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

The present invention relates to 1- (N-aryl) ethyl-1H-1,2,4-triazole ketals of the formula n which are useful for controlling plant diseases caused by fungi, molds and bacteria and as plant growth regulators.

I

CH -C -Ar / oo \ / z

6208C wherein Z is an alkylene group of the formula -CH₂-CH₂~ CH₂-,

-CH (CHg) -CH (CHg) - or -CH₂-CH (alkyl) -, wherein said alkyl contains 1 to 10 carbon atoms, and Ar is phenyl, substituted phenyl, thienyl, halothienyl, naphthyl or fluorenyl, wherein substituted phenyl represents a phenyl group having 1 to 3 substituents which may be independently haloenes, lower alkyloxy groups, cyano groups or nitro groups.

U.S. Patent No. 3,575,999 discloses 1- (β-aryl) ethylimidazole ketals having antibacterial and antifungal properties.

The triazole derivatives of the present invention differ from the previous derivatives e.g. in that the side chain attached to the triazole nitrogen atom is different.

Ketals of formula I are readily prepared by reacting 1H-1,2,4-triazole, which has previously been converted to its metal salt, for example by treatment with an alkali metal alkoxide, preferably sodium methoxide, with a halide of formula III y-ch₂

Λ ° \ / °

Ar

III wherein Ar and Z are the same as above and Y is halogen, preferably bromine. The reaction of 1H-1,2,4-triazole with a compound of formula III is preferably carried out in a suitable polar, reaction-inert organic solvent such as N, N-dimethylformamide, Ν, Ν-dimethylacetamide, acetonitrile, benzonitrile, etc. These solvents can be used for the reaction of others. with inert organic solvents such as benzene, methylbenzene, dimethylbenzene, and the like. If Y is bromine or chlorine, it is preferable to add an alkali metal iodide such as sodium or potassium iodide. To accelerate the reaction, it is preferable to use a slightly elevated temperature, and it is most convenient to carry out the reaction at the reflux temperature of the reaction mixture.

The ketal of formula I thus obtained is then separated from the reaction mixture in the usual manner, and, if desired, further purification is carried out with the aid of conventional purification methods such as crystallization, extraction, trituration, chromatography and the like.

The method described above is further clarified by the following diagram:

<img file="FI62080B_D0001.tif" />

H DMF, Nai

II

The starting materials of formula III, several of which are known compounds, can be prepared by known methods. Methods for preparing compounds wherein Z is -CH 2 -CH 2 -, -CH (CH 8) -CH-, -CH (CH 2) -CH (CH 2), or -CH 2 -CH 2 -CH 2 - are described in U.S. Patent No. 3,575. 999. In general, compounds of formula III can be prepared by ketalization between the corresponding ketone of formula IV, wherein Ar and Y are as previously defined, and the corresponding diol of formula V, using known ketalization methods described in the literature (e.g. Synthesis, 1974 (1)). 23).

The compounds of this invention are very potent fungicides useful in agriculture. They are very active against a wide variety of seals, such as those found as mildew in various plant species, e.g. Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podospharae leuchotricha, Sphaerotheca pannosa, e.g. Venturia inaequalis, Collectotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenuis, Thielaviopsis basicola, Helminthosporium gramineus, Penicillium digitatum.

They are very useful due to their preventive, curative and internal effect. Their strong antifungal effect on plants pathogenic to fungi is more evident from the experimental results that follow.

In several of these experiments, 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethylx71H-1,2,4-triazole of formula Ia has been used as a compound of formula I.

<img file="FI62080B_D0002.tif" />

A. Prevention of Erysiphe cichoracearum by compounds of formula I in the treatment of throat leaves.

Young throat seedlings, about 10 days old, were sprayed with an aqueous solution containing 250, 100 or 10 ppm of test compound; reference seedlings were not treated at all. Once the seedlings had dried, they were artificially infected with Erysiphe cichoracearum spores by lightly rubbing them with a very badly infected leaf. Fifteen days after infection, fungal growth was assessed by counting spots from seedlings. The results are shown in Table I, which gives the averages of the two plants, and the following system was used to calculate the points:

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

Table I

Prevention of Erysiphe cichoracearurn with compounds of formula I in the treatment of throat leaves

CH₉-c_^Ar /\

<td rowspan="2">Ar</td><td rowspan="2">R</td><td rowspan="2">Base or salt</td><td colspan="3">l Antifungal score '</td>

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

<td>2,4- (Cl)₂-CgH₃</td><td>B</td><td>base</td><td> -</td><td> 0</td><td>'' ί o</td>

<td>C, H ,. 6 5</td><td>B</td><td>base</td><td> -</td><td> 3</td><td>ä</td>

<td>4-NO.-CH 2 6 4</td><td>B</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>3-Cl-C, H 6 4</td><td>B</td><td>base</td><td> -</td><td> 2</td><td> -</td>

<td>2-C1-CH Ό 4</td><td>B</td><td>(COOH)</td><td> -</td><td> 0</td><td> __ *</td>

<td>4-Br-CH, o 4</td><td>B</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>2-Br-C, H. 6 4</td><td>B</td><td>(COOH)</td><td> -</td><td> 2</td><td> -</td>

<td>3-OCH -C, H 3 6 4</td><td>B</td><td>(COOH)</td><td> 1</td><td> -</td><td> -</td>

<td>2-0Η_ο-0, _Η_Λ 3 6 4</td><td>B</td><td>(COOH) 2</td><td> 0</td><td> -</td><td> -</td>

