DK143751B - FUNGICID, BACTERICID AND PLANT-GROWING REGULATORY EFFECTIVE TRIAZOLD DERIVATIVES FOR PLANT PROTECTION USE - Google Patents

Description

(19) DENMARK (^,

® (12) PUBLICATION NOTICE on 143751 B

DIRECTORATE OF

THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 5171/75 (51) lntC | s ς qj q 405/06 (22) Filing Day 17. noV. 1975 C 07 D 409/14 (24) Race day 17- ηον · 1975 A 01 N 43/64 (41) Aim. available May 19, 1976 (44) Presented Oct. 5 1 981 (86) International application no.

(86) International filing day ~ (85) Continuation day “(62) Stock Application No." (30) Priority 18 · Nov 1974, 524587 * US 9 · Oct 1975 * 620989 * υε (71) Applicant JANSSEN PHARMACEUTICA NV, Beerse, BE.

(72) Inventor Gustaaf Van Reet, BE: Jan Heeres, BE: Lourens Wals, BE.

(74) Attorney Th * Ostenfeld Patent bureau A / S.

(54) Fungicide, bactericide and plant = growth regulating active tria = zol derivatives for use in plant protection.

The present invention relates to novel fungicide, bactericidal and plant growth regulating active 1- (p-aryl) ethyl-1H-1,2,4-triazole ketals for use in plant protection.

IN USA. U.S. Patent No. 3,575,999 discloses 1- (β-aryl) ethyl imidazole ketal with anti-bacterial and anti-fungal properties, and in U.S.A. U.S. Patent No. 3,755,349 discloses 1-benzylimidazoles and 1-benzyl-1,2,4-triazoles with antimycotic properties. The compounds of the present invention are particularly distinguished by the compounds thus known in having a broader fungicidal activity spectrum.

In the prior art a number of triazole derivatives can also be found, some of which are described as fungicides or growth regulators. Among other differences, the compounds of the present invention differ from the known triazole derivatives by the nature of the side chain attached to the triazole nitrogen atom.

2 143751

The closest known technique for triazole derivatives is presumed to be represented by the following literature references:

Dutch patent application 69.13028 and French patent 2,200,012 - Derwent Week V25- Pharm. p.7.

The novel compounds of the invention are 1H-1,2,4-triazole derivatives of the formula:

__N

ΓΊ L d> CH_ —C — Ar c / \>

V

wherein Z represents an alkylene group in the form of -CH 2 -CH 2 -, -CH 2 -CH 2 - CH 2 -, -CH-CH- or -CH 2 -CH- H 3 C CH 3 alkyl wherein the alkyl group has from 1 to 10 carbon atoms, and

Ar represents a group in the form of phenyl, substituted phenyl, thienyl, halogen thienyl, naphthyl or fluorenyl wherein "substituted phenyl" means a phenyl group substituted from 1 to 3 substituents selected independently from the group consisting of halogen, C g alkyl, Chalky loxy, cyano and nitro or acid addition salts thereof.

As used above under the definition of Z, the term "alkyl" should include straight and branched hydrocarbon groups having from 1 to 10 carbon atoms, such as e.g. methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, butyl, pentyl, hexyl, heptyl, octyl and decyl.

As used under the definition of Ar, C 1-4 alkyl may be straight or branched hydrocarbon groups having from 1 to 6 carbon atoms, such as e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, pentyl and hexyl, and the term "halogen" is generic for halogen atoms of atomic weight less than 127, i.e. fluorine, chlorine, bromine and iodine.

Due to particularly high activity, especially against certain phytopathogenic fungi, 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 1 - [2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichl -orphenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-propyl-1,2,3 dioxolan-2-ylmethyl] -1H-1,2,4-triazole or acid addition salts thereof preferred compounds of the invention.

3 t437S1

The ketals of formula (I) are readily obtained by reacting 1H-1,2,4-triazole (II) which has been previously converted to a metal salt thereof, such as e.g. by treatment with an alkali metal alkoxide, preferably sodium methoxide, with a halide of formula (III) Y-CH- - C - Ar 2 / O p (III) . The reaction of 1H-1,2,4-triazole (II) with (III). is preferably carried out in a suitable polar for the reaction inert organic solvent, e.g. Ν, Ν-dimethylformamide, N, N-dimethylacetamide, acetonitrile or benzonitrile. Such solvents can be used in combination with other inert organic solvents, such as e.g. benzene, methylbenzene, dimethylbenzene and the like. When Y represents bromine or chlorine, it is appropriate to add an alkali metal iodide, such as e.g. sodium or potassium iodide. Slightly elevated temperatures are appropriate to increase the reaction rate and most preferably, the reaction is carried out at the reflux temperature of the reaction mixture.

The resulting ketone of formula (I) is then isolated from the reaction mixture in a conventional manner and, if desired, further purified according to conventional purification methods such as e.g. crystallization, extraction, trituration or chromatography.

