

The degree of contamination was determined after 8 days. Activity was calculated from percentage inhibition values. The commercial products Fundazol 50 WP 15 and Karathene LC 50 were used as controls.

The present invention also relates to fungicidal compositions containing as active ingredient an effective amount of at least one compound of general formula (I) (wherein R 1, R 2, R 3, R 4 and X are as defined above) or an acid addition salt thereof in admixture with suitable ineffective solid or liquid carriers. or with diluents.

Said fungicidal compositions are prepared by methods known per se.

pp. 88920

Table I

In vitro fungicidal activity against the test organism Erysiphe graminis 5 Test compound No. Concentration Inhibition% ED50

yUg / ml yUg / mL

37.5 50.6 10 50 72.6 75 83.0 1 LOO 85.3 32.9 L50 86.8 200 90.1 15 400 99.6 25 42.1 50 70.9

LOO 82rO

8,150 84.1 3LfL

20,200 91.9 -V- 400 98.8 25 20.3 50 42.8 10 LOO 76.4 56.9 25,200 $ 2, 7

... 400 90, L

25 49.2 50 71.6 6 100 85, L 27.9 - 30 200 89.5: 400 99.4 10 88920

Table I (continued)

Test Compound Concentration Inhibition%

tea no ED

5 °

yug / ml yUg / mL

25 40.8 50 6?, 7 22 100 79, ö 31.2 10 200 93.0 koo 96.9 12.5 2i |, 9

Karathane 2 «5 U6 9

LO 50 D

50 72.7 27, Ί Ί5 L00 87.9 50 55.3

Chinoin fun- 100 72.6 41.2 dazole 50 WP 200 89,] _ 400 9 ^, 6 20

The following examples illustrate the invention. Example 1 4- (1H-1,2,4-Triazol-1-yl) -7-chloroquinoline

A mixture of 1.98 g of 4,7-dichloroquinoline, 1.38 g of 1,2,4-triazole and 10 ml of dimethylformamide was stirred for 6 hours at 100 ° C and then the reaction mixture was poured into 100 ml of water and neutralized with 1 ml of: 11a 30 concentrated ammonium hydroxide solution. The precipitated product was isolated by filtration and recrystallized from ethanol. There was thus obtained 1.61 g of the desired product, yield 70%, m.p. 169-170 ° C.

U 88920

Example 2 4- (1H-1,2,4-triazol-1-yl) -2,8-dimethylquinoline

A mixture of 1.91 g of 2,8-dimethyl-4-chloroquinoline and 1.38 g of 1,2,4-triazole was melted at 120 ° C and stirred for 2 hours. The solidified melt was dissolved in a mixture of ethanol and water. The solution was poured into a solution of 0.84 g of sodium bicarbonate and 20 ml of water. The precipitated product was isolated by filtration.

There was thus obtained 1.97 g of the desired compound, yield 88%, 10 m.p. 99-100 ° C.

Example 3 4- (1H-1,2,4-triazol-1-yl) -2-methyl-6-methoxyquinoline A mixture of 2.44 g of 2-methyl-4-chloro-6-methoxyquinoline hydrochloride, 1, 38 g of 1,2,4-triazole 15 and 10 ml of dimethylformamide were stirred for 3 hours at 80 ° C and then the reaction mixture was poured into 100 ml of water and neutralized with 2 ml of concentrated ammonium hydroxide solution. The precipitated product was isolated by filtration. There was thus obtained 2.09 g of the desired compound, yield 87%, m.p.

20-117-118 ° C.

Example 4 4- (1H-1,2,4-triazol-1-yl) -2-methyl-6,8-dichloroquinoline A mixture of 2.46 g of 2-methyl-4,6,8-trichloro- quinoline, 1.82 g of 1,2,4-triazole sodium salt and 10 ml of dimethylformamide were stirred for 25 hours at 100 ° C and then the reaction mixture was poured into 100 ml of water. The precipitated product was isolated by filtration. There was thus obtained 2.59 g of the desired compound, yield 93%, m.p. 220-222 ° C.

Example 5 4- (1H-1,2,4-triazol-1-yl) -2,8-bistrifluoromethylquinoline____

A mixture of 3.0 g of 4-chloro-2,8-bistrifluoromethylquinoline, 1.38 g of 1,2,4-triazole, 1.38 g of potassium carbonate and 30 ml of acetone was heated at reflux for 23 hours and then the reaction mixture was poured into 100 ml of 12,889,920 water. The precipitated product was isolated by filtration, relied on 5 ml of ethanol and then 5 ml of water were added. The precipitated product was isolated by filtration. There was thus obtained 2.42 g of the desired compound, yield 73%, m.p. 106-107 ° C.