<td>4-FC H 6 4</td><td>B</td><td>(COOH)</td><td> 0</td><td> -</td><td> -</td>

<td>4-CH -CH 3 6 4</td><td>K</td><td>(COOH)</td><td> 0</td><td> -</td><td>! ! i</td>

<td>4-Cl-C_rB. 6 4</td><td>B</td><td>(COOH)₂B₂O</td><td> -</td><td> 0</td><td></td>

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

<td>2,5- (Cl) -CH 2 6 3</td><td>B</td><td>(COOH)</td><td> -</td><td> 0</td><td> -</td>

<td>4-CN-C_rB. 6 4</td><td>B</td><td>(COOH)</td><td> 0</td><td> -</td><td></td>

<td>3,4- (Cl)₂-C₆B₃</td><td>B</td><td>(COOH)</td><td> -</td><td> 3</td><td></td>

<td>2-OCH -CH 3 6 4</td><td>B</td><td>(COOH)₂</td><td> 1</td><td></td><td> —</td>

6208C

Table I (continued)

<td rowspan="2">Ar</td><td rowspan="2">R</td><td rowspan="2">base or Ξ salt</td><td colspan="3">»Anti-gingival score</td>

<td>250 ppm</td><td>10 ppm</td><td>1 0 ppm</td>

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

<td>2-fluorophenyl</td><td>B</td><td>base</td><td> 0</td><td> -</td><td> -</td>

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

<td>3 “Br, 4-CH-CH 3 6 3</td><td>B</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>2-CHg, 4-Br-CgHg</td><td>B</td><td>base</td><td> -</td><td> 2</td><td> -</td>

<td>2-CH-. , 4-Cl-C, H ~ 3 6 3</td><td>B</td><td>base</td><td> 0</td><td> -</td><td> -</td>

<td>3-Br-CH. 6 4</td><td>B</td><td>base</td><td> 2</td><td> -</td><td> -</td>

<td>4-IC, H. 6 4</td><td>B</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td> 3,5-(01)₂-C₆B₃</td><td>B</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2,3- (Cl)₂-C₆B₃</td><td>B</td><td>(COOH)₂</td><td> 0</td><td> -</td><td> -</td>

<td>³-N ° 2-^c6^B4</td><td>B</td><td>base</td><td> 1</td><td> -</td><td> -</td>

<td>2,4- (Br)₂-C₆B₃</td><td>B</td><td>(COOH)₂</td><td> -</td><td> 1</td><td> -</td>

<td>2,4,5- (Cl)₃-C₆B₂</td><td>B</td><td>(cooh)₂</td><td> 0</td><td> -</td><td> -</td>

<td>2-Cl, 4-OCHg-CgHg</td><td>B</td><td>(COOH)₂</td><td> -</td><td> 2</td><td> -</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>ch₃</td><td>hno₃</td><td> 0</td><td> -</td><td> -</td>

<td>2,4- (Cl)₂C₆B₃</td><td>^C2^B5</td><td>hno₃</td><td> -</td><td> 0</td><td> 0</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>nC₃^B7</td><td>hno₃</td><td> -</td><td> 0</td><td> 0</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>^nC4^B9</td><td>11/2 (COOH)</td><td> -</td><td> 2</td><td> -</td>

<td>2,4- (Cl)₂C₆B₃</td><td>^nC5^B11</td><td>hno₃</td><td> -</td><td> 0</td><td> 0</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>^nC6^B13</td><td>hno₃</td><td> 0</td><td> -</td><td> -</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>^nC7^B15</td><td>hno₃</td><td> -</td><td> 2</td><td> -</td>

<td>2,4- (Cl)₂-C₆B₃</td><td>^nC8^B17</td><td>hno₃</td><td> 0</td><td></td><td></td>

Ί

A. 1. Prevention of Erysiphe polyhaga by treatment of throat leaves.

Young throat seedlings with only one leaf were sprayed with an aqueous solution of 500, 250 or 124 ppm of a compound of formula Ia; reference seedlings were not treated at all. Artificial infestation with Erysiphe polyphaga spores was performed by rubbing the seedlings on the fourth, sixth, or eighth day after treatment with a very badly infected leaf. On the eighteenth and thirty-fourth days after treatment, the percentage of leaf area destroyed by the fungus was calculated as a percentage of separately infected leaves and separately burst leaves. The values ​​given in Table 1.1 are the averages of five plants and are expressed as percent loss compared to untreated seedlings.

Table I.1

Prevention of Erysiphe polyphaga by a compound of formula Ia by treatment of throat leaves

<img file="FI62080B_D0003.tif" />

620

B. Prevention of Erysiphe graminis infection by treatment of barley soil.

Barley seedlings were irrigated using 100 ml of aqueous solution containing 1,000, 100 or 10 ppm of a compound of formula Ia per seedling. The control seedlings received the same amount of liquid that did not contain Compound Ia. The natural infestation, which normally occurs when plants are kept in a greenhouse in the vicinity of infected plants, was assessed 16 days after treatment by counting the number of spots on the leaves. Five plants were used in each experiment, and the values ​​given in Table II are averages calculated as percent infection compared to controls.

Table II

Prevention of Erysiphe graminis infection in barley by treatment with a compound of formula Ia

<td>Dose mg of compound Ia per piece</td><td>Infection rate to control compared to</td>

<td>Control</td><td> 100</td>

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

<td>1 0 mg</td><td> 0</td>

<td>1 mg</td><td> 53</td>

C. Control of Erysiphe graminis in barley by treatment with leaves

Barley seedlings infected with Erysiphe graminis were sprayed with aqueous solutions containing the compound of formula Ia at the concentrations listed in Table III. On the sixteenth day after treatment, spots were counted on the seedlings. There were 5 taints in each experiment and Table III gives the results as means calculated as percent infection compared to the control.