The foregoing procedure is further illustrated by the following reaction scheme: Y-CH-C-Ar 2 / \ (III) li-Γ ° N 7 * J> NaOMC - _1- ()

H

DMF, Nal (Π)

The compounds of formula (I) thus obtained in base form can be converted to their acid addition salts by reaction with a suitable acid, such as e.g. an inorganic acid such as hydrogen halide, i.e. hydrogen chloride, hydrogen bromide or hydrogen iodide acid, sulfuric, nitric or thiocyanic acid, a phosphoric acid, an organic acid such as acetic, propionic, hydroxyacetic, α-hydroxypropionic, 2-oxopropionic, oxalic, malonic , amber, maleic, fumaric, apple, wine, 2-hydroxy-1,2,3-propane tricarboxylic, benzoic, 3-phenylpropionic, α-hydroxybenzeneacetic, methanesulfone, ethanesulfone -, hydroxyethanesulfone? 4-methylbenzenesulfone, α-hydroxybenzoic, 4-amino-2-hydroxybenzoic, 2-phenoxybenzoic or 2-acetyloxybenzoic acid. The salts can again be converted to the corresponding free bases in the usual manner, e.g. by reaction with base such as sodium or potassium hydroxide.

The starting materials of formula (III), a number of which are known compounds, can be prepared according to known methods. Compounds wherein Z represents -CH 2 -CH 2 -, -CH (CH 3) -CH 2 -, -CH (CH 3) -CH (CH 3) - or -CH 2 -CH 2 -CH 2 - and processes for their preparation are described in U.S.A. Patent No. 3,575,999. In general, the compounds of formula (III) can be prepared by the ketization of a suitable ketone of formula (IV) wherein Ar and Y have the above meanings, 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 process, both reactants are refluxed for several hours with azeotropic water removal in a suitable organic solvent, preferably in the presence of a simple alcohol, e.g. ethanol, propanol, butanol or pentanol, and in the presence of a suitably strong acid such as e.g. 4-methyIbenzensulfonsyre. Suitable organic solvents which may be used therefore include, for example, aromatic hydrocarbons such as benzene, methylbenzene, dimethylbenzene and the like and saturated hydrocarbons such as cyclohexane.

0

Ar-C-CH₂ Y + HO-Z-OH .. ± th e Iben zens Ulphonic Acid (III) 2 Butanol * (IV) (V)

The ketones of formula (IV) are well known in the art and can be prepared by methods known per se.

From formula (I), it is clear that several of the compounds of the present invention contain asymmetric carbon atoms in the structure and therefore may exist in various stereochemically optically isomeric forms. More particularly, when an alkyl group is present in the 4-position of the dioxolane nucleus, the carbon atom to which it is attached and the carbon atom in the 2-position of the dioxolane nucleus are asymmetric. The stereochemical optical isomers of the compounds of formula (I) can be separated and isolated by methods known per se. These isomers fall within the scope of the invention.

The compounds of formula (I) and the acid addition salts thereof are valuable agents for controlling fungi and bacteria. As such, the compounds of the invention are valuable for treating plants suffering from pathogenic microorganisms and for destroying microorganisms on materials.

The compounds of the invention are very potent agricultural fungicides. They are very active against a wide variety of fungi, such as those that cause the occurrence of mildew in various plant species, e.g. Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pannosa, Sphaerotheca mors-uvae. Uncinula necator and other fungi such as Venturis inaequalis, Colletotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenuis, Thielaviopsis basicola, Helminthosporium gramineum and Penicillium digitatum.

They are particularly valuable because of their prophylactic, as well as curative and systemic effects. Their powerful antifungal effect on phytopathogenic fungi is elucidated by the results referenced in the experiments below.

In a number of these experiments, the compound 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, (Ia), which is representative of the compounds of formula (I).

k-A-b-ci I-J (I-a)

It is to be understood that the compounds for which experimental test results are stated must exemplify the strong anti-fungal activity of all the compounds of formula (I).

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

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Young cucumber plants, ca. 10 days old, was sprayed with an aqueous solution containing 250, 100 or 10 ppm of the compound to be tested while control plants were not treated. After drying the plants, artificial infection was carried out with spores of Erysiphe cichoracearum by lightly rubbing the plants with a heavily infected leaf. On the 15th day after artificial infection, the degree of fungal attack was assessed by counting the number of spots per day. plant. The results listed in Table I are mean values for two plants and are expressed according to the following point system.

0 = 0 spots per plant 1 = 1-5 spots per. plant 2 = 6-10 spots per plant 3 = more than 10 spots per plant TABLE I: Prophylactic effect of compounds (I) against Erysiphe cichoracearum on cucumber plants by foliar treatment.

R-N

||

NV

in

CH

CT

Ar R Base or Antifungal Point Value _s all tf worm_250 ppm 100 ppm 10 ppm 2.4- (Cl) 2-C6H3 H base - 0 0 C6.H5 H base - 3 - 4-NO2-CgH4 H base 0 - 3 — Cl -CCH. H base - 2 - 6 4 2-ci-c6h4 H (cooh) 2 - 0 - 4-Br-CgH ^ H base 0 - 2-Br-CgH4 H (COOH) 2 2 3-OCH3-CgH4 H (COOH) 2 1 2-CH3-CgH4 H (COOH) 20 4-F-CgH4 H (COOH) 20 4-CH3-CgH4 H (COOH) 20 4-Cl-CgH4 H (C00H) 2, H2 O - O - 2-naphthyl H (COOH) 20 2.5- (Cl) 2-CgH3 H (COOH) 2- O-4-CN-CgH4 H (COOH) 20- - 3,4- (Cl) 2-CgH3 H (COOH) 2 3 7 143751

Table I (continued)

