Fungicide,bactericide or plant-growth regulating compositions containing triasole derivatives,and process for producing the active agents

(54) Name: Triazole derivatives with fungicidal, bactericidal or plant-regulating uses

The numbers in brackets indicate the international identification code. INID code. Letters in clamps indicate international document code

7512643-3

The present invention relates to a chemical compound with fungicidal, bactericidal or plant regulating uses.

The present compounds differ from known triazole derivatives, inter alia, by the nature of the side chain attached to the nitrogen atom in the triazole ring. The triazole derivatives disclosed in Dutch patent application 69.13028 and in French patent 2,200,012 are believed to be the derivatives most closely resembling the present triazole derivatives.

The present compound is characterized in that it consists of a 1-1B-aryl) ethyl-1H-1,2,4-triazole ketal of the formula

<img file="SE433495B_D0001.tif" />

CH₇- £ -Ar ^Z Or therapeutically active acid addition salts thereof, wherein Z represents the alkylene which is -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -,

-CH (CH 2) -CH (CH 2) - or -CH₂-CH (alkyl) - wherein the alkyl group has 1 to 10 carbon atoms and Ar represents 2,4-dihalophenyl.

Therapeutically active acid addition salts of the present compound are also included in the present invention.

The term alkyl is meant herein to include straight and branched hydrocarbon groups having 1-10 carbon atoms such as methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethyl; yethyl, butyl, pentyl, hexyl, heptyl, octyl, decyl and the like; low alkyl] refers to i. in the present case straight or branched saturated hydrocarbons having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, pentyl, hexyl and similar alkyl groups; the term halo includes halogen atoms with atomic weights less than 127, ie fluorine, chlorine, bromine and iodine.

The ketals of formula I are readily obtained by transferring 1H-1,2,4-triazole (II) previously to a metal salt, e.g. by treatment with an alkali metal alkoxide, preferably sodium methoxide, is reacted with a halide of formula (III)

Y-CHx— .C - Ar

V \ ^(m>

V wherein Ar and Z have the meanings given and Y represents halogen, preferably bromine. The reaction between 1H-1/1-triazole (II) and (III) is conducted against advantage in a suitable polar reaction inert organic

7512643-3 solvents such as N, N-dimethylformamide, Ν, Ν-dimethylacetamide, acetonitrile, benzonitrile or the like. Such solvents may be used in combination with other reaction-inert organic solvents such as benzene, methylbenzene, dimethylbenzene or the like. When Y represents bromine or chlorine, it is appropriate to add an alkali metal iodide, e.g. sodium or potassium iodide. Slightly elevated temperatures increase the reaction rate and preferably the reaction is carried out at the reflux temperature of the reaction mixture.

The formed ketal of formula (I) is then isolated from the reaction mixture by conventional methods and optionally further purified by any conventional purification process, for example, by crystallization, extraction, trituration, chromatography, etc.

The procedure described can be further illustrated as follows:

<img file="SE433495B_D0002.tif" />

H -> —->

(II) DMF, Nal (I)

The compounds of formula (I) thus obtained, in base form, can be converted into therapeutically useful acid addition salts by reaction with a suitable acid, such as an inorganic acid, such as a hydrogen halide, ie hydrogen chloride, hydrogen bromide or hydrogen iodide, sulfuric acid, nitric acid or thiocyanic acid or thiocyanic acid a phosphoric acid, an inorganic acid such as acetic acid, propionic acid, hydroxyacetic acid, hydroxypropionic acid, 2-oxopropionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, 2-hydroxy succinic acid, 2,3-dihydroxy succinic acid, 2-hydroxy-1,2,3-propane tricarboxylic acid, benzoic acid, 3-phenylpropionic acid, phyto-hydroxybenzoacetic acid, methanesulfonic acid, ethanesulfonic acid, sulfonic acid, hydroxyethanesulfonic acid, 4 , 4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid or 2-acetyloxybenzoic acid. The salts are in turn transferred to the corresponding free bases in the usual manner, e.g. by reaction with alkali, such as sodium or potassium hydroxide.

3 ° The starting materials of formula (III), some of which are known compounds, can be prepared according to known processes, Such compounds wherein Z represents a group -CH (CH 2) -CH₂-,

-CH (CH₂) -CH (CH₂) - and -CH₂-CH₂-CH₂ - and methods for preparing these compounds are described in U.S. Patent No. 3,557,999.

7512643-3

The compounds of formula (III) are prepared by catalysing a suitable ketone of formula (IV), wherein Ar and Y have the meanings defined, with a suitable diol of formula (V) according to known ketalization methods described in the literature (see e.g. Synthesis,

1974 (1), 23).

According to a preferred method, the two reactants are refluxed together for several hours, whereby water is azeotropically removed in a suitable organic solvent, preferably in the presence of a simple alcohol such as ethanol, propanol, butanol, pentanol or the like, and in the presence of a suitable strong acid. , such as 4-methylbenzenesulfonic acid. Suitable organic solvents which can be used for this purpose are, for example, aromatic hydrocarbons such as benzene, methyl benzene, dimethylbenzene and the like, and saturated hydrocarbons such as cyclohexane.

II

<img file="SE433495B_D0003.tif" />

The ketones of formula (IV) are known and can be prepared by methods known to those skilled in the art.

From formula (I), it is apparent that several of the compounds of the present invention have asymmetric carbon atoms in the structure and, consequently, they may exist under various stereochemical optical isomeric forms. When an alkyl group is in the d-position of the dioxolane nucleus, the carbon atom to which the alkyl group is attached and the carbon atom in the 2-position of the dioxolane nucleus are asymmetric. The stereochemical and optical isomers of the compounds of formula (I) can be separated and isolated by methods known to those skilled in the art. The indicated isomers fall within the scope of the invention.

The compounds of formula (I) and the acid addition salts thereof are useful agents in the control of fungi and bacteria. The compounds of the invention are valuable in the treatment of plants, animals and humans affected by pathogenic microorganisms, as well as for the destruction of microorganisms on materials.

The compounds of the invention are very strong fungicides which can be used in agriculture. They are very active against a large number of fungi, e.g. against the fungi responsible for the appearance of apple mildew on various plants, against Erysiphe graminis, Erysiphe polygon !, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pannosa, Sphaerotheca rnors-uvae, Uncinula

7512643-3 necator, etc, and other fungi, e.g. Venturia inaequalis, Colletotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenius, Thielaviopsis basicola, Helminthosporium gramineum, Penicillium degitatum, etc.

They are particularly useful because of their prophylactic as well as curative and systemic effects. Their strong effect on phytopathogenic fungi is illustrated more clearly by the results obtained in the following experiments.