6208C

Table III

Control of Erysiphe graminis infection in barley by treatment of leaves with a compound of formula Ia

<td>Contained in the injected solution</td><td>Percentage of infection</td>

<td>the concentration of compound Ia</td><td>compared to control</td>

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

<td>1,000 ppm</td><td>⁰</td>

<td>10 ppm</td><td> 1,5</td>

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

D. Inhibitory effect of a compound of formula Ia on Podosphaera leuchotricha in apple orchards when sprayed.

One-year-old apple seedlings were sprayed with aqueous solutions containing Compound Ia in the amounts listed in Table IV. The seedlings were artificially inoculated with Podosphaera leuchotricha spores as in point A one day after treatment and incubated for 36 hours. Fungal infection was assessed 25 days after treatment by counting the number of spots. There were 2 plants in each experiment, and Table IV shows the results as means calculated as percent infection compared to the control.

Table IV

Inhibitory effect of Podosphaera leuchotricha on apple seedlings by spraying with compounds of formula Ia

<td>Contained in the spray solution</td><td>Percentage of infection</td>

<td>the concentration of compound Ia</td><td>compared to control</td>

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

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

<td>1 0 ppm</td><td> 6</td>

6208

E. Activity against Thielaviopsis sp. 5 mm thick potato and leek slices were dipped in aqueous solutions of the compound of formula Ia in the amounts indicated in Table V. After dipping, the slices were placed on filter paper on a large plastic tray, and the tray was covered with glass. Artificial infection was performed on the day of treatment by injecting the slices with a suspension rich in Thielaviopsis sp. Spores, and the slices were incubated at room temperature. Fungal growth was assessed on slices six days after treatment by counting the mold-infected area. Table V shows the results expressed as percent infection compared to controls.

Table V

Activity of a compound of formula Ia against Thielaviopsis sp

<td rowspan="2">Concentration of compound Ia in the test solution in ppm</td><td colspan="2">Percentage of infection compared to control</td>

<td>Potato</td><td>Leek</td>

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

<td> 1 000</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>

6208

In addition, the compounds of the formula I have valuable plant growth-regulating properties. Depending on various factors, such as the plant species being treated or the amount of active substance, the effect may manifest itself as growth acceleration or growth inhibition. Thus, the compounds of the invention are useful plant growth regulators. Thus, they can be used as inhibitors or retarders of plant growth and in particular as inhibitors of root growth, for example in tobacco seedlings. Under certain conditions, they can also be used as plant growth accelerators.

The plant growth regulating properties of the compounds of formula I are clarified by the following experiments using compound Ia.

F. The effect of tomato seedlings on soil treatment.

Young, 3.5 to 4 cm tall tomato seedlings were planted in separate pots. The pots were soaked in test solutions of the compound of formula Ia in the amounts indicated in Table VI. Growth was assessed by determining plant length and weight 28 days after treatment. The results are given in Table VI as the average of 5 plants, calculated as a percentage of the reference plants.

Table VI

Growth regulating effect of a compound of formula Ia on tomato seedlings by treatment of the soil

<td>A dose of compound Ia</td><td>Seedling length pro-</td><td>Seedling weight pro-</td>

<td>per piece</td><td>cents control</td><td>cents control</td>

<td></td><td>compared to</td><td>compared to</td>

<td>none</td><td> 100</td><td>100 i</td>

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

<td> 1</td><td> 127</td><td> 1 34</td>

<td> 0,1</td><td> 122</td><td> 166</td>

G. Regulation of barley growth by treatment of leaves. Young barley seedlings with 3-4 leaves were sprayed with test solutions containing the compound of formula Ia in the amounts indicated in Table VII. The effect of the compound on seedling growth was evaluated 24 days after treatment by determining the weight of the seedlings. The results given in Table VII are the averages of 10 seedlings calculated as a percentage of the control seedlings.

Table VII

Growth-regulating effect of a compound of formula Ia on barley by treatment of leaves

<td>Concentration of compound Ia (ppm) in the test solution</td><td>Average weight of seedlings as a percentage of the control</td>

<td>none</td><td> 100</td>

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

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

H. Restriction of root growth of tobacco seedlings. Tobacco seedlings, variety Xanthi, were grown in a greenhouse and were topped at an early bud stage. After five days

620 80 foliage was sprayed with an aqueous suspension of compound (Ia) so that the spray rates were 3 and 1.5 kg of active substance per hectare. Each treatment was repeated 3 times. Twelve days after treatment, the growth of root suckers compared to topped and untreated control plants was evaluated.

Root growth increased by 100% at 3.0 kg / ha and by 90% at 1.5 kg / ha.

I. Growth prevention of soybean seedlings.

Soybean seedlings, variety Hark, were grown in pots in a growing cabinet at 23 ° C under 20,000 lux lighting and 14 hours of daytime. After the third trifoliate had opened, the seedlings were sprayed with aqueous suspensions of compound (Ia) at 1000, 500, 100 and 50 ppm as active ingredient.

after one day, the inhibition of growth of the treated seedlings was evaluated as a percentage compared to the control seedlings. The following results were obtained:

Table VIII

<td>Handling</td><td>Inhibition of growth</td>

<td>(Ia) 1000 ppm of active ingredient</td><td> 70 %</td>

<td>500 ppm active ingredient</td><td> 40 %</td>

<td>100 ppm active ingredient</td><td> 25 %</td>

<td>50 ppm active ingredient</td><td> 0 %</td>

<td>Control</td><td> 0 %</td>

Using a concentration of 1000 ppm, a stronger green color was observed in the foliage.