Ar R Base or Antifungal Point Value _ Salt Form_250 ppm 100 ppm 10 ppm 2-OCH3-CgH4 H (C00H) 2 1 2-thienyl H (COOH) 2 2 2- fluorenyl H base o - -5-Cl-2-thienyl H base 2 3- Br, 4-CH3-C6H3 H base 0 2-CH3,4-Br-CgH3 H base - 2 2- CH3,4-Cl-CgH3 H base 0 - 3- Br-CgH4 H base 2 4- I -CgH4 H (COOH) 20 3f5- (Cl) 2-CgH3 H (COOH) 2 2 2.3- (Cl) 2-CgH3 H (COOH) 20 3-NO2 ~ CgH4 H base 1 2.4- (Br) 2 -CgH3 H (COOH) 2 -1-2,4 / 5- (Cl) 3-CgH2 H (COOH) 20 2-Cl, 4-OCH3CgH3 H (COOH) 2 2 2.4- (Cl) 2 "CgH3 CH3 HN03 0 2.4- (Cl) 2 "CgH3 C2H5 HN03 - 0 0 2.4- (Cl) 2-CgH3 nC3Hy HN03 0 0 2.4- (Cl) 2-CgH3 nC4H9 11/2 (COOH) 2 - 2- 2.4- (Cl ) 2-CgH3 nC5Hi; L HN03 - 0 0 2.4- (Cl) 2-CgH3 nCgHi3 HN03 0 2.4- (ci) 2-CgH3 nC7H15 HN03 2 2.4- (Cl) 2-CgH3 nC8H17 HNOg 0 All Prophylactic effect against Erysiphe on cucumbers by foliar treatment.

Young single-leaf cucumber plants were sprayed with an aqueous solution containing 500, 250 or 125 ppm of (I-a), while the control plants were not treated. Artificial infection with spores of Erysiphe polyphaga was done by lightly rubbing the plants with a heavily infected leaf on the 4th, 6th or 8th day after treatment. On the 18th and 34th days after treatment, the percentage of leaf surfaces that were attacked by the fungus was determined separately for the infected leaves and for the newly formed leaves. The results presented in Table 1.1 are mean values for 5 plants and are expressed in percent attack versus untreated.

8 143751 TABLE 1.1: Prophylactic effect on (I-a) of Erysiphe polyphaga on cucumber by foliar treatment

Assessment time 18 days after treatment 34 days after treatment Infected on indicated day after treatment 468 468

Infected leaves (a) 'or newly formed leaves (b) ababab ababab

Concentration of "(I-a) in syringe solution

Untreated 100 100 100 100 100 100 100 100 100 100 100 100 500 dpm 000000 000000 250 dpm 000000 000000 125 dpm 000000 000000 B. Prophylactic effect of Erysiphe graminis on barley by soil treatment.

Barley plants were treated by irrigation at 100 ml. plant of an aqueous solution containing 1000, 100 or 10 ppm of (I-a). Control plants received the same volume of solution without (I-a). Natural infection, which usually occurs when the plants are kept in a greenhouse near infected plants, was assessed 16 days after treatment by counting the number of spots on leaves. For each object, 5 plants were used, and the results in Table II are mean values expressed in percent attacks compared to the control plants.

TABLE II: Prophylactic effect of (I-a) on Erysiphe graminis on barley by soil treatment.

Dose in mg (I-a) per plant% attack versus control

Control 100 100 mg 0 10 mg 0 1 mg 53 C. Curative effect on Erysiphe graminis on barley by leaf treatment.

Barley plants attacked by Erysiphe graminis were sprayed with an aqueous solution containing (I-a) at the indicated concentration. On the 16th day after treatment, the number of spots per day was determined. plant. Pr. 5 plants were used and the results listed in Table III are 9 143751 mean values expressed as a percentage of attack versus control.

TABLE III; Curative effect of (I-a) on Erysiphe graminis on barley by leaf treatment.

Concentration of (I-a)% attack relative to spray solution for control_ 0 100 1000 ppm 0 100 ppm 1/5 10 ppm 25 D. Prophylactic effect of (I-a) against Podosphaera leuchotricha on apple cuttings by spraying.

One year old apple cuttings were sprayed with an aqueous solution containing (I-a) at the indicated concentration. The plants were artificially infected as described in experiment "A" with spores of Podosphaera leuchotricha 1 day after treatment and incubated for 36 hours. The degree of fungal attack was assessed 25 days after treatment by counting the number of spots. Two plants were used per object and the results , which are listed in Table IV, are mean values expressed as percent attack versus control.

TABLE IV: Prophylactic effect of (I-a) on Podosphaera leucotricha on apple cuttings by spraying.

Concentration of (I-a)% attack relative to syringe solution for control_ 0 100 100 ppm 0 10 ppm 6 E. Activity against Thielaviopsis sp.

Slices of potato and leek, 5 mm thick, were dipped in an aqueous test solution containing (I-a) at the indicated concentration. After dipping, the slices were placed on filter paper in a large plastic tray and the tray was covered with glass. 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.

Mushroom growth on the slices was assessed 6 days after treatment by estimating the surface affected by the fungus. The results, which are listed in Table V, are expressed in percentage attacks relative to the control.

TABF-T. V; Activity of (I-a) against Thielaviopsis sp.

Concentration of (I-a) in% of attack compared to the test solution in ppm. control_ _ Potato leek 0 100 100 1000 0 0 100 0 0 10 0 42.8 1 11 100

In addition to the antimicrobial effects, the compounds of formula I possess valuable plant growth regulating properties. Depending on various factors, such as the plant species under treatment and the dose of active ingredient administered, the observed effect may be both growth stimulation and growth inhibition. As such, the compounds of the invention are valuable as plant growth regulators. More particularly, they can be used as plant growth inhibitors or stimulators, especially as inhibitors of wild shoots or side shoots, e.g. on tobacco plants. However, under certain circumstances, they can also be used as plant growth stimulants.