In several of these experiments, the compound 1- [2- (2,4-dichloro-phenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, (Ia) is used as a representative type. of the compounds of formula (I).

<img file="SE433495B_D0004.tif" />

The compounds for which experimental results are given have not been given to limit the invention to these compounds but merely to exemplify the strong action against fungi of all compounds within the scope of formula (I).

A. Prophylactic effect of compounds of formula (I) against Erysiphe cichoracearum on cucumber in leaf treatment.

Young cucumber plants, about 10 days old, were sprayed with an aqueous solution containing 250, 100 or 10 ppm of the compound to be tested, while the comparison plants were untreated. When the plants had dried, they were artificially infected with spores of Erysiphe cichoracearum by rubbing heavily infected leaves against the plants. On the 15th day after the artificial infection, the degree of fungal infestation is evaluated by counting the number of spots per plant. The results given in Table I are averages for two plants and are expressed according to the following scoring system.

0 = 0 spots per plant = 1-5 spots per plant = 6-10 spots per plant = more than 10 spots per plant

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Table I

Prophylactic effect of compounds (I) against Erysiphe cichoracearum on cucumber surfaces in leaf treatment N n ~ ii

V (: h

0^

Jl

Are

<td rowspan="2">Are</td><td rowspan="2">R</td><td rowspan="2">Basal salt form</td><td colspan="3">Effect against fungus, 1 point</td>

<td>250 npm</td><td>100 npm</td><td>10 ppm</td>

<td>2,4- (Cl)₂-C₆hrs₃</td><td>hrs</td><td>base</td><td> -</td><td> 0</td><td> 0</td>

<td>^C6^hrs5</td><td>hrs</td><td>base</td><td> -</td><td> 3</td><td> -</td>

<td>4-NO₂-C₆^hrs4</td><td>hrs</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>3-Cl-C₆hrs₄</td><td>hrs</td><td>base</td><td> -</td><td> 2</td><td> -</td>

<td>2-Cl-C₆hrs₄</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 0</td><td> -</td>

<td>4-Br C₆hrs₄</td><td>hrs</td><td>Base</td><td> 0</td><td> -</td><td> -</td>

<td>2-Br-C₆hrs₄</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>3-AND, -C, H 3 6 4</td><td>hrs</td><td>(COOH)₂</td><td> 1</td><td> -</td><td> -</td>

<td>2-CH, -C_Ahrs₄</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>4-FC₆^hrs4</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>4-CH₃-C₆^hrs4</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>4-Cl-C₆hrs₄</td><td>hrs</td><td>(COOH)_?.HRS_?0</td><td> -</td><td> 0</td><td> -</td>

<td>2-naphthyl</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>2.5- (CI)₂-C₆hrs₃</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 0</td><td> -</td>

<td>4-CN ~ C₆hrs₄</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>3,4 (Cl)₂-C₆hrs₃</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 3</td><td> -</td>

<td>²-°^CH3-^C6^hrs4</td><td>hrs</td><td>(COOH)₂</td><td> 1</td><td> -</td><td> -</td>

<td>2-thienyl</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2-fluoro-enyl</td><td>hrs</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>5-Cl-2-thienyl</td><td>hrs</td><td>base</td><td></td><td> 2</td><td> -</td>

7512643-5 .Table I, cont.

<td rowspan="2">Are</td><td rowspan="2">R</td><td rowspan="2">Basal salt form</td><td colspan="3">Effect against fungus, points</td>

<td>250ppm</td><td>lOOppm</td><td>10 ppm</td>

<td>3-Br, 4-CH, -C_AHRS,</td><td>hrs</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>CH 2-S, 4-Br-C_AHRS,</td><td>hrs</td><td>base</td><td> -</td><td> 2</td><td> -</td>

<td>2-CH_r 4-Cl-C ^ H ^</td><td>hrs</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>3-Br-C, H</td><td>hrs</td><td>base</td><td> 2</td><td> -</td><td> -</td>

<td>4 IC₆hrs₄</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>3,5- (C1)_?-C_AH</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2,3 (C1)₂-C_éhrs₃</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>3-NO₂-C₆^hrs4.</td><td>hrs</td><td>Base</td><td> 1</td><td> -</td><td> - -</td>

<td>2,4- (Bx)_?-C_AH</td><td>HRS ·</td><td>(COOH)₂</td><td> -</td><td> 1</td><td> -</td>

<td>2,4,5 (Cl)₃-C₆hrs₂</td><td>hrs</td><td>(COOH)₂</td><td> 0</td><td> -</td><td></td>

<td>2-Ct 4-AND₃-C_Ahrs₃</td><td>hrs</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2,4- (C1)_?-C_Ahrs₃</td><td>^CH3</td><td>HNO₃</td><td> 0</td><td> -</td><td>w</td>

<td>2,4- (C1)_?-C_Ahrs₃</td><td>^C2^hrs5</td><td>HNO₃</td><td> -</td><td> 0</td><td> 0</td>

<td> 2 _s 4- (C1)₇-C_Ahrs₃</td><td>n₃hrs_?</td><td>HNO₃</td><td> -</td><td> 0</td><td> 0</td>

<td>2,4- (C1)_?-C_Ahrs₃</td><td>ⁿ4^hrs9</td><td>11/2 (COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2,4- (C1)₂-C_Ahrs₃</td><td>ⁿ5^hrshrs</td><td>HNO₃</td><td> -</td><td> 0</td><td> 0</td>

<td>I 2.4-₂-C₆hrs₃</td><td>ⁿ6^hrs13</td><td>HNO₃</td><td> 0</td><td> -</td><td> -</td>

<td>I 2.4- (Cl)₂-C₆hrs₃</td><td>ⁿ7^hrs15</td><td>I4NO₃</td><td> -</td><td> 2</td><td> *</td>

<td>J 2.4- (Cl)₂-C₆hrs₃</td><td>^Ac8^hrs17</td><td>HNO₃</td><td> 0</td><td></td><td></td>

7512643-3

Al Prophylactic action against Erysiphe polyphaga on cucumber during leaf treatment.

Young cucumber plants in the single leaf stage were sprayed with an aqueous solution containing 500, 250 or 125 ppra of (Ia), while the comparison plants were untreated. An artificial infection with spores of Erysiphe polyphaga was carried out by rubbing heavily infected leaves against the plants on the 4th, 6th or 8th day after treatment. On the 18th and 54th day after the treatment, the proportion of leaf surfaces, which were attacked by the fungus separately for infected leaves and newly formed leaves, was determined. The results given in Table 1.1 are averages for 5 plants and expressed as a percentage of attack compared to the untreated plants.