J. Results of comparative tests.

The fungicidal activity of the compounds according to the invention and two known compounds (U.S. Pat. No. 3,575,999 and DE-OS 2,201,063) was determined (see Tables a, b). the seedling was about 10 cm high. After the seedlings had dried, fungal conidia were sprayed on them, and after about 2 weeks, the fungicidal efficacy was evaluated. The degree of fungal damage was assessed as follows:

Damage (%) &lt;0.9 &lt;2.3 &lt;4.6 8.2 14.0 23.3 38.2 62.0 100%

Activity value 123456789 (very active) (inactive)

The test compounds are listed in Table IXa, the sets are shown in Table IXb.

Table ^IXa ό 2 0 S 0 and new compounds

Compound Number R_

B

B

B

B

B

B

B

B

B

B

1 B

B

3 B

4 B

5 B

6 B

B

8 B

9 B

B

B

B

B

B

B

B

B

8 B

B

B

<img file="FI62080B_D0004.tif" />

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

B

2-CH₃

2-OCH₃

2-C1

2- Br

3- CH₃3-OCH₃3-C1 3-Br

3- NO₂

4- CH₃4-OCH₃4-F 4-C1 4-Br 4-1 4-NO₂4-CN

2.3- di-Cl

2.4- di-Cl

2.5- di-Cl

3.4- di-Cl

3.5-di-Cl 2,4-di-Br

2- CH₃: 4-Cl

3- Br: 4-CH₃2-Cl: 4-OCH₃2-CH₃: 4-Br 2,3,4-tri-Cl

2,4,5-tri-Cl

As mono-oxalate As mono-oxalate

As a mono-oxalate

Mono oxalate Mono oxalate Mono oxalate Mono oxalate

As a mono-oxalate

As mono-oxalate As mono-oxalate

Mono-oxalate Mono-oxalate Mono-oxalate

As a mono-oxalate

As a mono-oxalate

Table IXa (continued)

<td>Compound- number</td><td>R¹</td><td>r £</td><td>X</td><td>Note.</td>

<td> 31</td><td>ch₃</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 32</td><td>^C2^B5</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 33</td><td> &lt;^CH2&gt;2^CH3</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 34</td><td>(ch₂)₃ch₃</td><td>B</td><td>2,4-dichloro</td><td>As sesquioxalate</td>

<td> 35</td><td>^ICH2&gt;4^CH3</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 36</td><td>(CH?) _[.CH₃</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 37</td><td></td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 38</td><td>(CH_?)₇CH₃</td><td>B</td><td>2,4-dichloro</td><td>As nitrate</td>

<td> 39</td><td>ch₃</td><td>ch₃</td><td>2,4-dichloro</td><td> -</td>

Known compounds

<img file="FI62080B_D0005.tif" />

US 3,575,999

<img file="FI62080B_D0006.tif" />

f O CH f II I 3

CH -CH-CC-CH ² II

DE-OS 2 202 063

<img file="FI62080B_D0007.tif" />

Cl

6208C

Table IXb

E.cichoracearum E.graminis E.cichoracearum U.appendiculatus Dose. Dose concentration Dose concentration Dose concentration

(mg / 1) (mg / 1) (mg / plants) (mg / 1)

00 1 0 1 100 10 1 0 1 250 1 00 50 25

2

7

9

9

9

9

9

9

9

9

9

5

9

9

9

9

9

9

4

8

9

9

3

9

9

8

5

9

9

1

4

5

7

8

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

9 1

8 1

9 1

9 1

9 4

8 1

9 1

9 5

9 1

9 1

9 1

9 9

9 1

9 9

9 5

9 1

4 1

8 1

7 1

9 1

9 8

9

1 1 9 9 9 9 9 9 9 1 9 9 9 9 9 9 1

9 9

9 9 9 9 9 9 1 1 8 9 9

6 8

1 3

1 1

4 6

1 1

Table IXb (continued)

E.cichoracearum E.graminis E.cichoeacearum U.appediculatus compound tested Dose concentration Dose concentration Dose concentration

(mg / 1) (mg / 1) (mg / 1) tng / 1)

<td></td><td> 100</td><td> 10</td><td> 1</td><td> 100</td><td> 10</td><td> 10</td><td> 1</td><td> 250</td><td> 100</td><td> 50</td><td> 25</td>

<td> 36</td><td> 1</td><td> 1</td><td> 5</td><td> 1</td><td> 8</td><td> 9</td><td> 9</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td> 37</td><td> 1</td><td> 6</td><td> -</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td> 38</td><td> 3</td><td> 8</td><td> 9</td><td> 1</td><td> 7</td><td> 9</td><td> 9</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td> 39</td><td> 1</td><td> 5</td><td> 9</td><td> 1</td><td> 6</td><td> 1</td><td> 3</td><td> 1</td><td> 1</td><td> 1</td><td> 5</td>

<td> 40</td><td> 8</td><td> 9</td><td> 9</td><td> 1</td><td> 7</td><td> 8</td><td> 9</td><td> 8</td><td> 9</td><td> 9</td><td> 9</td>

<td> 41</td><td> 7</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> 9</td><td> -</td><td> 9</td>

<td></td><td>Above</td><td colspan="3">described</td><td colspan="2">antifungal</td><td colspan="4">., antibacterial</td><td> -</td>