The plant growth regulating properties of the compounds of formula I are further elucidated by the results obtained in the following experiments in which compound (I-a) was used as representative of the compounds of the invention. The results obtained with (I-a) are set forth to exemplify the valuable plant growth regulating properties of all the compounds of formula I.

F. Growth-regulating effect on tomato plants by soil treatment.

Young tomato plants 3.5-4 cm tall were planted in separate pots. Each pot was watered with a test solution containing the indicated amount of (I-a). Growth was assessed by determining the length and weight of the plants 28 days after treatment.

The results listed in Table VI are the mean values of five plants expressed as a percentage compared to the control plants.

U 143751 TABLE VI: Growth regulating effect of (I-a) on tomato plants by soil treatment.

Dose of (I-a) Length of plants in% Weight of plants in% in mg / plant_ compared to control_ compared to control none 100 100 10 114 118 1 127 134 0.1 122 116 G. Growth-regulating effect on barley by foliar treatment.

Young barley plants in the 3-4 leaf stage were sprayed with a test solution containing (I-a) at the indicated concentration. The effect on plant growth was assessed 24 days after treatment by determining the weight of the plants. The results listed in Table Will are the mean values of 10 plants expressed as a percentage compared to the controls.

TABLE_Vfl'The growth regulating effect of (I-a) on barley by foliar treatment.

Concentration of (I-a) in Average weight of plants in test solution in ppm percent of control_ none 100 125 126 60 116 H. Control of wild shoots or side shoots of tobacco plants.

Tobacco plants, var. "Xanthi" was grown in greenhouses and topped in the early bud city.

After 5 days, foliar spray treatment was carried out with an aqueous suspension of compound (I-a) at amounts equal to 3 and 1.5 kg of active ingredient per day. ha.

Each treatment was repeated three times. Twelve days after application, the subsequent growth of wild shoots or lateral shoots was compared with the growth of the topped and untreated control plants.

The recorded reductions in the growth of wild shoots or side shoots were 100% at 3.0 kg / ha applied amount and 90% at 1.5 kg / ha.

I. Growth inhibition on soybean plants.

Soybean plants, var. Hark was grown in pots in growth chamber at 23 ° C, 20,000 Lux and a daylength of 14 hours. When the third trifoliate leaf was unfolded, the plants were sprayed with an aqueous suspension of compound (I-a) at concentrations of 1000, 500, 100 and 50 ppm active ingredient.

Percent growth inhibition of the treated plants compared to the control was examined after 14 days.

The following results were obtained:

Treatment_% growth inhibition (I-a) 1000 ppm a-i- 70% 500 ppm a.i. 40% 100 ppm a.i. 25% 50 ppm a.i. 0% control 0%

At the concentration of 1000 ppm, a more intense green color of the leaf was observed.

COMPARISON TRIALS

The following compounds of the invention: ir-f

CH2-R

No. R

Cl 1? C \ p> -ci

L_I

Cl 2> c- <q) -ci 0 oN— '1 _Lch3 13 WW1

No. Cl 3 VcC (C) - C10 oN - 1 -L CAH9 (n)

Cl 4 -sM-ci 0 oN— 1 _i— (n) o o 11

R

Cl

«> Cc \ p) -CI

0 o '-' 1 -Lc2h5 H3C J-Lch3 was compared with the compound: U "" ν'-ς® ''

LJ

14 143751 according to U.S. Patent No. 3,575,999 and the compound

U

B I

C (W2> C <H

0 0 | J hydrochloride ch3 ch3 according to US Patent No. 3,755,449 in respect of fungicidal activity.

15 143761

Test Methods 1. Effect against Puccinia triticina on wheat plants (Residual protection) 6 day old wheat plants were sprayed wet dripping with a substrate (containing 600, 200, 60 and 20 ppm active ingredient) made from a wettable powder of the active ingredient.

Twenty-four hours later, the treated plants were uniformly infected with a summer spore suspension of the fungus. After incubation for 48 hours at 95 - 100% relative humidity and about 20 ° C, the infected plants were placed in a greenhouse at ca. 22 ° C. The number and size of the infected areas served as a criterion for assessing the activity of the test compound. Wheat plants treated with Compounds Nos. 1 to 7 were slightly shorter than those treated with Comparative Compounds A and B as well as the untreated control plants.

2. Effect against Venturia inaequalis on apple tree cuttings (Residual protective action) Apple cuttings with new shoots of 10 - 20 cm length were sprayed with a spray emulsion (containing 600, 200 and 60 ppm active ingredient) prepared from a wettable powder of the active ingredient. After 24 hours, the treated plants were infected with a conidia spore suspension of the fungus. The plants were then incubated for 5 days at 90 - 100% relative humidity and transferred for an additional 10 days to a greenhouse at 20 - 24 ° C. An assessment of scab attacks was made 15 days after the plants had become infected.

3. Effect on Cercospora arachidicola on peanut plants (residual protective effect)

Peanut plants 10 to 15 cm tall sprayed red a spray substrate (containing 200, 60, 20 and 6 ppm active ingredient) made from a wettable powder of the active ingredient and infected 48 hours later with a conidium suspension of fungus. The infected plants were incubated for 24 hours at ca. 21 ° C

16 143751 and high humidity and then placed in a greenhouse until the appearance of the typical leaf spots. Assessment of the fungicidal effect based on the number and size of the spots was made 12 days after infection.

