DE2551560A1 - 1- (BETA-ARYL) -AETHYL-1H-1,2,4-TRIAZOLKETALS AND THEIR SALES, METHOD FOR THEIR PRODUCTION AND FUNGICIDALS AND PLANT REGULATORY AGENTS - Google Patents

Description

¹¹ 1- (ß-Aryl) -äthyl-1K-1,2,4-triazole ketals and their salts, process for their preparation and fungicidal agents and plant growth regulating agents "

Priority: November 18, 1974, V.St.A., No. 524 587 October 9, 1975, V.St.A., no.620 989

The invention relates to the subject matter characterized in the claims.

US Pat. No. 3,575,999 discloses 1- (β-aryl) ethylimidazole ketals, which are effective against bacteria and fungi. Various triazole derivatives are also known that are fungicidal or have plant growth regulating properties.

The triazole derivatives prepared according to the invention differ differs from the corresponding known compounds, inter alia, by the one of the nitrogen atoms of the triazole ring bound side chain. Similar triazole derivatives are also made. Dutch patent application 69.13 028 sov / ie

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I COPYT

Fr.2.200.012, Derwent Week V25, Pharm .., p. 7.

Specific examples of straight or branched alkyl radicals with 1 to 10 carbon atoms are the methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, butyl, pentyl, Hexyl, heptyl, octyl and decyl groups.

Specific examples of straight or branched alkyl radicals with 1 to 6 carbon atoms are the methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, pentyl and hexyl groups.

Specific examples of halogen atoms are fluorine, chlorine, bromine and iodine atoms.

The ketals of the general formula prepared according to the invention I are easily made from 1H-1,2,4-triazole of formula II, this initially by reacting with, for example, an alkali metal alkoxide, preferably with sodium methoxide, into a Metal salt is transferred. This metal salt is then reacted with a halide of the general formula III, in the Y preferably represents a bromine atom. The reaction of 1H-1,2,4-triazole with a halide of the general formula III is preferably carried out in an organic inert polar solvent, such as Ν, Ν-dimethylformamide, N, N-dimethylacetamide, Acetonitrile and benzonitrile. Such solvents can also be used in combination with other organic inert solvents, such as benzene, methylbenzene and dimethylbenzene are used

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will. If Y in the general formula III is a bromine or chlorate, the addition is necessary to carry out the reaction of an alkali metal iodide, in particular of sodium or Potassium iodide, preferred. The reaction is preferably carried out at a higher temperature, in particular at the reflux temperature of the reaction mixture.

The resulting ketal of the general formula I is isolated in a customary manner from the reaction mixture and, if appropriate, in Purified in the usual way, for example by crystallization, extraction, digestion or chromatography.

The aforementioned implementation is carried out by the following equation explained:

Y-CH ₂ -C-Ar

rf ⁰ O ^{0 (III)}

HI > · :> ■ (I)

DMF, NaI

The compound of the general formula I obtained can be converted into the corresponding salt with an acid, for example by reaction with an inorganic acid such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, Nitric acid, thiocyanic acid or phosphoric acid, or an organic acid such as acetic acid, propionic acid, hydroxyacetic acid, α-hydroxypropionic acid, 2-oxopropionic acid, oxalic acid, propanedicarboxylic acid, 1,4-butanedicarboxylic acid, Z-2-butenedicarboxylic acid,

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^Γ - k - 255156 (P.

E-2-butenedicarboxylic acid, 2-hydroxy-1,4-butanedicarboxylic acid, 2,3-dibydroxy-1,4-butanedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, Benzoic acid, 3-phenylpropenecarboxylic acid, α-hydroxybenzene acetic acid, methanesulphonic acid, ethanesulphonic acid, Hydroxyethanesulfonic acid, 4-methylbenzenesulfonic acid, oc-hydroxybenzoic acid, 4-amino ~ 2-hydroxybenzoic acid, 2-phenoxybenzoic acid and 2-acetyloxybenzoic acid. The obtained salts with acids can in the usual way by reacting with a free base, for example with sodium or potassium hydroxide, in the appropriate free bases are transferred.

The starting compounds of the general formula III are known in various ways and can be prepared in a manner known per se. Such compounds in which Z represents the group -CH ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₇ ) - or -CH ₂ -CH ₂ -CHg- and their preparation are described in US Pat. No. 3,575,999. In general, the compounds of the general formula III by ketalysing a corresponding ketone of the general formula IV

Ax-I-CH ₂ Y < ^IV >

in which Ar and Y have the above meaning with a corresponding diol of the general formula V

HO-Z-OH. (V)

in the Z has the preceding meaning, with the implementation takes place in the usual way (cf. Synthesis, Vol. 1 (1974), p. 23).