<td>sn and</td><td>growth</td><td colspan="6">in the light of regulatory activities</td><td>this</td><td colspan="2">invention</td><td></td>

<td>r joaa</td><td colspan="2">valuable</td><td colspan="2">mixtures,</td><td>which:</td><td>contain</td><td colspan="2">invention</td><td colspan="2">to -</td><td>be</td>

ketals of formula I or their acid addition salts as active ingredients in a solvent or solid, semi-solid or liquid diluent or carrier, and further the present invention provides an effective method of controlling fungal and bacterial growth using the amount of these ketals or salts thereof of formula I . The compounds of the invention may be used in suitable diluents or solvents in the form of emulsions, suspensions, dispersions or ointments, in suitable solid or semi-solid carriers, ordinary or synthetic soaps, detergents or dispersants, and, if desired, with other anti-mucus compounds. preventive, antifungal and / or antibacterial effects or with inactive additives.

Solid carriers suitable for the preparation of powder mixtures include e.g. various inert, porous and powdered inorganic or organic mixing agents such as tricalcium phosphate, calcium carbonate in the form of chalk or ground limestone, kaolin, bolus, bentonite, talc, diatomaceous earth and boric acid, powdered cork and other sawdust, and sawdust;

62C8C

The active ingredient is mixed with the carriers, e.g. by co-grinding, or alternatively the active ingredient is absorbed as a solution in a volatile solvent, and then the solvent is removed by heating or suction filtration under reduced pressure. By adding wetting and / or dispersing agents, these powder preparations can be easily made into aqueous suspensions.

Inert solvents used in liquid preparations should not be highly flammable and should be as odorless as possible and as toxic as possible to warm-blooded animals or exposed plants. Suitable solvents for this purpose are high-boiling oils, e.g. vegetable oils, and low-boiling solvents with a flash point of at least 30 ° C, such as polyethylene glycol, isopropanol, dimethyl sulfoxide, hydrogenated naphthalenes and alkylated naphthalenes. It is also possible to use solvent mixtures. Solutions can be prepared in the usual manner and, if necessary, solubilizers can be used. Other useful liquid forms include emulsions or suspensions of the active compound in water or suitable inert solvents, or concentrates for the preparation of such emulsions, which can be directly adjusted to the desired concentration. The active ingredient may be mixed with a dispersing or emulsifying agent. The active ingredient may also be dissolved or dispersed in a suitable inert solvent in which the dispersing or emulsifying agent is mixed, simultaneously or afterwards.

It is also possible to use semi-solid carriers in the form of creams, pastes or waxes, in which case the active ingredient may be incorporated, if necessary, with the aid of solubilizers and / or emulsifiers. Examples of semi-solid carriers are petrolatum and other ointment bases.

In addition, it is possible to use the active ingredient in aerosol form. In this case, the active ingredient is dissolved or dispersed, if necessary with the aid of inert solvents, such as difluorochloromethane, which boils below atmospheric pressure at room temperature, or other volatile solvents. In this way, pressurized solutions are obtained which, when sprayed, produce aerosols which are very well suited for controlling or controlling fungi and bacteria, e.g. enclosed cabinets and storage rooms, and for the treatment of vegetation to eradicate root sludge or to prevent infections by fungi or bacteria.

The treatment with the compounds of the invention or mixtures thereof can be carried out by conventional methods. For example, the fungal or bacterial culture or the material to be protected from fungi and bacteria may be treated with the compounds of the invention or mixtures thereof by dusting, spraying, spraying, brushing, dipping, lubricating, impregnating or other suitable means.

If the compounds of the invention are used with suitable carriers, e.g. solutions, suspensions, dusts, powders, creams, emulsions and the like, very strong activity can be observed over a very wide range of dilutions. For example, 0.1 to 10% by weight of active substance, based on the weight of the whole mixture, has been found to be effective in controlling fungi and bacteria. Of course, higher concentrations can also be used depending on the situation.

The following examples illustrate the invention. Unless otherwise indicated, all parts are by weight.

Manufacture of starting materials.

A. 1- (4-chloro-2-methoxyphenyl) ethanone

A stirred and cooled (0 ° C) solution of 30 parts of 1- (4-amino-2-methoxyphenyl) ethanol in 360 parts of concentrated hydrochloric acid, one part of water and 30 parts of acetic acid is diazotized with a solution of 17.25 parts of sodium nitrite in 200 parts of water . The mixture is stirred for 30 minutes at 0 [deg.] C. and, with stirring, poured into a solution of 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid. The mixture is stirred for 1 hour at 60 ° C. The mixture is cooled to room temperature and extracted twice with 2,2'-oxybispropanil. The combined extracts are washed with water, dilute sodium hydroxide solution and twice more with water, dried, filtered and evaporated. 28 parts (76%) of 1- (4-chloro-2-methoxyphenyl) ethanone are obtained, m.p.

B. 2- (Bromomethyl) -2- (4-bromo-2-methylphenyl) -1,3-dioxolane

To a stirred mixture of 78.8 parts of 2-bromo-1- (4-bromo-2-methylphenyl) -1-ethanone and 200 parts of butanol are added 3 parts of 4-methylbenzenesulfonic acid and 225 parts of benzene. 33.5 parts of 1,2-ethanediol are then added dropwise. After the addition, stirring is continued overnight at reflux temperature with a water separator. The reaction mixture is evaporated and the residue is dissolved in 2,2'-oxybispropane. 15 parts of concentrated sodium hydroxide solution are mixed with the solution. The layers are separated and the aqueous phase is extracted with 2.2¹-oxybispropane. The combined organic layers are washed with water until neutral, 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-dioxalane, m.p. 86 ° C.