Table 1.1

Prophylactic effect of (Ia) against Erysipe polyphaga on cucumber during leaf treatment

<td>Evaluation day</td><td colspan="6">18 days after treatment</td><td colspan="6">34 days after treatment</td>

<td>Infected on specified day eft. treatment</td><td colspan="2"> 4</td><td colspan="2"> 6</td><td colspan="2"> 8</td><td colspan="2"> 4</td><td colspan="2"> 6</td><td colspan="2">⁸ in</td>

<td>Infected leaves (a) or newly formed leaves (b)</td><td>A</td><td>b</td><td>A</td><td>b</td><td>A</td><td>b</td><td>A</td><td>b</td><td>A</td><td>b</td><td>A</td><td>b</td>

<td>Concentration of (Ia) in spray solution untreated 500 ppm 250 ppm 125 ppm</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td><td> 100 0 0 0</td>

IN

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B. Prophylactic action against Erysiphe graminis on grain during soil treatment.

Barley plants were treated by irrigating each plant with 100 ml of an aqueous solution containing 1000, 100 or

10 ppm (Ia). Comparative plants received the same volume of solution, which however did not contain (Ia). The natural infection, which usually occurs when the plants are kept in greenhouses near infected plants, was evaluated 16 days after treatment by counting the number of spots on the leaves. Five plants were used per test series and the results in Table XX are averages, expressed as a percentage of attack relative to the comparison plants.

Table II

Prophylactic effect of (Ia) against Erysiphe graminis on grain during soil treatment

<td>Dose in mg (Ia) per plant</td><td>Attack in% relative to comparison plant</td>

<td>comparison Plantation</td><td> 100</td>

<td>100 mg</td><td> 0</td>

<td>10 mg</td><td> 0</td>

<td>1 ”g</td><td> 53</td>

C. Healing effect against Erysiphe graminis on barley during leaf treatment.

Barley plants infested by Erysiphe graminis were sprayed with an aqueous solution containing (Ia) at the indicated concentration. On the 16th day after treatment, the number of spots per plant was determined. Five plants per test series were used and the results given in Table III are averages, expressed as a percentage of attack relative to the comparison plants.

Table III

Healing effect of (Ia) against Erysiphe graminis on barley during leaf treatment

<td>Concentration of (Ia) in the spray solution</td><td>Attack holding plants</td><td>in 2 in front of comparison-</td>

<td> 0</td><td></td><td> 100</td>

<td>1000 ppm</td><td></td><td> 0</td>

<td>100 ppm</td><td> •</td><td> 1,5</td>

<td>J 10 ppm</td><td></td><td> 25</td>

rTfiSy. ·

7512643-3 /’

D. Prophylactic effect of (Ia) against Podospaera leuchotricha on dilute apple plants when sprayed.

One year old apple seedlings were sprayed with an aqueous solution containing (Ia) at the indicated concentration. The plants were artificially infected as described in Sample A with spores of

Podosphaera leuchotricha 1 day after treatment and incubated for 36 hours. The degree of fungal infestation was evaluated 25 days after the treatment by counting the number of stains. Two seedlings per experimental series were used and the residuals given in Table IV constitute averages, expressed as a percentage of infestation in relation to the seedlings.

Table IV

Prophylactic effect of (Ia) against Podosphaera leucotricha on dilute apple plants when sprayed

<td>Concentration of (Ia) in the spray solution</td><td>Attack in * in relation to comparison plants</td>

<td> 0</td><td> 100</td>

<td>100 ppm</td><td> 0</td>

<td>10 ppm</td><td> 6</td>

E. Effect on Thielaviopsis sp.

mm thick slices of potato and leek were dipped in an aqueous sample solution containing (Ia) at indicated concentrations

The plates were placed after dipping on filter paper on a large plastic tray and the tray was covered with glass. An artificial infection was performed on the day of treatment by spraying the slices with a concentrated suspension of spores of Thielaviopsis sp. and the slices were incubated at room temperature.

The growth of fungi on the slices is evaluated 6 days after treatment by estimating the fungal infestation on the surface. The results given in Table v are expressed as a percentage of attack relative to the comparison plants.

Table V

The effect of (Ia) on Thielaviopsis sp.

<td rowspan="2">Concentration of (Ia) in the sample solution in ppm</td><td colspan="2">Attack in 2 in relation to comparison plants</td>

<td>Potato</td><td>Puree onion</td>

<td> 0</td><td> 100</td><td> 100</td>

<td> 1000</td><td> 0</td><td> 0</td>

<td> 100</td><td> 0</td><td> 0</td>

<td> 10</td><td> 0</td><td> 42,8</td>

<td> 1</td><td> 11</td><td> 100</td>

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/.

The compounds of formula (I) are also very active against a large number of fungi, which are pathogenic to humans and animals. For example, they are active against fungi such as Microsporum canis, Trichophyton mentagrophytes, Trichophyton rubrum, Aspergillus fumigatus, Phialo5 phora verucosa, Cryptococcus neoformans, Candida albicans, Candida tropicalis, etc. The extremely good effect on Candida albicans is more clearly evident in the following attempt.

F. The effect of (Ia) on Candida attack on the requirement of turkeys. Young turkeys (14 days old) were artificially infected by forcibly adding a suspension containing 4.10 3 CFU (colony forming units) of Candida albicans.

When the animals were infected, they received either their normal diet (the comparison group), or a drug-containing diet containing 125 ppm of (Ia). Two weeks later, all the turkeys were sacrificed, cultures were made of the claim and the number of Candida colonies per gram of claim was calculated.

The results are summarized in Table VI.

Table VI

Number of colonies of Candida albicans per gram required in the turkeys treated with (Ia) - (125 ppm) or placebo.

<td>Treatment</td><td>Number of animals</td><td>Number of Candida Colonies 1 per gram require</td>

<td>Comparison-</td><td> 1</td><td> 3 520 000</td>

<td>dj ur</td><td> 2</td><td> 848 700</td>

<td></td><td> 3</td><td> 3 132 000</td>

<td></td><td> 4</td><td> 1 909 000</td>

<td>(Ia)</td><td> 1-</td><td> 0</td>

<td>(125 ppm)</td><td> 2</td><td> 247 200</td>

<td></td><td> 3</td><td> 6 742</td>

As can be seen from the results in Table VI, the compound (Ia) at a concentration of 125 ppm is particularly effective against attack on the requirement in relation to the corresponding untreated animals.

G. Effect of (Ia) against vaginal Candida attacks on rats On female 100 g body rats, the ovaries and uterus were removed. About 3 weeks later, all animals were given a weak subcutaneous injection of 100 mg of estradiol undecylate and they were infected intravaginally with a suspension containing 8.10³ CFU

Ii

7512643-3 by Candida albicans.