Example 6 4- [TH-1,2,4-triazol-3 (5) -yl-5-5 (3) -mercapto] -2-trichloromethyl-8-chloroquinoline_

A mixture of 3.16 g of 2-trichloromethyl-4,8-dichloroquinoline, 1.48 g of the sodium salt of 3 (5) -mercapto-1,2,4-triazole and 10 ml of dimethylformamide was stirred for 18 hours at 100 ° C: in. After completion of the reaction, the reaction mixture was poured into water, and the precipitated product was isolated by filtration and recrystallized from ethanol. There was thus obtained 2.1 g of the desired compound, yield 55%, m.p. 188-183 ° C.

Example 7 4- {5 (3) -Ethyl-1H-1,2,4-triazol-3 (5) -ylmercapto] -2,8-dimethylquinoline_

A mixture of 1.32 g of 4-chloro-2,8-dimethylquinoline, 1.55 g of 3 (5) -mercapto-5 (3) -ethyl-1,2,4-tri-20 azole and 20 g of ml of ethanol, was stirred for 20 hours at 30 ° C. The reaction mixture was poured into 50 ml of water, neutralized with 1 ml of concentrated ammonium hydroxide, and the precipitated product was isolated by filtration. There was thus obtained 2.41 g of the desired compound, yield 85 t, m.p. 176-177 ° C.

Example 8 2- (1H-1,2,4-triazol-1-yl) -3-methylquinoline

A mixture of 1.78 g of 2-chloro-3-methylquinoline and 0.69 g of 1,2,4-triazole was melted and allowed to stand at 120 ° C for 4 hours. The melt was cooled, then dissolved in 10 ml of ethanol, poured into 20 ml of water and neutralized with 1 ml of concentrated ammonium hydroxide. The precipitated product was isolated by filtration. There was thus obtained 1.49 g of the desired compound, yield 71%, m.p. 80-81 ° C.

13 88920

Example 9 2- (1H-1,2,4-Triazol-1-yl) -4-methylquinoline hydrochloride A mixture of 1.78 g of 2-chloro-4-methylquinoline, 0.76 g of 1.2, 4-Triazole and 10 ml of chlorobenzene, stirred for 5 hours at 100 ° C. The reaction mixture was cooled, the precipitated product was isolated by filtration, dissolved in 5 ml of ethanol and precipitated by adding 10 ml of ethyl ether. The precipitated product was isolated by filtration. There was thus obtained 1.72 g of the desired compound, yield 70%, m.p. 193-10194 ° C.

Example 10 2- (1H-1,2,4-triazol-1-yl) -7-chloro-3,8-dimethylquinoline

A mixture of 2.26 g of 2,7-dichloro-3,8-dimethyl-15-quinoline, 1.1 g of 1,2,4-triazole sodium salt and 10 ml of dimethylformamide was stirred for 25 hours at 100 ° C. The reaction mixture was poured into 100 ml of water and the precipitated product was isolated by filtration. There was thus obtained 2.48 g of the desired compound, yield 96%, m.p. 147-148 ° C.

Example 11 2- (3-methyl-1H-1,2,4-triazol-1-yl) -4,6-bistrichloromethylquinoline

A mixture of 3.99 g of 2-chloro-4,6-bistrichloromethylquinoline, 1.26 g of the sodium salt of 3-methyl-1,2,4-triazole and 10 ml of dimethylformamide was stirred for 20 minutes. hours at 100 ° C. The reaction mixture was poured into 100 ml of water, the precipitated product was isolated by filtration and recrystallized from 10 ml of ethanol. There was thus obtained 2.76 g of the desired compound, yield 62%, m.p. 169-170 ° C.