C \ _

Following the procedure used in Example B, but using the corresponding 1-aryl-2-bromo-1-ethanone in place of 2-bromo-1- (4-bromo-2-methylphenyl) -1-ethanone, the following 2-aryl-2-bromomethyl-1 is obtained, 3-dioxolanes:

4- [2- (bromomethyl) -1,3-dioxolan-2-yl] benzonitrile, m.p. 92.4 ° C, and 2- (bromomethyl) -2- (2-naphthalenyl) -1,3-dioxolane, m.p. 64 ° C.

D. 2- (Bromomethyl) -2- (5-chloro-2-thienyl) -1,3-dioxolane A portion of 1- (5-chloro-2-thienyl) -1-ethanone is dissolved in 220 parts of 1,2-ethanediol. ° C. Over the course of one hour, 64 parts of bromine are added dropwise with stirring without external heating. The mixture is stirred for 1 hour at room temperature, and then 4 parts of 4-methylbenzenesulfonic acid and 360 parts of benzene are added. The mixture thus obtained is stirred at reflux overnight with a water separator. The reaction mixture is evaporated and the residue is dissolved in 2,2'-oxybispropane. The solution thus obtained is washed successively once with dilute sodium hydroxide solution and then three 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, b.p. 125-127 ° C at 0.1 torr .

0 8C

E.

Following the procedure described in Example D, but using an equivalent amount of 1-aryl-1-ethanone in place of 1- (5-chloro-2-thienyl) -1-ethanone, the following 2-aryl- (bromomethyl) -1,3-dioxolanes are obtained:

2- (bromomethyl) -2- (9H-fluoren-2-yl) -1,3-dioxolane, m.p. 90 ° C,

2- (bromomethyl) -2- (3-bromo-4-methylphenyl) -1,3-dioxolane, b.p. 126-130 ° C at 0.1 torr,

2- (bromomethyl) -2- (4-iodophenyl) -1,3-dioxolane, m.p. 74 ° C,

2- (bromomethyl) -2- (4-chloro-2-methoxyphenyl) -1,3-dioxolane, m.p. 110 ° C,

2- (bromomethyl) -2- (2,4-dibromophenyl) -1,3-dioxolane, m.p. 96 ° C. Example 1

A. 1- [2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole

To a stirred solution prepared by dissolving

To 2.3 parts of sodium is added to 120 parts of methanol, 6.9 parts of 1H1,2,4-triazole are added to 150 parts of dimethylformamide. The methanol is removed under normal pressure until the internal temperature is 130 ° C. At this point, 25 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) are added.

1,3-dioxolane. The reaction mixture is stirred at reflux for one hour. It is allowed to cool to room temperature and poured into water. The precipitated product is collected by filtration and crystallized from diisopropyl ether (activated carbon) to give 12 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl].^-1H-1,2,4-triazole, m.p. 109.9 ° C.

B. The nitrate salt portion of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole is converted to the nitrate 2.2 ^{1 * 3 * * 6}in oxybispropane. After cooling, the salt is filtered and crystallized twice from 2-propanone to give 3 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate, m.p.

172.7 ° C.

C. The sulfate salt portion of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole is converted to sulfate in 2,2'-oxybispropane. The sulfate obtained is filtered off and crystallized from 2-propa22. The product is filtered off, recrystallized from ethanol (activated carbon) and dried to give 6 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole sulphate, m.p. 207.1 ° C.

Example 2

1- [2- (2,4-Dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate

To a stirred solution prepared by dissolving

2.3 parts of sodium 80 parts of methanol. 6.9 parts of 1H-1,2,4-triazole and 2 parts of sodium iodide in 100 parts of Ν, Ν-dimethylformamide are added. The methanol is removed under normal pressure until the internal temperature is 130 ° C. At this point, 34.4 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolane are added, and the mixture thus obtained is stirred under reflux for 3 hours. The reaction mixture is poured into water and the product is extracted twice with diisopropyl ether. The combined extracts are washed with water and excess concentrated nitric acid is added. The crude nitrate is filtered off and crystallized from a mixture of 2-propanol and diisopropyl ether. 15 parts of 1- [3- (2,4-dichlorophenyl) -4-methyl-1,3-dioxoan-2-ylmethyl] -1H-1,2,4-triazolinitrate are obtained, m.p. 137.8 ° C.

Example 3

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

To a stirred sodium methoxide solution containing 48 parts of methanol dissolved in 2.8 parts of sodium is added 8.3 parts of 1H-1,2,4-triazole. The mixture is stirred for 30 minutes at room temperature, then 135 parts of Ν, Ν-dimethylformamide are added and the methanol is evaporated. 24.3 parts of 2- (bromomethyl) -2-phenyl-1,3-dioxolane and 3 parts of potassium iodide are then added, and the mixture thus obtained is stirred at reflux for 3 hours. The reaction mixture is cooled to room temperature and poured into water. When scratched, the product precipitates. The product is filtered off with suction, washed with water, dried and crystallized from ethanol and 2.2¹-oxybispropane (1: 5 by volume) to give 10.9 parts (43.7%) of 1- (2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, sp. 127.3 ° C.