Groups of 4 rats were then orally treated for 14 consecutive days with either a solvent (PEG 200) or (Ia). The administered dose of the compound was 40 mg / kg orally. Vagina samples were taken on all animals at the end of the treatment period (ie, 14 days), and these were grown on Sabouraud agar medium containing penicillin (20 IU / ml) and Streptomycin (40 µg / ml) and the number of Candida colonies was then counted. .

Table VII summarizes the results obtained with (Ia) against vaginal Candida infestation in rats.

Table VII

Number of animals per cultural assessment

<td>Treatment</td><td>Number of DJs</td><td>Day after treatment</td><td>• x) culture Assessment 0 12 3 4</td>

<td>Comparison (PEG 200)</td><td> 4</td><td> 14</td><td> 0 0 0 1 3</td>

<td>(Ia) (40 mg / kg orally)</td><td> 4</td><td> 14</td><td> 3 10 0 0</td>

x) Cultural assessment: 0 = no plant = 1-25 colonies = 26-100 colonies => 100 colonies = countless colonies

As can be seen from the results in Table VII, (Ia) is very effective against vaginal Candida attacks on rats,

H. Effect of (Ia) on systemic Candida attacks on guinea pigs. Adult male guinea pigs were intravenously infected with Candida albicans, which induces a general systemic candidosis.

Subsequently, 7 guinea pigs were orally treated for 14 consecutive days with either solvent (PEG 200) or (Ia). The dose used was 40 mg / kg body weight.

Four days after the last day of treatment, all 20 animals were sacrificed, the kidneys were removed and cultured on Sabouraud agar medium containing penicillin (20 IU / ml) and Streptomycin (40 yug / ml) and the number of isolated colonies of Candida albicans per gram of kidney was counted. Table VIII shows the detailed results obtained with (Ia) against systemic deep mycosis in guinea pigs.

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Table VIII

<img file="SE433495B_D0005.tif" />

From the results in Table VIII, one can conclude that (Ia) is an extremely potent agent for systemic deep mycosis in guinea pigs.

Apart from the antimicrobial effects, the compounds of formula (I) have valuable plant regulatory properties. Depending on various factors, such as the nature of the plants under treatment and the dose of the active ingredient supplied, the observed effect may be either growth stimulant or growth inhibitory. The present compounds, as such, are useful in regulating the growth of plants. In particular, they can be used as plant inhibitors or as plant retardants, especially as inhibitors for growth of root shoots, e.g. on tobacco plant. However, under certain circumstances, they can also be used as growth stimulants for plants.

The plant regulating properties of the compounds of formula (I), which are naturally intended to fall within the scope of the present invention, are more clearly illustrated by the results obtained in the following experiments, wherein the compound (Ia) is used as representative of the compounds of the invention. The results obtained with (Ia) are not intended to limit the invention but merely to exemplify the useful plant regulating properties of all compounds within the scope of formula (I).

I. Plant-regulating effect on tomato plants during soil treatment.

Young tomato plants, 3.5 to 4 cm tall, were planted in separate pots. Each pot was watered with a test solution, which

7512643-3 contained the indicated amount of (Ia). The plant was evaluated by determining the length and weight of the plants 28 days after treatment.

The results given in Table IX are averages for five plants and are expressed as a percentage of the comparison plants. Table IX

Plant regulating effect of (Ia) on tomato plants during soil treatment

<td>Dose of (Ia)</td><td>Length of plants in 2</td><td>The weight of the plants in 2</td>

<td rowspan="2">in mg / plant</td><td>relative to</td><td>relative to</td>

<td>j the comparison plants</td><td>j the comparison plants</td>

<td>No</td><td> 100</td><td> 100</td>

<td> 10</td><td> 114</td><td> 118</td>

<td> 1</td><td> 127</td><td> 134</td>

<td> 0,1</td><td> 122</td><td> 116</td>

J. Plant-regulating effect reaching grains in leaf processing.

Young seedlings in the 3-4 leaf stage were sprayed with a test solution containing (Ia) of the indicated concentrations. The effect on plant growth was evaluated 24 days after treatment by determining the weight of the plants. The results given in Table X are averages for 10 plants and are expressed as a percentage in relation to the comparison plants.

Table X

Plant-regulating effect of (Ia) on barley during leaf treatment

<td>Conc. of (Ia) in the sample solution (ppm)</td><td>The average weight of the plants in 2 of the comparison plants</td>

<td>No</td><td> 100</td>

<td> 125</td><td> 126</td>

<td> 60</td><td> 116</td>

K. Impact of growth of root shoots on tobacco plants.

Tobacco Plant, var. Xanthi, was raised in greenhouses and peaked in the early bud stage.

After 5 days, a leaf spray treatment was carried out with an aqueous suspension of compound (Ia) in amounts corresponding to 3 and 1.5 kg ai / ha.

Each treatment was repeated three times. Twelve days after treatment, the growth of the root canals was estimated in comparison with the topped and untreated comparison plants.

7512643-3 .¹⁴

The recorded reductions in rofstock growth were 100% at 3_s0 kg / ha and 90% at 1.5 kg / ha.

L. Plant inhibition on soybean plants.

Soybean plant, var. Hark was grown in pots in a culture chamber at 5 ° C, 20,000 Lux and a day length of 14 hours. When the third trifoliate leaf had been unfolded, the plants were sprayed with an aqueous suspension of compound (Ia) at concentrations of 1000, 500, 100 and 50 ppm active ingredient.

The percentage plant inhibition of the treated plants relative to the comparison plants was determined after 14 days.

The following results were obtained:

<td>Treatment</td><td>...... ..........- % plant inhibition</td>

<td>(Ia) 1000 ppm ai</td><td> 70 %</td>

<td>500 ppm ai</td><td> 40 ?</td>

<td>- 100 ppm ai</td><td> 25 %</td>

<td>50 ppm ai</td><td> ' 0 %</td>

<td>comparison Seedlings</td><td>0 i</td>

At the concentration of 1000 ppm, a more intense green color of the foliage could be observed.

Due to the stated fungicidal, antibacterial and plant-regulating properties of the compounds, according to the present invention, valuable compositions comprising the ketals (I) or acid addition salts thereof, such as the active ingredient in a solvent or a solid, semi-solid or liquid, diluent or carrier material can be prepared. . In addition, the invention encompasses

Is an effective method for controlling fungal or bacterial growth by using an effective bactericidal or fungicidal amount of such ketals (I) or salts thereof. The present compounds may be used in suitable solvents or diluents, in the form of emulsions, suspensions, dispersions or ointments, on suitable solid or semi-solid carrier substances, in natural or synthetic soaps, detergents or dispersion media, optionally in conjunction with other compounds with arachnid, insecticidal, ovicidal, fungicidal and / or bactericidal properties or together with inactive additives.