4. Effect against Erysiphe qraminis on barley plants (Residual protective effect)

Barley plants of approx. Height of 8 cm was sprayed with a spray emulsion (containing 200, 50, 20, 6 and 2 ppm of active ingredient) prepared from a wettable powder of the active ingredient.

After 48 hours, the treated plants are powdered with conidia spores by the fungus. The infected barley plants were stored in a greenhouse at approx. 22 ° C and the fungal attack was assessed after 10 days.

5. Effect against Puccinia triticina on wheat plants (Systemic effect) 5 day old wheat plants were irrigated with a substrate (60, 20 and 6 ppm active ingredient) made from a wettable powder of the active ingredient. Care was taken to ensure that the substrate did not come into contact with the plant's air portions. After 48 hours, the treated plants were uniformly infected with a summer spore suspension of the fungus. Ether incubation for 48 hours at 95 - 100% relative humidity and approx. At 20 ° C, the infected plants were placed in a greenhouse at approx. 22 ° C. The number and size of the infected areas served as a criterion for assessing the activity of the test compound. Wheat plants treated with Compounds Nos. 1 to 7 were slightly shorter than those treated with Comparative Compounds A and B as well as the untreated control plants.

6. Effect against Erysiphe qraminis on barley plants (Systemic effect) 8 cm tall barley plants were irrigated with a substrate (60, 20, 6 and 2 ppm active ingredient) made from a wettable powder of the active ingredient. After 48 hours, the treated plants are powdered with conidia spores by the fungus. The infected barley plants were placed in a greenhouse at approx. 22 ° C and the fungal attack was assessed after 10 days.

17 143751

Test results

The results obtained are shown in Table VIII below, where the concentration of the active ingredient is given in ppm (600 ppm = 0.06% active ingredient), in experiments 1-4 (residual activity) with respect to test substrate and in experiments 5-6 (systemic activity) in terms of soil volume.

The activity is expressed as the percentage attack compared to untreated control plants (= 100%). The percentage attack falls in one of the following four areas: 0 = 0 - 5% attack 1 = 5 - 20% attack 2 = 20 - 50% attack 3 = 50 -100% attack (connection inactive)

Each experiment was performed twice.

18 143751 cm cm h cm cs cs h «—ii — i cm cm η h« -n cm 'η h con

^ vo HH rHrH (- (ΓΊ iH rH rH rH CM CM rH rH N N ^ H

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D. p O.

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CT JJ

p ^ w

w w 2 OO O O O O O O O O O O O O O O CMH

^ VD HH rH CS HH rH fsj O rH τ-HtH O O HH HH

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vD HH O rH Η N O rH CM CM O Ή O O HH HH

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vO C rH O O O O O O N CM rH rH ΟΉ CM H CM CS

t3 Ή O • ιΗ Ιβ O

C 3 CM H rH C O O O O O „-O rH rH (Μ O O CSCS H {v | Ή Ό υ · Η 0 tn o

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p_, μ vo OO O O O O O O O O O O O O Ή cm rH, -h

S

-H 0) Λ tn M i — i

h> S nrHCS H Sj- H VO Γ- C PQ

In view of the aforementioned antifungal, antibacterial and growth regulating effects, the present invention provides valuable compositions comprising the present ketals (I) or the acid addition salts thereof as active ingredient in a solvent or solid, semi-solid or liquid diluent or carrier, and it provides further, an effective method for controlling fungal or bacterial growth using an effective anti-fungal or anti-bacterial amount of such ketals (I) or salts thereof.

The present compounds can be used in suitable solvents or diluents in the form of emulsions, suspensions, dispersions or ointments, on suitable solid or semi-solid carriers in ordinary or synthetic soaps, detergents or dispersion media, if desired, together with other compounds with arachnicide, insecticide, ovicide, fungicidal or bactericidal effects or together with inactive additives.

Solid carriers suitable for the preparation of powder form compositions comprise various inert, porous and powdery distribution agents of inorganic or organic nature, such as e.g. tricalcium phosphate, calcium carbonate in the form of formed chalk or ground limestone, kaolin, bolus, bentonite, talc, silica and boric acid; powdered cork, sawdust and other fine powdery materials of vegetable origin are also suitable carrier substances.

The active ingredient is mixed with these carrier substances, e.g. by being ground therewith. Alternatively, the inert carrier is impregnated with a solution of the active component in a slightly volatile solvent, and the solvent is then eliminated by heating or by filtration under suction at reduced pressure. By the addition of wetting and / or dispersing agents, such powdered preparations can also be made slightly wettable with water so that suspensions are obtained.

Inert solvents used in the preparation of liquid preparations should preferably not be easily combustible and should, as far as possible, be odorless and, as far as possible, non-toxic to warm-blooded animals or plants in the relevant environment. Suitable solvents for this purpose are high boiling oils, e.g. of vegetable origin or lower boiling solvents having a flash point of at least 30 ° C, such as e.g. polyethylene glycol, isopropanol, dimethyl sulfoxide, hydrogenated naphthalenes and alkylated naphthalenes. Of course, it is also possible to use mixtures of the solvent. Solutions may be prepared in the usual manner, if necessary with the aid of solution-promoting agents. Other liquid forms which may be used consist of emulsions or suspensions of the active compound in water or suitable inert solvents or concentrates to prepare such emulsions which can be adjusted directly to the desired concentration. For this purpose, the active ingredient may e.g. mixed with a dispersant or emulsifier. The active ingredient may also be dissolved or dispersed in a suitably inert solvent, and at the same time or later mixed with a dispersing or emulsifying agent.