Example 4

Proceed as described in Example 3, but use an equivalent amount of 2-aryl-2- (bromomethyl) 1,3-dioxolane instead of 2- (bromomethyl) -2-phenyl-1,3-dioxolane,

6 / * »/ λ / z O ο v the following 1,2,4-triazoles are obtained:

1- [2- (4-nitrophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 160.1 ° C

1- [2- (3-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 1 13.9 ° C,

1- [2- (4-bromophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 135.9 ° C,

1- [2- (3-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 105.4 ° C,

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

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

Example 5

1- / 2- (2,3,4-Trichlorophenyl) -1,3-dioxolan-2-ylmethyl71H-1,2,4-triazole

To a stirred sodium methoxide solution prepared by dissolving 48 parts of methanol in 1.6 parts of sodium is added 4.9 parts of 1H-1,2,4-triazole. The mixture is stirred for 1 hour at room temperature and then 135 parts of N, N-dimethylformamide are added. The methanol is distilled off under normal pressure until the internal temperature is 130 ° C. 17.4 parts of 2- (bromomethyl) -2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are then added successively. The mixture thus obtained is stirred while refluxing overnight. The reaction mixture is cooled to room temperature and poured into water. When scraped, the product precipitates, is filtered off and washed with water. The product is dissolved in trichloromethane and purified by column chromatography on silica gel using trichloromethane with 5% methanol as eluent. The pure fractions are collected or made and the eluent is evaporated. The residue is crystallized from a mixture of 2,2'-oxybispropane and methanol (9: 1 by volume) to give

9.3 parts (55.5%) of 1- [2- (2,3,4-trichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 181.4 ° C.

Example 6

Proceed as described in Example 5, but using equivalent amounts of starting materials; the following are obtained

1,2,4-triazoles:

1- [2- (9H-fluoren-2-yl) -1,3-dioxolan-2-ylmethyl]^-1H-1,2,4-triazole, m.p. 186.8 ° C,

1- [2- (5-chloro-2-thienyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 117.4 ° C,

1- [2- (3-bromo-4-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 120.7^OC_z

- [2- (4-bromo-2-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 148.1 ° C_Z and

1- [2- (4-chloro-2-methylphenyl) -1,3-dioxolan-2-ylmethyl]^-1H~

1.2.4- triazoles, m.p. 147.9 ° C.

Example 7

1- [2- (2-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate

To a stirred sodium methoxide solution prepared by dissolving 2.8 parts of sodium in 56 parts of methanol is added a mixture of 8.3 parts of 1H-1,2,4-triazole and 135 parts of N, N-dimethylformamide. The methanol is removed under normal pressure until the internal temperature is 130 ° C. At this stage, a mixture of 27.8 parts of 2- (bromomethyl) -2- (chlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide is added. The mixture thus obtained is stirred at reflux for 6 hours. After cooling to room temperature, the reaction mixture is poured into water and extracted three times with 1,1'-oxybisethane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is converted into the oxalic acid salt in 4-methyl-2-pentanone. The salt is filtered and crystallized from 4-methyl-2-pentanone to give 16 parts of 1- [2- (2-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate, m.p. 156.5 ° C.

Example 8

Proceed as described in Example 7, but using equivalent amounts of starting materials. The following are obtained

1.2.4- Triazole oxalates:

<img file="FI62080B_D0008.tif" />

Ar

<img file="FI62080B_D0009.tif" />

Ar_ Acid salt Melting point ° C

<td>2-Br-CH^{6 4}</td><td>(COOH)₂</td><td> 172,1</td>

<td>3-OCH -C, H 3 6 4</td><td>(COOH)</td><td> 155,6</td>

<td>2-CH₃-C₆B₄</td><td>(COOH)</td><td> 177,1</td>

<td>⁴-^F'^C6^B4</td><td>(COOH)</td><td> 185,5</td>

<td>4-CH.-C H. 3 6 4</td><td>(COOH)₂</td><td> 151 ,2</td>

<td>4-Cl-C, H. 6 4</td><td>(COOH)₂.B₂O</td><td> 169,1</td>

<td>4-OCH -C, H 3 6 4</td><td>(COOH)₂</td><td> 187,1</td>

<td>2-naphthalenyl</td><td>(COOH)₂</td><td> 175,0</td>

<td>2,5- (Cl)₂-C₆B₃</td><td>(cooh)₂</td><td> 173,7</td>

<td> 4-_CNC₆^B4</td><td>(COOH)₂</td><td> 186,3</td>

<td>3,4- (Cl)₂-C₆B₃</td><td>(COOH)₂</td><td> 182,2</td>

<td>2-thienyl</td><td>(COOH)₂</td><td> 144,5</td>

<td>2,4- (Br)₂-C₆B₃</td><td>(COOH)₂</td><td> 190,3</td>

Example 9

1- [2- (2-Methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate

To a stirred sodium methoxide solution prepared by dissolving 2.3 parts of sodium in 48 parts of methanol is added 6.9 parts of 1H-1,2,4-triazole. The mixture is stirred for 30 minutes at room temperature and then 135 parts of N, N-dimethylformamide are added. The methanol is evaporated off under normal pressure until the internal temperature is 130 ° C. At this stage, 3 parts of potassium iodide and 16.4 parts of 2- (bromomethyl) -2- (O-methoxyphenyl) -1,3-dioxolane are added successively. The mixture thus obtained is stirred at reflux for 18 hours. After cooling to room temperature, the reaction mixture is poured into water and the solution thus obtained 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 trichloromethane with 5% methanol as eluent. The pure fractions are collected and the eluent is evaporated. The residue is converted into the oxalic acid salt in 4-methyl-2-pentanone. The salt is filtered off and crystallized from 2-propanone and 2.2¹-oxybispropane (2: 1 by volume) to give 5.5 parts (26%) of 1- [2- (2-methoxy-phenyl) -1,3-dioxolan-2-ylmethyl] -1H^-1,2,4-triazole oxalate, m.p. 166.4 ° C.