Solid carrier substances suitable for the preparation of powder form compositions include various inert, porous and powdery dispersants of inorganic or organic nature.

7512643-3 such as tricalcium phosphate, calcium carbonate, in the form of processed chalk or limestone, kaolin, tree trunks, bentonite, talc, diatomaceous earth or boric acid, as ground; powdered cork, sawdust and other fine powder materials of vegetable origin can also be used as carrier substances.

The active ingredient is mixed with these carrier substances, e.g. by painting them; alternatively, the inert carrier substance is impregnated with a solution of the active component in a volatile solvent and the solvent is then removed by heating or suction filtration at reduced pressure. By adding wetting agents and / or dispersants, such powder formulations can also be easily wetted with water so that suspensions are obtained.

The inert solvents used for the preparation of liquid preparations should not be flammable and should, as far as possible, be odorless and non-toxic to warm-blooded animals or to plants in the surrounding environment. Solvents suitable for this purpose are high boiling oils, e.g. of vegetable origin, and low boiling solvents having a flash point of at least 30 ° C, such as polyethylene glycol, isopropanol, dimethyl sulfoxide, hydrogenated naphthalene and alkylated naphthalene. Of course, it is also possible to use mixtures of solvents. The solutions can be prepared in the usual manner and, if necessary, solution-promoting agents are used. Other liquid forms which may be used consist of emulsions or suspensions of the active compound in water or suitable inert solvents, or also concentrates for preparing such emulsions which can be directly adjusted to the desired concentration. For this purpose, for example, the active ingredient may be mixed with a dispersant or emulsifier. The active component may also be dissolved or dispersed in a suitable inert solvent and simultaneously or subsequently mixed with a dispersant or emulsifier.

It is also possible to use semi-solid carrier substances of ointment-like, paste-like or wax-like nature, wherein the active component is incorporated, if necessary, by means of solvent-promoting agents and / or emulsifiers. Vaseline and other ointment bases are examples of semi-solid carrier substances.

It is further possible to use the active ingredient in the form of aerosols. For this purpose, the active ingredient is dissolved or dispersed, if necessary by appropriate inert

7512643-3

/.

solvents such as carrier liquids, e.g. difluorodichloromethane, which at atmospheric pressure boils at a temperature below room temperature, or in other volatile solvents. In this way, pressurized solutions are obtained which, when sprayed, provide aerosols which are particularly suitable for controlling or controlling fungi, bacteria, e.g. in closed rooms and storage rooms, as well as for application to vegetation for the eradication or prevention of infections of fungi or bacteria.

The present compounds and compositions thereof can be applied by conventional methods. Fungi or bacteria or a material to be treated or protected against attack by fungi or bacteria may be treated with the present compounds and their compositions by dusting, irrigation, spraying, brushing, dipping, lubricating, impregnating or otherwise appropriate.

When the present compounds are used in conjunction with suitable carriers, for example, in solution, suspension, powders, powders, ointments, emulsions and similar forms, high activity is observed within a very large dilution range. For example, concentrations of the active ingredient of 0.1 to 10% by weight, based on the weight of the composition used, have been found to be effective in controlling fungi or bacteria. Of course, higher concentrations can also be used if a particular situation gives rise to this.

The following examples are intended to illustrate, but not to limit, the present invention. Unless otherwise stated, all parts refer to parts by weight.

Example 1. A stirred and cooled (0 ° C) solution of 30 parts of 1- (4-amino-2-methoxyphenylethetanone) in 360 parts of concentrated hydrochloric acid solution, parts of water and 30 parts of acetic acid is diazotized with a solution of 17.25 parts of sodium nitrite in 200 ml. After stirring for 30 minutes at 0 ° C, the whole is poured into a solution of 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid solution with stirring, and the mixture is heated for 1 hour at 60 ° C. When the product is cooled to room temperature, it is extracted twice with 2,2'-oxybispropane. The combined extracts are washed successively with water, a dilute sodium hydroxide solution and then twice again with water, dried, filtered and evaporated to give 28 parts (76 l- (4-chloro-2-methoxyphenyl) ethanone, m.p. 55 ° C.

Example 2. A stirred solution of 78.8 parts of 2-bromo-1- (4-bromo-2-methylphenyl) -1-ethanone and 200 parts of butanol is added with 3 parts.

4-methylbenzenesulfonic acid and 225 parts of benzene. Then it is added

7512643-3 dropwise 33.5 parts of 1,2-ethanediol. After completion of the reaction, stirring is continued overnight at reflux temperature with water separation. The reaction mixture is evaporated and the residue is dissolved in 2,2'-oxybispropane. The solution is stirred with 15 parts of concentrated sodium hydroxide solution. The layers are separated and the aqueous phase is extracted with 2,2'-oxybispropane. The combined organic layers are washed with water (to neutralize), dried, filtered and evaporated.

The solid residue is crystallized from methanol to give 30.5 parts of 2- (bromomethyl) -2- (4-bromo-2-methylphenyl) -1,3-dioxolane, m.p.

86 ° C.

Example 3. Following the procedure described in Example 2 and using an equivalent amount of a suitable 1-aryl-2-bromo-1-ethanone instead of 2-'orom-1- (4-bromo-2 -methylphenyl) -1-ethanone, the following 2-aryl-2-bromomethyl-1,3-dioxolanes can be prepared:

4-Z'2- (bromomethyl) -1,3-dioxolane-2-yL7-benzonitrile, mp 92.4 ° C, and

2- (bromomethyl) -2- (2-naphthalenyl) -1,3-dioxolane, mp 64 ° C.

Example 4. 57 parts of 1- (5-chloro-2-thienyl) -1-ethanone are dissolved in 220 parts

1,2-ethanediol at 50 ° C. Stirring is added dropwise under one

1- hour period 64 parts of bromine without external heating. After stirring for 20 hours at room temperature, 4 parts of 4-methylbenzenesulfonic acid and 30 parts of benzene are added. The whole is stirred and refluxed overnight under separation of water, the reaction mixture is evaporated 1 and the residue is taken up in 2,2'-oxybispropane. The resulting solution is successively washed once with dilute sodium hydroxide solution and several times with water, dried, filtered and evaporated. The residue is distilled to give 73 »3 parts (64.5%) of 2- (bromomethyl) -2- (5 'chloro-2-thienyl) -1,3' dioxolane boiling point 125-127 ° C at 13 Pa. Example 5, Following the procedure described in Example 4, using an equivalent amount of suitable 1-aryl-1-ethanone instead of 1- (5-chloro-2-thienyl) -1-ethanone the following 2-aryl-2- (bromomethyl) 1,3-dioxolanes are prepared:

2- (Bronimethyl) ~ 2- (9H-fluoren-2-yl) -1,3-dioxolane, mp 90 ° C

2- (bromomethyl) -2- (3-bromo-4-methylphenyl) -1,3 'dioxolane, bp 126-130 ° C at 13 Pa »

2- (bromomethyl) -2- (4-iodophenyl) -1,3-dioxolane, mp 74 ° C;

2- (bromomethyl) -2- (4-chloro-2-methoxyphenyl) -1,3 dioxolane, mp 110 ° C, and 2- (bromomethyl) -2- (2,4-dibromophenyl) -1,3-dioxolane dioxolane, mp 96 ° C.