L. J

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"5- 255156 (p

In a preferred embodiment of the method according to the invention the two reactants are together for several hours in an organic solvent, for example in an aromatic hydrocarbon such as benzene, methylbenzene and dimethylbenzene, or in a saturated hydrocarbon, like cyclohexane, and in the presence of a strong acid, v / iε 4-methylbenzenesulfonic acid, heated under reflux. To the educated To separate off water azeotropically, a further organic solvent, preferably a simple alcohol, such as ethanol, propanol, butanol and pentanol are used. the Implementation is explained by the following equation.

Il 4-Methvlbonzenesulfonsäure ^ / _TTT \

Ar-C-CH ₀ Y + HO-Z-OH * - "? Ul-U

2 butanol

(IV) (V) ^Benzo1

The ketones of the general formula IV are known and can be prepared by known processes.

From the general formula I it can be seen that the invention Compounds produced have an asymmetric carbon atom and therefore in the form of stereochemically different optical isomers are present. If, for example, there is an alkyl radical in the 4-position of the dioxolane structure, are the carbon atom to which the alkyl radical is attached and the carbon atom in the 2-position of the dioxolane skeleton asymmetrical. The optical isomers obtained by the process according to the invention can be isolated in a customary manner.

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255156CP

The compounds prepared according to the invention of the general Formula I and its salts with acids are valuable for combating "certain fungi and bacteria. These compounds are used for the treatment of plants, animals and humans, each of which is caused by the action of pathogenic microorganisms

men are sick.

The compounds prepared according to the invention are valuable fungicides for use in agriculture. They are very effective against a large number of fungi, for example against those fungi that are found in different plant species lead to the formation of powdery mold, such as Erjrsiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pannosa, Sphaerotheca mors-uvae and Uncinula necator, as well as against other fungi such as Venturia inaequalis, Colletotrichum Lindemuthianum, Fusarium oxysporum, Alternaria tenuis, Thielaviopsis basicola, Helminthosporium gramineum and Penicillium digitatum.

The compounds prepared according to the invention are both in terms of valuable for both their prophylactic and therapeutic effects. The effect of these compounds as opposed to phytopathogenic fungi is illustrated by the following experiments.

In several of these experiments, 1- / 2 ^ (2,4-dichlorophenyl) -1 j ^ - ^ -! , 2,4-triazole of the formula I-a

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(i-a)

used.

A. Prophylactic effect of compounds of general Formula I versus Erysiphe cichoracearum on cucumbers by treating the leaves.

10-day-old cucumber plants are each 250, 100 or

the
10 ppm of the / compound to be examined containing aqueous solution sprayed. For comparison, some of these plants are left untreated. After the plants have dried, spores of this fungus are transferred to them by light rubbing with a leaf heavily infected with Erysiphe cichoracearum. 15 days after this artificial infection, the degree of fungus formation is assessed by counting the number of spots per plant. The results are summarized in Table I, the values given each being the mean values of two plants.

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Connections used;

Table I.

(Ha)

Ar R. bast
or
■ - .. salt. Judgement - - 100 ppm 10 ppm 2.4- (Cl) ₂ -C ₆ H ₃ H base 250 ppm O O ^C 6 ^H 5 H base - 3 - 4-NO ₂ -C ₆ H ₄ , H base - - - 3-Cl-C ₆ H ₄ H base O 2 - - 2-Cl-C / H.
6 4 H (COOH) ₂ O 4-Br-C ₆ H ₄ H base ^: - '- ■ - 2-Br-C ₆ H ₄ - H
H (COOH) ₂
(COOH) ₂ O 2 : 2-CH.-C, H.
3 6 4 H (COOH) ₂ 1 • -. - ■ ■■ 4-FC / H.
6 4 H (COOH) ₂ O - ■ -. - 4-CH_-C, H.
3 6 4 H (COOH) ₂ O - 4-Cl-C, H,
6 4 H (COOH) ₂ -H ₂ Q O O 2-naphthyl H (COOH) ₉ - - · - * · ■.-.- ■ ' 2.5- (Cl) ₂ -C ₆ H ₃ H (COOH) ₂ O O ■■ - - 4-CN-C ₆ H ₄ H (COOH) ₂ -. - - H (COOH) ₂ O 3 to » 2-OCH -0, H,
3 6 4 H (COOH) ₂ - - 2-thienyl
2-fluorenyl H
H (COOH) ₂
base 1 2 5-Cl-2-thienyl H •Base O 2 - -