It is also possible to use semi-solid carrier substances of a creamy ointment, paste or waxy nature in which the active component can be incorporated if necessary by means of solvents and / or emulsifiers. Vaseline and other cream bases are examples of semi-solid carrier substances.

Furthermore, it is possible to use the active component in the form of aerosols. To this end, if necessary, the active component is dissolved or dispersed by suitable inert solvents, such as carrier liquids, such as difluorodichloromethane, which, at atmospheric pressure, boil at a temperature below room temperature or in other volatile solvents. In this way, pressurized solutions are obtained which, upon spraying, form aerosols which are particularly suitable for the control or control of fungi and bacteria, e.g. in enclosed chambers and storage rooms and for application to vegetation to eradicate or prevent fungal or bacterial infections.

The present compounds and compositions thereof can be applied by conventional methods. Eg. For example, a fungal or bacterial attack or material to be treated or protected against fungal or bacterial attack may be treated with the compounds and compositions thereof by powdering, splashing, spraying, brushing, dipping, lubricating, impregnating or by means of other suitable agents.

When the present compounds are used in combination with suitable carriers, e.g. in solution, suspension, powder, powder, ointment, emulsion and similar forms, a high activity over a very large dilution range is observed. Eg. For example, it has been found that concentrations of the active ingredient ranging from 0.1 to 10% by weight based on the weight of the composition used are effective in controlling fungi or bacteria. Of course, higher concentrations can also be used if desirable in a given situation.

The following examples illustrate the preparation of compounds of the invention and their intermediates. Unless otherwise stated, all parts are parts by weight.

Example 1

A stirred and cooled (0 ° C) solution of 30 parts of 1- (4-amino-2-methoxyphenylethethanone in 360 parts of concentrated hydrochloric acid, 75 parts 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 After stirring for 30 minutes at 0 ° C, the whole is poured onto a solution of 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid while stirring. The mixture is heated for 1 hour at 60 ° C. After cooling to room temperature, the product is extracted twice. The combined extracts are washed sequentially with water, dilute sodium hydroxide solution and again twice with water, dried, filtered and evaporated to give 28 parts (76%) of 1- (4-chloro-2-methoxy) -phenyl) ethanone, m.p. 55 ° C.

Example 2

To a stirred mixture of 78.8 parts of 2-bromo-1- (4-bromo-2-methyl-phenyl) -1-ethanone and 200 parts of butanol are added 3 parts of 4-methylbenzenesulfonic acid and 225 parts of benzene. Next, 33.5 parts of 1,2-ethanediol are added dropwise. When this has happened, stirring is continued overnight at reflux temperature with water separator. 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 2,21-oxybispropane. The combined organic layers are washed with water (for neutralization), 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

Using the procedure of Example 2 and using an equivalent amount of a suitable 1-aryl-2-bromo-1-ethanone instead of the one used 2-bromo-1- (4-bromo-2-methylphenyl) -1 Ethanol is prepared from the following 2-aryl-2-bromomethyl-1,3-dioxolanes: 4- [2- (bromomethyl) -1,3-dioxolan-2-yl] benzonitrile, m.p. 92.4 ° C, 2- (bromomethyl) ) -2- (2-naphthalenyl) -1,3-dioxolane, m.p. 64 ° C.

22 143751

Example 4 57 parts (1- (5-chloro-2-thienyl) -1-ethanone are dissolved in 220 parts 1,2-ethanediol at 50 ° C. With stirring, 64 parts of bromine are added dropwise over a period of 1 hour. After stirring for 1 hour at room temperature, 4 parts of 4-methylbenzenesulfonic acid and 360 parts of benzene are added, all stirred and refluxed overnight with water separator. The reaction mixture is evaporated and the residue is collected in 2,2'-oxybispropane. The solution is washed successively once with dilute sodium hydroxide solution and three times with water, dried, filtered and evaporated to give 73.3 parts (64.5%) of 2- (bromomethyl) -2- (5-chloro-2). -thienyl) -1,3-dioxolane, boiling point 125-127 ° C at 0.1 mm pressure.

Example 5

By analogy to the procedure of Example 4 and using an equivalent amount of an appropriate 1-aryl-1-ethanone instead of the one using 1- (5-chloro-2-thienyl) -1-ethanone, the following 2-aryl 2- (bromomethyl) -1,3-dioxolanes: 2- (bromomethyl) -2- (9H-fluoren-2-yl) -1,3-dioxolane, m.p. 90 ° C, 2- (bromomethyl) -2- ( 3-bromo-4-methylphenyl) -1,3-dioxolane, bp 126-130 ° C at 0.1 mm pressure, 2- (bromomethyl) -2- (4-iodophenyl) -1,3-dioxolane, m.p. ° C, 2- (bromomethyl) -2- (4-chloro-2-methoxyphenyl) -1,3-dioxolane, m.p. 110 ° C, and 2- (bromomethyl) -2- (2,4-dibromophenyl) -1 , 3-dioxolane, m.p. 96 ° C. Example 6 A. To a stirred solution of 2.3 parts sodium in 120 parts methanol is added 6.9 parts 1H-1,2,4-triazole in 150 parts dimethylformamide. The methanol is removed under normal pressure to an internal temperature of 130 ° C. Next, 25 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -1,3-dioxolane are added. The reaction mixture is stirred and refluxed for 3 hours. It is left to cool to room temperature and poured on water. The precipitated product is filtered off and crystallized from diisopropyl ether (activated charcoal) to form 12 parts of 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4- triazole, mp 109.9 ° C.