Example 10

Proceed as described in Example 9, but using equivalent amounts of starting materials. The following 1,2,4-triazole oxalates are obtained:

1- [2- (4-iodophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate, m.p. 169.8 ° C_Z

- [2- (3,5-dichlorophenyl) -1,3-dioxolan-2-ylmethyl]^-1H^_, 2,4-triazole oxalate, m.p. 204.4 ° C,

1- [2- (2,3-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate, m.p. 188.4 ° C_Z

1- [2- (4-chloro-2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl]^-1H1, 2,4-triazole oxalate, m.p. 173.2 ° C_Z

- [2- (2,4,5-trichlorophenyl) -1,3-dioxolan-2-ylmethyl]^_'^1H“

1,2,4-triazole oxalate, m.p. 178.4 ° C, and

1- [2- (2-chloro-4-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate, m.p. 188.2 ° C.

Example 11

1- [2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate

To a stirred mixture of 9.5 parts of 1H-1,2,4-triazole and 225 parts of N, N-dimethylformamide are added in small portions 4.2 parts of a 78% dispersion of sodium hydride. The mixture is stirred until foaming ceases, after which 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 2.2¹-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by column chromatography over silica gel using trichloromethane with 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is converted to the nitrate 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%) of 1 - [- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1 H-1,2,4-triazoline nitrate, m.p. 132.6 ° C.

Example 12

1- [2- (2,4-Dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate

To a stirred sodium methoxide solution prepared by dissolving 3.8 parts of sodium in 40 parts of methanol. 11.5 parts of 1H-1,2,4-triazole and 225 parts of N, N-dimethylformamide are added. Methanol is distilled off until the internal temperature is 150 ° C. At this point, 19 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane are added, and the mixture thus obtained is stirred under reflux 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 using trichloromethane with 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is converted to the nitrate in 2,2'-oxybispropane. The salt is filtered off and recrystallized from 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-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazoline nitrate, m.p. 119.8 ° C.

Example 13

The procedure is as described in Example 12, but using equivalent amounts of starting materials to give the following 1,2,4-triazole acid addition salts:

1- [4-butyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole sesquioxalate, m.p. 111.6 ° C

1- (2- (2,4-dichlorophenyl) -4-pentyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate, m.p. 130.3 ° C,

1- (2- (2,4-dichlorophenyl) -4-hexyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate, m.p. 106.2 ° C

[2- (2,4-dichlorophenyl) -4-heptyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate, m.p. 96 ° C, and

1- [2- (2,4-dichlorophenyl) -4-octyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolinitrate, m.p. 110.6 ° C.

Example 14

Proceed as described in Example 1-A, but replacing the 2- (bromomethyl) -2- (2,4-dichlorophenyl) -1,3-dioxolane used therein with an equivalent amount of the corresponding 2- (bromomethyl) -2-aryl-1,3-dioxolane, whereby the following compounds of formula I are obtained:

1- [2- (2,4,6-trichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4 triazole,

1- [2- (2,6-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, and

1- [2- (2-chloro-4-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole.

Example 15

The procedure described in Example 2 can be used to prepare compounds of formula I wherein Z is -CH 2 -CH (CH 2) or -CH (CH 2) -CH (CH 2) -. Using an equivalent amount of 2-aryl-2- (bromomethyl) -4-methyl-1,3-dioxolane or 2aryl-2- (bromomethyl) -4,5-dimethyl-1,3-dioxolane, the following compounds are obtained as nitrates:

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

1- [5- (4-chlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole,

1- [5- (2-chlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole,

<img file="FI62080B_D0010.tif" />

- [4-methyl-2- (4-methylphenyl] -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole,

1- [2- (4-methoxyphenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole,

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

Example 16

The procedure described in Example 1-A can be used to prepare compounds of formula I wherein Z is -CR 2 -CR 2 -CR 2 -. Using an equivalent amount of the corresponding 2-aryl-2- (bromomethyl) -1,3-dioxolane as starting material, the following compounds are obtained:

1- (2-phenyl-1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole,

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

1- [2- (4-chlorophenyl) -1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (4-methylphenyl) -1,3-dioxan-2- ylmethyl7 ~ 1H-1,2,4-triazole,

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

1- [2- (2-thienyl) -1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole, and 1- [2- (2-naphthyl) -1,3-dioxan 2-ylmethyl-7H-1,2,4-triazole.

The compounds of the invention are generally used in the form of suspensions, dustable powders, solutions, ointments, etc. Examples are the following mixtures in which the parts are by weight unless otherwise indicated.

1) Suspension kg of 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2350 ml of water methylmethyl7-1H-1,2,4-triazole technical xylene surfactant in such a quantity as to achieve the desired active ingredient the concentration of the substance

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) The dustable powder is part of 1- [2- (2,4-dichlorophenyl) -r 1,3-dioxolan-2-methylmethyl] -1H-1,2,4-triazole and

360 part of the talc is ground in a ball mill, then 8 parts of olein are added and the grinding is continued, and finally a part of the slaked lime is mixed into the mixture.

The powder thus obtained can be sprayed satisfactorily and has good adhesion. It can be used for pollination and plant protection.

3) A solution of a portion of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole is dissolved in a portion of alkylated naphthalene and the solution thus obtained is sprayed onto fungi-infected targets, or walls, floors or other places you want to protect from fungi.