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Table I - continued

Ar R. base
or Judgement . .- .. 100 ppm 10 ppm salt 250 ppm - - 3-Br, 4-CH ₃ -C ₆ H ₃ H base O 2 - 2-CH ₃ , 4-Br-C ₆ H ₃ H Base' - - - • 2-CH., 4-Cl-C, H
j OO H base O - - 3-Br-C ₆ H ₄ H base 2 - - 4-1-C ₆ H ₄ H (COOH) ₂ O 2 - 3,5- (Cl) ₂ -C ₆ H ₃ H (COOH) ₉
Cl - - - - 2,3 (Cl) ₂ -C ₆ H ₃ H (COOH) ₉
Ct O - "- - 3-NO ₂ -C ₆ H ₄ H base 1 1 - 2,4- (Br) ₂ -C ₆ H ₃ H · (COOH) ₂ - - - 2,4,5- (Cl) ₃ -C ₆ H ₂ H (COOH) ₂ O 2 - 2-01,4-OCH ₃ -C ₆ H ₃ H (COOH) ₂ - - - 2,4- (Cl) ₂ -C ₆ H ₃ CH ₃ ENT ₃ O O O 2,4- (Cl) ₂ -C ₆ H ₃ ^C 2 ^H 5 ENT ₃ - O O 2,4- (Cl) ₂ -C ₆ H ₃ HC ₃ H ₇ ENT ₃ - 2 - 2,4- (Cl) ₂ -C ₆ H ₃ ^nC 4 ^H 9 11/2 (COOH) ₂ - O O 2,4- (Cl) ₂ -C ₆ H ₃ ENT ₃ - - - 2,4- (Cl) ₂ -C ₆ H ₃ D ^. J, χ ENT ₃ O 2 - 2,4- (Cl) ₂ -C ₆ H ₃ ENT ₃ - - - 2,4- (Cl) ₂ -C ₆ H ₃ ^nC 8 ^H ! 7 ENT ₃ O

no spot per plant 1 Ms 5 spots per plant 6 to 10 spots per plant over 10 spots per plant.

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A -'- i prophylactic effect against Erysiphe polyphaga Cucumbers by treating the leaves.

Young cucumber plants in the single-leaf stage v / ground with each

the
500, 250 or 125 ppm of the / Compound Ia containing aqueous solution sprayed. As a control, some plants are left untreated. Spores of this fungus are transferred to these plants by light rubbing with a leaf strongly infected with Erysiphe polyphaga, this artificial infection taking place on the 4th, 6th or 5th day after the treatment with the compound Ia. On the 18th and 34th day after this treatment with the compound, the percentage of the leaf surface attacked by the fungus is determined for both the infected leaves and the newly developed leaves. The results, which in each case represent the mean values of 5 plants, are summarized ^{in Table I 1.}

Table I ¹

"Judgement . 18 days after treatment
with connection Ia a b 6th a b 8th a b 34 days after handling £
ment with connection Ia £ a b 6th a b • i a ^b Infected after
Days 4th 100
0
0
0 100
0
0
0 100
0
0
0 100
0
0
0 100
0
0
0 100
0
0
0 4th 100
0
0
0 100
0
0
0 100
0
0
0 100
0
0
0 100
0
0
0 ι
100 j
1
0 '
0 Infected leaves
ter (a) or
newly developed
Leaves (b) Concentration _r
the connection
Yes in the spray
solution
untreated
500 ppm
250 ppm
125 ppm

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B. Prophylactic effect against Erysiphe graminis on barley by treating the soil

Barley plants are watered by watering with 100 ml / plant of an aqueous solution of the compound I-a, the is present in a concentration of 1000, 100 or 10 ppm. As a control, the same plants are treated with the same amount of water doused. A natural infection is caused to these plants, which usually happens when these plants are kept in a glass house next to infected plants. 16 days after the treatment with the aforementioned solution, the number of spots on the leaves of the plants is determined. The results, each representing the mean values of 5 plants are summarized in Table II.

Table II

Connection Ia,
mg / plant % Infestation, control
100 mg
10 mg
1 mg 100
0
0
53

C. Therapeutic effect on Erysiphe graminis Barley by treating the leaves.

Barley plants infested by Erysiphe graminis are each with sprayed an aqueous solution of the compound I-a in the concentrations given below. 16 days after treatment the number of spots per plant is determined. The result

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nits, each representing mean values of 5 "plants summarized in Table III.

Table III

Concentration of the Ver
binding Ia in the
SprühlöDU.np; % Infestation O
1,000 ppm
100 ppm
10 ppm 100
0
1.5
25th

D. Prophylactic effect against Podospliaera leuchotricha on apple seedlings by spraying ■ ■ -

One year old apple seedlings are treated with an aqueous solution of the compound I-a in the concentrations given below sprayed. The plants are artificial 1 day after the treatment with Podosphaera leuchotricha spores infected and incubated for 36 hours. 25 days after the treatment with the compound I-a, the fungal attack is determined by determining the Number of stains assessed. The results, which in each case represent the mean values of 2 plants, are summarized in Table IV.

Table IV

Concentration of the Ver
binding Ia in the
Spray solution % Infestation 0
100 ppm
10 ppm 100
0
6th

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E. Action against Thielaviopsis sp.