23 T437δ 1 Β. 6 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole are converted to the nitrate salt of 2,2'-oxybispropane. After cooling, the salt is filtered off 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-triazole , nitrate, m.p. 172.7 ° C.

C. 6 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole are converted to the sulfate salt in 2,2'-oxybispropane. The sulfate salt formed is filtered off and crystallized from 2-propanol. The product is filtered off and recrystallized from ethanol (activated charcoal) to form 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

To a stirred solution of 2.3 parts sodium in 80 parts methanol is added 6.9 parts 1H-1,2,4-triazole and 2 parts sodium iodide in 100 parts Ν, Ν-dimethylformamide. The methanol is removed under normal pressure to an internal temperature of 130 ° C. Next, 34.4 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-methyl-1-1,3-dioxolane are added and the whole is 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 concentrated nitric acid 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-1,3-dioxolan-2-ylmethyl] -1 1,2,4-triazole, nitrate, mp 137.8 ° C.

Example 8

To a stirred sodium methoxide solution prepared from 2.8 parts of sodium in 48 parts of methanol is added 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. Next, 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 3 hours. The reaction mixture is cooled to room temperature and poured onto water. Upon scraping, the product precipitates. It is sucked off, washed with water, dried and crystallized from a mixture of ethanol and 2,2'-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, m.p. 127.3 ° C.

24 143751

Example 9

By analogy to the procedure of Example 8 and using an equivalent amount of an appropriate 2-aryl-2- (bromomethyl) -1,3-dioxolane instead of the one that used 2- (bromomethyl) -2-phenyl-1,3 -dioxolane is obtained from the following 1,2,4-triazoles: 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, 1- [2- (4-bromophenyl) -1 , 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 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. , 4 ° C, and 1- [2- (3-nitrophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 154.1 ° C.

Example 10

To a stirred sodium methoxide solution prepared from 1.6 parts of sodium in 48 parts of methanol is added 4.9 parts of 1H-1,2,4-triazole. After stirring for 1 hour at room temperature, 135 parts of N, N-dimethylformamide are added. The methanol is distilled off under normal pressure to an internal temperature of 130 ° C. Next, 17.4 parts of 2- (bromomethyl) -2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are added successively. It is all stirred and refluxed overnight. After cooling to room temperature, the reaction mixture is poured onto water. Upon scraping, the product precipitates, which is filtered off and washed with water. The product, dissolved in trichloromethane, is purified by column chromatography over silica gel using a mixture of trichloromethane and 5% 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 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, mp 181.4 ° C.

Example 11

By analogy to the procedure of Example 10 and using equivalent amounts of the appropriate starting materials, the following are prepared: 1- [2- (9H-fluoren-2-yl) -1,3-dioxolan-2-ylmethyl] -1H-1,2 , 4-triazole, mp 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 ° C, 1- [2- (4-bromo-2-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 148.1 ° C, and 1- [2- ( 4-chloro-2-methylphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 147.9 ° C.

Example 12

To a stirred sodium methoxide solution prepared from 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 Ν, Ν-dimethylformamide. The methanol is removed under normal pressure until an internal temperature of 130 ° C is reached. Next, 27.8 parts of 2- (bromomethyl) -2- (2-chlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are added. It is all stirred and refluxed for 6 hours. The reaction mixture is allowed to cool to room temperature, poured onto water and the product is extracted three times with 1,1'-oxybisethane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is converted to ethanedioate salt in 4-methyl-2-pentanone. The salt is filtered off and recrystallized from 4-methyl-2-pentanone to give 16 parts of 1- [2- (2-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolethanedioate, m.p. 156.5 ° C.

Example 13

By analogy to the procedure of Example 12 and using equivalent amounts of the appropriate starting materials, the following 1,2,4-triazolethanedioate salts are prepared:

ISLAND

In Ar CHiK>

i_I

26 143751

Ar Acid salt Melting point

2- Br-CgH 4 (COOH) 2 172.1 ° C

3- OCH3-C6H4 (COOH) 2 155.6 ° C

2-CH3-CgH4 (COOH) 2 177.1 ° C

4- F-C, H. (C00H) 9 185.5 ° C

4-CH3-CgH4 (COOH) 2 151.2 C

4-Cl-CgH 4 (COOH) 2, H 2 O 169.1 ° C

4-OCH3-CgH4 (COOH) 2 187.1 ° C

2-naphthalenyl (COOH) 2 175 ° C

2.5- (Cl) 2-CgH3 (COOH) 2 173.7 ° C

4-CN-CCH. (COOH) ~ 186.3 ° C

3.4- (Cl) 2-CgH3 (COOH) 2 182.2 C

2-thienyl (COOH) 2 144.5 ° C

2.4- (Br) 2-c6h3 (COOH) 2. 190.3 ° C

Example 14

To a stirred sodium methoxide solution prepared from 2.3 parts of sodium in 48 parts of methanol is added 6.9 parts of 1H-1,2,4-triazole. After stirring for 30 minutes at room temperature, 135 parts of N, N-dimethylformamide are added. The methanol is distilled off under normal pressure to an internal temperature of 130 ° C. Next, 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. After cooling to room temperature, the reaction mixture is poured onto 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 5% methanol as eluent. The pure fractions are collected and the eluent is evaporated. The residue is converted to the ethanedioate salt in 4-methyl-2-pentanone. The salt is filtered off and recrystallized from a mixture of 2-propanone and 2,21-oxybispropane (2: 1 by volume) to give 5.5 parts (26%) of 1- [2- (2-methoxyphenyl) - dioxolan-2-ylmethyl-1H-1,2,4-triazolethanedioate, m.p. 166.4 ° C.