Example 6

A. A stirred solution of 2.3 parts of sodium in 120 parts of methanol is added with 6.9 parts of 1H-1,2,4-triazole in 150 parts of dimethylformamide.

7512643-3 'Ϊ8 / The methanol is removed under normal pressure until the internal temperature reaches 130 ° C. Then 25 parts of 2- (bromomethyl) -2- (2,4dichlorophenyl) -1,3-dioxolane are added. The reaction mixture is stirred and refluxed for 3 hours. It is allowed to cool to room temperature and poured into water. The precipitated product is filtered off and crystallized in isopropyl ether (activated carbon) to give 12 parts

1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 109.9 ° C.

B. 6 parts of 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H10 1,2,4-triazole were transferred to the nitrate salt of 2,2'-oxybispropane. After cooling, the salt is filtered off and crystallized twice

2-propanone to give 3 parts of 1- [2- (2,4-dichlorophenyl) -1,2-dioxolan-2-ylmethyl] -1H-1,2,4-triazole nitrate, mp 172.7 ° C.

C. 6 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H15 1,2,4-triazole are transferred to the sulfate salt in 2,2'-oxybispropane. The resulting sulfate is filtered off and crystallized from 2-propanol. The product is filtered off and recrystallized from ethanol (activated carbon) to give, after drying, 6 parts of 1- [2- (2,4-dichlorophenyl) 1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole sulfate, m.p. 207.1 ° C.

Example 7. A stirred solution of 2.3 parts of sodium in 80 parts of methanol is added with 6.9 parts of 1H-1,2,4-triazole and 2 parts of sodium iodide in 100 parts of Ν, Ν-dimethylformamide. The methanol is removed under normal pressure until the internal temperature reaches 130 ° C. Then 34.4 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-methyl-1 are added._in3 ”dioxolane and it is all stirred and refluxed for 3 hours. The reaction mixture is poured into water and the product is extracted twice with diisopropyl ether. The extract is washed with water and an excess of a conc. Nitric acid solution is added. The crude nitrate salt is filtered off and crystallized from a mixture of 2-propanol and diisopropyl ether to give 15 parts of 1- [2- (2,4-dichlorophenyl) 4-methyl-1]₃3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole nitrate, mp 137.8 ° C. Example 8. A stirred sodium methoxide solution prepared from 2.8 parts of sodium in 48 parts of methanol is added with 8.3 parts of 1H-1,2,4-triazole. After stirring for 30 minutes at room temperature, 135 parts of Ν, Ν-dimethylformamide are added and the methanol is evaporated. Then a mixture of 24.3 parts of 2- (bromomethyl) -2-phenyl-1,3-dioxolane and 3 parts of potassium iodide is added, and the whole is stirred and refluxed for three hours. The reaction mixture is cooled to room temperature and poured into water. When scraping, the product falls out.

It is extracted, washed with water, dried and crystallized from one

7512643-3 mixture of ethanol and 2,2'-oxybispropane (1: 5 v / v) to give 10.9 parts (43.7 2) of 1- (2-phenyl-1,3 'dioxolane-2ylmethyl) -1H -1,2,4-triazole, mp 127.3 ° C.

Example 9 · Following the procedure described in Example 8 and using an equivalent amount of a suitable 2-aryl-2- (bromomethyl)

1,3-dioxolane Instead of a 2- (bromomethyl) -2-phenyl-1,3-dioxolane used in the example given, the following 1,2,4-triazoles are obtained:

1- [2- (4-nitrophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 160 °, 1 ° C;

1- [2- (3-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 113.9 ° C_in£2-(ⁱⁿin "bromophenyl) -1,3-dioxolan-2-ylmethyl] -1 H-1,2,4-triazole, mp 135.9 ° C;

1- [2- (3-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 105.4 °;

1- [2- (3-bromophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 115.4 ° C, and

1- [2- (3-nitrophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 154.1 ° C.

Example 10. A stirred sodium methoxide solution prepared from 1.6 parts of sodium in 48 parts of methanol is added with 4.9 parts of 1H-1,2,4-triazole. After stirring for 1 hour at room temperature, 135 parts of Ν, Ν-dimethylformaride are added. The methanol is distilled off under normal pressure until the internal temperature reaches 130 ° G. Then 17.4 parts of 2- (bromomethyl) ~ are added successively

2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts potassium iodide. It is all stirred and refluxed overnight. After cooling to room temperature, the reaction mixture is poured into water. Upon scraping, the product precipitates, which is filtered off and washed with water. The product, dissolved in trichloromethane, is purified by column chromatography on silica gel using a mixture of trichloromethane and methanol as eluent. The pure fractions are collected and the eluent is evaporated. The residue is crystallized from a mixture of 2,2'-oxybispropane and methanol (9: 1 v / v) to give 9.3 parts (55.5 2) of 1- [2- (2,3,4-trichlorophenyl) -1,3-dioxolane-2ylmethyl / -1H-1,2,4-triazole, mp 181, 4 ° C.

Example 11. Following the procedure described in Example 10 and using equivalent amounts of suitable starting materials, the following 1,2,4-triazoles can be prepared:

1-Z2- (9H-fluoren-2-yl) -1,3 'dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 866.8 ° C;

7512643-3

1- [2- (5-chloro-2-thienyl) -1, J-dioxolan-2-ylmethyl] -1H1,2,4-triazole, mp 117.4 ° C;

1- / 2- (3 "bromo-5-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole, mp 120.7 ° C;

1- [2- (4-bromo-2-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H, 2,2-tri-triazole, m.p.Ι.δ, ΙθΟ, and

1- [2- (ft-Chloro-2-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole, m.p.

Example 12. A stirred sodium methoxide solution prepared from 2.8 parts of sodium in 56 parts of methanol is added with a mixture of 8.3 parts of 1H-1, 2,4-triazole and 135 parts of N, N-dimethylformamide. The methanol is removed at normal pressure until its internal temperature reaches 130 ° C. Then a mixture of 27.8 parts of 2- (bromomethyl) -2- (2-chlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide is added. The whole is stirred and refluxed for 6 hours. The reaction mixture is allowed to cool to room temperature, then it is poured into water and the product is extracted three times with Ι, Ι'-oxybisethane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is transferred to the ethanedioate salt of ph-methyl-2-pentanone. The salt is filtered off and crystallized from ph-methyl-2-pentanone to give 16 parts of 1- [2- (2-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2, ph-triazole-ethanedioate, mp 156.5 ° C.