Example 12 2- [5 (3) -Methyl-1H-1,2,4-triazol-3 (5) -ylmercapto] -3-methylquinoline hydrochloride_

A mixture of 1.78 g of 2-chloro-3-methylquinoline, 1.38 g of 3 (5) -mercapto-5 (3) -methyl-1,2,4-triazole 35 and 10 ml of chlorobenzene was stirred for 2 hours. 100 ° C. The reaction mixture was cooled, the precipitated product was isolated by filtration and washed with diethyl ether. There was thus obtained 2.8 g of the desired compound, yield 96%, m.p. 190-192 ° C. Example 13 2- [TH-1,2,4-triazol-3 (5) -ylmercapto] -4,8-dimethylquinoline hydrochloride________

A mixture of 1.92 g of 2-chloro-4,8-dimethylquinoline and 1.21 g of 3 (5) -mercapto-1,2,4-triazole was melted and allowed to stand at 120 ° C for one hour. The cooled reaction mixture was treated with 5 mL of hot ethanol, cooled and isolated by filtration. There was thus obtained 1.90 g of the desired compound, yield 65%, m.p. 201-202 ° C.

Example 14 4- (1H-1,2,4-Triazol-1-yl) -2,8-dimethyl-5-chloroquinoline A mixture of 2.26 g of 4,5-dichloro-2,8- dimethylquinoline, 1.38 g of 1,2,4-triazole and 0.1 g of 90% sulfuric acid were stirred for 3 hours at 70 ° C. The reaction mixture was poured into 50 ml of water and neutralized with 1 ml of concentrated ammonium hydroxide solution. The precipitated product was isolated by filtration and washed with water. There was thus obtained 2.0 g of the desired compound, yield 77.4%, m.p. 117-118 ° C.

Example 15 4- [5 (3) -Methyl-1H-1,2,4-triazol-3 (5) -ylmercapto] -2-methyl-7,8-dichloroquinoline A mixture of 2.46 g of 2-methyl -4,7,8-Trichloroquinoline, 1.38 g of 3 (5) -mercapto-5 (3) -methyl-1,2,4-triazole and 10 ml of dimethylformamide were stirred for 8 hours at 100 ° C. The reaction mixture was poured into 100 ml of water, neutralized and the precipitated product was isolated by filtration. There was thus obtained 3.10 g of the desired compound, yield 95%, m.p. 156-158 ° C.

is 88920

Example 16 2- (1H-1,2,4-triazol-1-yl) -3-methyl-7-ethylquinoline

A mixture of 2.05 g of 2-chloro-3-methyl-7-ethylquinoline, 1.05 g of 1,2,4-triazole hydrochloride, 0.69 g of 1,2,4-triazole and 10 ml of dimethylformamide , stirred for 6 hours at 100 ° C. The reaction mixture was poured into 100 ml of water, neutralized, and the crude product was recrystallized from a mixture of ethanol and hexane. There was thus obtained 1.52 g of the desired compound, yield 64%, m.p. 72-73 ° C.

Example 17 2- [1H-1,2,4-triazol-3 (5) -ylmercapto] -4-methylquinoline

A mixture of 1.78 g of 2-chloro-4-methylquinoline, 1.21 g of 3 (5) -mercapto-1,2,4-triazole and 10 ml of dimethylformamide was stirred for 3 hours at 40 ° C: in. The reaction mixture was poured into 100 ml of water, neutralized and isolated by filtration. There was thus obtained 2.37 g of the desired compound, yield 98%, m.p. 96-98 ° C.

Example 18 3- / 5 (3) -Ethyl-1H-1,2,4-triazol-3 (5) -ylmercapto-3,8-dimethylamino] _____

1.91 g of 2-chloro-3,8-dimethylquinoline and 1.55 g of 3 (5) -mercapto-5 (3) -ethyl-1,2,4-triazole were reacted in the same manner as in Example 16. The crude product was crystallized. again from a mixture of chloroform and ethanol. There was thus obtained 1.93 g of the desired compound, yield 68%, m.p. 190-192 ° C.

The other compounds were prepared according to the methods described in the previous examples. The compounds are shown in the following table. The number 30 in the column "Method" means the the number of the example used to prepare the compound.