Example 15

By analogy to the procedure of Example 14 and using equivalent amounts of a suitable starting material, the following 1,2,4-triazolethanedioate salts are prepared: 1- [2- (4-iodophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1, 2,4-triazolethanedioate, m.p. 169.8 ° C, 1- [2- (3,5-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole-ethanedioate, m.p. 204.4 ° C, 27 143751 1- [2- (2,3-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole-ethanedioate, m.p. 188.4 ° C , 1- [2- (4-Chloro-2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolethanedioate, m.p. 173.2 ° C, 1- [2- ( 2,4,5-trichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolethanedioate, m.p. 178.4 ° C, and 1- [2- (2-chloro-4- methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazolethanedioate, m.p. 188.2 ° C.

Example 16

To a stirred mixture of 9.5 parts of 1H-1,2,4-triazole and 225 parts of Ν, Ν-dimethylformamide is added portionwise 4.2 parts of a 78% sodium hydride dispersion. After stirring until foaming ceases, 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 onto 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 a mixture of trichloromethane and 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is converted 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%) of 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl ] -1H-1,2,4-triazole, nitrate, mp 132.6 ° C.

Example 17

To a stirred sodium ethoxide solution prepared from 3.8 parts of sodium in 40 parts of methanol are added 11.5 parts of 1H-1,2,4-triazole and 225 parts of Ν, Ν-dimethylformamide. The methanol is distilled off to an internal temperature of 150 ° C. After adding 19 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane, it is all stirred and refluxed for 4 hours. The reaction mixture is cooled and poured onto 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 a mixture of trichloromethane and 2% methanol as eluent. The first fraction is collected and the eluent is evaporated. The residue is converted to the nitrate salt 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-ylmethylJ-1H-1H-triazole nitrate, mp 119.8 ° C.

28 143751

Example 18

By analogy to the procedure of Example 17 and using equivalent amounts of a suitable starting material, the following 1,2,4-triazoleic acid addition salts are prepared: 1- [4-butyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl ] -1H-1,2,4-triazole sesquiethandioate, mp 111.6 ° C, 1- [2- (2,4-dichlorophenyl) -4-pentyl-1,3-dioxolan-2-ylmethyl] -1H-1.2.4 triazole, nitrate, m.p. 130.3 ° C, 1- [2- (2,4-dichlorophenyl) -4-hexyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, nitrate, m.p. 106.2 ° C, 1- [2- (2,4-dichlorophenyl) -4-heptyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, nitrate, m.p. 96.8 ° C and 1- [2- (2,4-dichlorophenyl) -4-octyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, nitrate, m.p. 110.6 ° C.

Example 19

A 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 30 minutes with water separator. Next, 7.1 parts of 1- [2- (2,4-dichlorophenyl) -2,2-dimethoxyethyl] -1H-1,2,4-triazole-4-methylbenzenesulfonate are added and refluxing is continued for 4 hours. The reaction mixture is cooled, diluted with 1,1'-oxybisethane, and the whole is washed with a dilute solution of sodium hydroxide and with water. A concentrated nitric acid solution is added and the nitrate salt precipitates. It is filtered off and crystallized from a mixture of 2-propanol and 2,2'-oxybispropane to give 2.2 parts (39%) of 1- [2- (2,4-dichlorophenyl) -1,3-dioxane-2- ylmethyl] -1H-1,2,4-triazole, nitrate; mp 143.1 ° C.

Example 20

A mixture of 1.8 parts of 2,3-butanediol, 1 part of 4-methylbenzenesulfonic acid and 90 parts of methylbenzene is azeotropically distilled to dryness (1 hour). Next, 7.1 parts of 1- [2- (2,4-dichlorophenyl) -2,2-dimethoxyethyl] -1H-1,2,4-triazole-4-methylbenzenesulfonate are added and stirred for approx. 16 hours at reflux temperature. The reaction mixture is cooled and diluted with a sodium hydroxide solution. The product is extracted with 1,1'-oxybispropane. The extract is washed with water, dried, filtered and evaporated. The residue is converted to the nitrate salt in 2,21-oxybispropane. The salt is filtered off and crystallized from a mixture of acetonitrile and 2,2'-oxybispropane. The product is filtered off and dried to give 4.6 parts of 1-12- (2,4-dichlorophenyl) -4,5-dimethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4- triazole, mononitrate; mp 125 ° C.

Example 21.

The compounds of the invention are used in the usual forms for the control of fungi or bacteria, e.g. such as suspensions, powders or solutions. This aspect of the invention is further elucidated below, with all parts being parts by weight, unless otherwise stated.

(1) SUSPENSION: 1 kg ... 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 21 ... technical xylene , 350 ml ... surfactant, water ... dilute to desired concentration of active ingredient.

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

(2) POWDER: 20 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole are triturated with 360 parts of talc on a ball mill, then 8 parts olein is added and the comminution is continued and finally the mixture is mixed with 4 parts of slaked lime. The powder formed can be sprayed satisfactorily and has good deicing power. It can be used for powdering or for plant protection purposes.

(3) SOLUTION: 5 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole are dissolved in 95 parts of alkylated naphthalene and used as a spray for treatment of fungus-infected subjects or on walls, floors or other objects to prevent fungi infection.