Example 13. Following the procedure described in Example 12 and using equivalent amounts of suitable starting material, the following 1,2,4-triazolethanedioate salts can be prepared:

CH.

-Ar '0

7512643-3

<td>Are</td><td>acid Salt</td><td>Melting point</td>

<td>²’^Br-^C6^hrs4</td><td>(COOH)₂</td><td>172. l'C.</td>

<td>3-OCH₃-C₆hrs₄</td><td>(COOH)₂</td><td> 155.6-0.</td>

<td>2-CH_vC_Ahrs₄</td><td>(COOH)₂</td><td>177. l'C.</td>

<td></td><td>(COOH)₂</td><td>185. 5'C.</td>

<td>4-CH₃-C₆hrs₄</td><td>(COOH)₂ -</td><td>151,2'C.</td>

<td>4-Cl-C₆hrs₄</td><td>(COOH)₂ . hrs₂O</td><td>169.1 ° C.</td>

<td>4-OCH₃-C₆hrs₄</td><td>(COOH)₂</td><td>187.1'C.</td>

<td>2-naphthalenyl</td><td>(COOH)₂</td><td>175-C.</td>

<td>2, 5- (Cl)_?-C_AHRS,</td><td>(COOH)₂</td><td>173. 7 ° C.</td>

<td>4-CN-C₆hrs₄</td><td>(COOH)₂</td><td>186. 3 ° C.</td>

<td>3,4- (Cl)₂-C₆hrs₃</td><td>(COOH)₂</td><td>182. 2'C.</td>

<td>2-thienyl</td><td>(COOH)₂</td><td>144.5 ° C</td>

<td>2,4- (Br)₂-C₆hrs₃</td><td>(COOH)₂</td><td>190. 3-C.</td>

<td>L4. A stir</td><td>sodium methoxide,</td><td>as a producer</td>

starting from 2.3 parts sodium in 48 parts methanol, is added with 6.9 parts 1H-1,2,4-triazole. After stirring for 30 minutes at room temperature, 135 parts of Ν, Ν-dimethylformamide are added. The methanol is distilled off under normal pressure until the internal temperature reaches 130 ° C. Then 3 parts of potassium iodide and 16.4 parts of 2- (bromomethyl) -2- (o-methoxyphenyl) -1,3 'dioxolane are added successively. It is all stirred and refluxed for 18 hours. The reaction mixture is poured after cooling to room temperature in water and the resulting solution is extracted three times with trichloromethane. The combined extracts are washed four times with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel using a mixture of trichloromethane and methanol as eluent. The pure fractions are collected and the eluent is evaporated. The residue is converted to ethanedioate salts in 4-methyl-2-pentanone. The salt is filtered off and crystallized from a mixture of 2-propanone and 2,2'-oxybis propane (volume ratio 2il) to give 5.5 parts (26%) of 1 - [2- (2-methoxyphenyl) -1 3-dioxolan-2-ylmethyl-1H1,2,4-triazole-ethanedioate, mp 116.6 ° C

Example 15. Following the procedure described in Example

14, and using equivalent amounts of suitable starting materials, the following 1,2,4-triazole-ethane diodate salts can be prepared:

1- [2- (4-iodophenyl) -1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole-ethanedioate, m.p.

7512643-3

1- / 2- (3,5-dichlorophenyl) -1,3-dioxolan-2-ylmethyl U-1H1,2,4-triazole-ethanedioate, mp 204.4 ° C:

1- / 2- (2,3-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -lHl, 2₃4-triazole-ethanedioate, mp 188.4 ° C;

1- / 2- (4-chloro-2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl / -1Hl₅2₃4-triazole-ethanedioate, mp 173.2 ° C;

1- [2- (2,4,5-trichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole-ethanedioate, mp 178.4 ° C, and

1- [2- (2-chloro-4-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole-ethanedioate, mp 188.2 ° C,

Example 16. A stirred mixture of 9.5 parts of 1H-1,2,4-triazole and 225 parts of Ν, Ν-dimethylformamide is added portionwise with 4.2 parts of a sodium hydride dispersion (78%). The mixture is stirred until the evolution of smoke ceases, then 16 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-propyl, 1,3-dioxolane are added and stirring is continued for 5 hours at reflux temperature. The reaction mixture is cooled and poured into water. The product is extracted three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel with a mixture of trichloromethane and 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is transferred to the nitrate salt in 2,2'-oxybispropane. The salt is filtered off and crystallized from a mixture of

2-propanone and petroleum ether to give 8.2 parts (45%}

1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4 triazole nitrate, mp 132.6 ° C.

Example 17. A stirred sodium methoxide solution prepared from 3.8 parts of sodium in 40 parts of methanol is added 11.5 parts of 1H-1, 2,4-triazole and 225 parts of Ν, Ν-dimethylformamide. The methanol is distilled off until the internal temperature reaches 150 ° C.

After the addition of 19 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-ethyl1,3-dioxolane, it is stirred and refluxed for 4 hours, the reaction mixture is cooled and poured into water. The product is extracted three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel with a mixture of trichloromethane and 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is transferred to the nitrate salt in 2,2'-oxybispropane. The salt is filtered off and recrystallized in a mixture of 4-methyl-2-pentanone and 2,2'-oxybispropane to give 10.5 parts (49%) of 1- / 2- (2,4-dichlorophenyl) -4 -ethyl-1,2,3-dioxolan-2-ylmethyl-1H-1,2₃4-triazole nitrate, mp 119.8 ° G.

7512643-3 '23

Example 18. Following the procedure described in Example 17 and using equivalent amounts of suitable starting material, the following 1,2,4-triazoleic acid addition salts can be prepared:

1- [4-Butyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] 71H1,2,4-triazole sesquietanedioate, m.p.

1- [2- (2,4-dichlorophenyl) -4-pentyl-1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole nitrate, mp 130.3 ° C;

1- [2- (2,4-dichlorophenyl) -4-hexyl] -1,3 "dioxolan-2-ylmethyl] -1H1,2,4-triazole nitrate, mp 106.2 ° C

1- [2- (2,4-dichlorophenyl) -4-heptyl] -1,3 ”dioxolan-2-ylmethyl] -1H1,2,4-triazole nitrate, mp 96.8 ° C

1- [2- (2,4-dichlorophenyl) -4-octyl-1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole nitrate, mp 110.6^ISLANDC.