16 88920

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Claims (14)

A triazolylquinoline compound of the formula 5 N N LsEf j Tol 2 S / S> 4 10 3 wherein R x is hydrogen, methyl, trihalomethyl or carboxy, R 2 is hydrogen, halogen, C 1 -C 4 alkyl, hydroxy, C C4 alkoxy, amino, acetamino, C1-C4 dialkylamino, acetyl, carboxy, ethoxycarbonyl, nitro or trihalomethyl, R3 is hydrogen, C1-C4 alkyl or C or ethyl and x are a valence bond or -S-, provided that R 4 is not methyl, where R 3, R 2 and R 3 simultaneously represent hydrogen; and acid addition salts thereof. 2. A compound according to claim 1, characterized in that it has the formula R 3, where R 1, R 2, R 3 and R 4 are the same as above, and acid addition salts thereof. 35 3. A compound according to claim 1, characterized in that it has the formula 36 wherein R 1, R 2, R 3 and R 4 are the same as above, and acid addition salts thereof. 4. A compound according to claim 1, characterized in that it has the formula R 2 Where Rx, r2, r3 and R4 are the same as above, and acid addition salts thereof. 5. A compound according to claim 1, characterized in that it has the formula 30 'Vxw' 'where Rx, R2, R3 and R4 are the same as above, and acid addition salts thereof. Compound according to claim 1, characterized in that it is 4- (1H-1,2,4-triazol-1-yl) -7-chloroquinoline, 4- (1H-1,2,4). -triazol-1-yl) -2-methyl-6-methoxyquinoline, 4- [1-H, 2,4-triazol-3 (5) -ylmercapto] -2-methyl-8-chloroquinoline, 4- [5 ( 3) -methyl-1H-1,2,4-triazole-3 (5) -ylmercapto] -7-chloroquinoline, 4- [5 (3) -methyl-1H-1,2,4-triazole-3 ( 5) -ylmercapto] 2-methylquinoline, 4- [5 (3) -methyl-1H-1,2,4-triazol-3 (5) -ylmercapto] -2,8-dimethylquinoline, 4- [5 (3) -methyl-1H-1,2,4-triazol-3 (5) -ylmercapto] 2.8-dimethyl-7-chloroquinoline, 2- (1H-1,2,4-triazol-1-yl) -3-methylquinoline , 2- [1H-1,2,4-triazole-3 (5) -ylmercapto] -3,6-dimethyl-quinoline, or 2- [1H-1,2,4-triazole-3 (5) - yl mercapto] -3,7-dimethylquinoline. A process for the preparation of triazolylquinoline compounds of formula I and their acid addition salts, 25 Wherein formula Rx is hydrogen, methyl, trihalomethyl or carboxy, R2 is hydrogen, halogen, C1-C4 alkyl, hydroxy, C1-C4-alkoxy, amino, acetamino, Cj-C ^ dialkylamino, acetyl, carboxy, ethoxycarbonyl, nitro or trihalomethyl methyl, R är is hydrogen, C - - alkyl alkyl or C S-, provided that R 4 is not methyl, where R 1, R 2 and R 3 simultaneously represent hydrogen, characterized in that a halogen quinoline derivative of the formula Cl 10 J * 1 (II) R 3 R 1 Cp (III) R 3 where R 1, R 2 and R 3 are the same as above, are reacted with a 1,2,4-triazoline of the formula 25 Two 1 (IV) or 30 HN-N | where R4 represents the same as above, in the presence of or without a solvent and in the presence of an acid or base or without them, at a temperature of 0-200 eC, 39 88920 and if desired, the obtained the product in the form of free base or acid addition salt. Process according to claim 7 for the preparation of compounds of formula (Ia), characterized in that a 4-chloroquinoline derivative of formula (II) is reacted with a 1,2,4-triazoline of formula (IV). . Process according to claim 7 for the preparation of compounds of formula (Ib), characterized in that a 4-chloroquinoline derivative of formula (II) is reacted with a 3-mercapto-1,2,4-triazoline with formula (V). A process according to claim 7 for the preparation of compounds of formula (Ie), characterized in that a 2-chloroquinoline of formula (III) is reacted with a 1,2,4-triazoline of formula (IV). 11. A process according to claim 7 for the preparation of compounds of formula (Id), characterized in that a 2-chloroquinoline derivative of formula (III) is reacted with a 3-mercapto-1,2,4-triazoline with formula (V). 12. A fungicide composition, characterized in that it contains as an active ingredient an effective amount of at least one compound according to claim 1 or acid addition salt thereof in admixture with suitable inert solid or liquid carriers or diluents. Process for preparing a fungicide composition according to claim 12, characterized in that at least one compound according to claim 1 or an acid addition salt thereof is mixed with suitable, inert solid or liquid carriers or diluents. A method for controlling fungal diseases, characterized in that an effective amount of a fungicide composition according to claim 13 is applied to plants, parts of them or their plant environment or to fungi or to objects to be protected.