Example 19. Repeating the procedure of Example 6-A and replacing 2- (bromoethyl) -2- (2,4-dichlorophenyl) -1,3-dioxolane to an equivalent amount of suitable 2- (bromomethyl) -2-aryl -1,3-dioxolane, the following compounds of formula (I) can be prepared:

1- / 2- (2,4,6-trichlorophenyl) -l, 3-dioxolan-2-ylmethyl / LH-l, 2,4-triazole; 1- [2- (2,6-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolyl-Z'2- (2-chloro-4-methylphenyl) -1, 3 ~ dioxolan-2-ylmethyl / H-l, 2,4-triazole. Example 20. The process of Example 7 can be used to prepare compounds of formula (I) wherein Z represents -CHL 2 -CHCCH 2) or -CH (CH 2) -CH (CH 2) -. Accordingly, by adding an equivalent amount of suitable 2-aryl-2- (bromomethyl) -4-methyl-1,3 'dioxolane or 2-aryl-2- (bromomethyl) -4,5-dimethyl-1,3-dioxolane dioxolane produces the following compounds in the form of the nitrate salt:

1- (4-methyl-2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole oil

2- / 2- (4-chlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl-7H-1,2,4-triazole; 1- [2- (2-chlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolyl] -4-methyl "2- (4-methylphenyl) -1, 3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole I "Z2" (4-methoxyphenyl) -4-methyl-1,3-dioxolan-2-ylmethyl-1H-1, 2,4-triazole 1- [4,5-diraethyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H, 2,4-triazole 1- (4,5- dimethyl-2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole and

1- [2- (4-chlorophenyl) -4,5-dimethyl-1,3-dioxolan-2-ylmethyl] -1H1,2,4-triazole.

Example 21. The process described in Example 6-A can be used to prepare the compounds of formula (I) wherein Z represents -CHg-CHg-CHg-. Accordingly, by adding an equivalent amount of suitable 2-aryl, -2- (bromomethyl) -1,3-dioxane as starting material obtain the following compounds:

L- (2-phenyl-l, 3-dioxane-2-ylmethyl) -LH-l, 2,4-triazole;

1- / 2- (2,4-dichlorophenyl) -1,3-dioxan-2-ylmethyl / LH-l, 2,4-triazole;

1- / 2- (4-chlorophenyl) -1,3-dioxane-2-ylmety17-1H-1,2,4-triazole;

1- / 2- (4-methylphenyl) -1,3 'dioxane-2-ylmetyl7-H-l, 2,4-triazole;

1- [2- (4-methoxyphenyl) -1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole;

1- / 2- (2-thienyl) -l, 3-dioxane ~ 2-ylmetyl7-H-L_in2,4-triazole and 1- [2- (2-naphthyl) -1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole.

Example 22. The compositions of the present invention are used in the forms commonly used to control fungi or bacteria, e.g. such as suspensions, powders, solutions, creams and the like. The following examples are intended to further illustrate the invention and the parts are by weight unless otherwise indicated (1) Suspension:

<td>1 kg</td><td>1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan1H-1,2,4-triazole</td><td>2-ylmetyL7-</td>

<td>. 2 lit.</td><td>technically xylene</td><td></td>

<td>350 ml</td><td>surfactant</td><td></td>

<td>water</td><td>diluted to the desired concentration of constituent.</td><td>active</td>

1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole forms a stable aqueous suspension when dissolved in xylene and emulsified with a surfactant.

(2) Powder;

parts 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H1,2,4-triazole are milled with 360 parts of talc in a ball mill, then 8 parts of olein are added and the painting is continued and finally, the mixture is mixed with 4 parts quenched lime. The powder formed can be sprayed satisfactorily and has good adhesive ability. It can be used for germination or for plant protection.

parts 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H1,2,4-triazole are dissolved in 95 parts of alkylated naphthalene and used as a spray to treat fungal infections or on walls, floors, or other objects to prevent fungal infection.

(4) cream;

parts 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl-7H1,2,4-triazole are dissolved in a hot liquid mixture of 400 parts of polyethylene glycol 400 and 590 parts of polyethylene glycol 1500, the solution if stirred during cooling and used as a cream for treating fungal couples and bacteria.

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Example 23.

OCK_ i Λ.

ί "-Ο-ννΗU. >

4-methylbenzene + HOCH.-CK.-CHpOH - £ ->

ir 2 methylDensen d (HNO)

R>

NOW \ t

Cl k

CH₂

Λ¹ VCI

CA 0

LJ

HNO.

The mixture of 1.7 parts of 1,3-propanediol, 1 part of 4-methylbenzenesulfonic acid and 90 parts of methylbenzene is stirred and refluxed for 31 minutes with a water separator. Then, 7.1 parts of 1 / 2- (2,2-i-dichloroferyl) -2,2-etherethoxyethyl / -1H-1,2,4-triazole-4-methylbenzenesulfonate are added and stirring under reflux is continued. for 4 hours. The reaction mixture is cooled, diluted with 1,1'-oxybisethane and the whole washed with a dilute sodium hydroxide solution and with water. A concentrated hydrochloric acid solution is added and the nitrate salt precipitates. The mixture is filtered off and crystallized from a mixture of 2-propane and 2,2'-oxybispropane to give 2.2 parts (39%) of^f 2,4-dichlorophenyl) -1,3-dioxan-2-ylmethyl / -1H-1,2,4-triazole nitrate mp 143.1¹

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Example 2ft,

<img file="SE433495B_D0006.tif" />

CH₂OK +

OH OH

CH -CH-CH-CH,

4-methylbenzenesulfonic acid C methylbenzene D (HNO4)

CH.

<img file="SE433495B_D0007.tif" />

HNO, ²XM

C CH,

H, C

O

A mixture of 1.8 parts of 2,3-butanediol, in part 4-methylbenzenesulfonic acid and 90 parts of methylbenzene is distilled azeotropically to dryness (1 hour). Then 7.1 parts of 1- / 2- (2,4-dichlorophenyl) 2,2-dimethoxyethyl / -1H-1,2,4-triazole-4-methylbenzenesulfonate are added and stirred overnight at reflux temperature. The reaction mixture is cooled and diluted with a sodium hydroxide solution. The product is extracted with 1, I¹oxybispropane. The extract is washed with water, dried, filtered and evaporated. The residue is transferred to the nitrate salt in the 2,2'oxybispropane. The salt is filtered off and crystallized from a mixture of acetonitrile and 2,2'-oxybispropane. The product is filtered off and dried, yielding 4.6 parts of 1- [2- (2,4-dichlorophenyl) -ft, 5 "dimethyl-1,3" dioxolan-2-ylmethyl] -1H-1,2,4-triazole mononitrate; mp 125 ° C.

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