5 mm thick potato and leek slices each ground in one aqueous solution of the compound I-a is immersed in the concentrations given below. Then the slices placed in a large plastic tray on a filter paper, and the bowl is covered with a glass lid. On the same day that the said disks were treated with the compound I-a v / ground these by spraying with a concentrated suspension of spores of Thielaviopsis sp. artificially infected and then incubated at room temperature. 6 days later, the mushroom growth on the slices is determined by estimating the amount of the Fungus infested surface assessed. The results are summarized in Table V.

Table V

Concentration of the conn
dung Ia in the test solution,
ppm % Infestation leek 0 potato 100 1,000 100 0 100 0 0 10 0 42.8 1 0 100 11

The compounds of general formula I are also effective against fungi, which are pathogenic for humans and animals Have properties. For example, these compounds are against fungi such as Microsporum canis, Trichophyton

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mentagrophytes, Trichophyton rubrum, Aspergillus fumigatus, Phialophora verucosa, Cryptococcus neoformans, Candida albicans χιηά Candida tropicalis. The excellent effect against Candida albicans is explained below.

F. Effect of compound Ia against candidiasis in goiters of turkeys.

14 day old turkeys are grounded by administering a suspension, the 4 × 10 CFU (Colony Forming Units) of Candida albicans and inserted into the goiter using a probe is artificially infected. Then receive the Animals either their normal feed (control) or a medicinal feed containing 125 ppm of compound Ia. 2 weeks later all turkeys are killed and cultures are put on each with the turnips. It will count the number of Candida » Colonies detected per gram of goiter. The results are summarized in Table VI.

Table VI

number
the animals Number of candida
Colonies per g des
Krorcfes control
Yes,
125 ppm 1
2
3
4th
1
3 3,520,000
848 700
3,132,000
1 909 000
0
247 200
6 742

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From Table VI it can be seen that the compound Ia at a dose of 125 ppm in comparison with a corresponding Blind experiment is very effective.

G. Effectiveness of Compound Ia against Candidiaas in the vagina of rats

V ^"r eibliche be Hatten g with a body weight of approximately 100 and ovariectomiert hysterectoraiert. About 3 weeks later, each animal received a weekly subcutaneous injection of 100 mg estradiol undecylate and was infected intravaginally with a suspension containing 8-10 CFU of Candida albicans. Groups of 4 rats each are then treated orally for 14 consecutive days either with a solvent (FEG 200) or with the compound Ia. The administered dose of the compound is 40 mg / kg. After the 14 days mentioned, a vaginal smear is taken from each animal and cultivated in a Sabouraud agar hedium containing 20 IU / ml penicillin and 40 μg / ml streptomycin. The number of Candida colonies is then counted. The results are summarized in Table VII.

Table VII

number of
animals Days after
the treatment 14th Judge
Culture ""' 1 2 1 4th PEG 200 4th lung 14th 0 0 0 0 3 Yes 4th 0 1 0 0 3

x) 0 = no growth

1 = 1-25 colonies

2 = 26-100 colonies

3 => 100 colonies

4 = countless colonies

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Γ Π

It can be seen from Table VII that Compound Ia is very effective.

H. Efficacy of Compound Ia Against Systemic Candidiasis in guinea pigs

male
Adults / guinea pigs are infected intravenously with Candida albicans, which induce a general system! See candidiasis. Subsequently, in each case a group of 7 of the guinea pigs is administered orally either a solvent (PEG 200) or the compound Ia for 14 consecutive days. The dose of the compound is 40 mg / kg.

All animals are sacrificed 4 days after the last day of treatment. The kidneys of the animals are removed and cultured according to G. Then the number of isolated Candida colonies counted per g kidney. The results are summarized in Table VIII.

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Table VIII

Number of animals

Number of Canclida colony n per κ kidney j

PEG 200

1 2 3 4 5 6

182

2,838

25 220

385 19 800

113.

345

1 2

3 4 5 6 7

18 0

0 0

53 0

From Table VIII it can be seen that the compound Ia is very effective against severe systemic mycosis in guinea pigs v / is ineffective.

In addition to their antimicrobial properties, the compounds have of the general formula I valuable plant growth-regulating properties. Depending on the type of treated plant and the administered dose stimulate or delay growth. In particular these compounds are suitable for retarding plant growth, especially the growth of saplings, for example in tobacco plants. Under these circumstances, however, rain

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these compounds also promote plant growth.

The plant growth-regulating properties of the compounds of general formula I are illustrated below using the example Compound Ia explained.

I. Growth-regulating effect on tomato plants through treatment of the soil

Young tomato plants 3.5 to 4 cm high are separated from each other Pots planted. Each pot is poured with a test solution which contains the following amount of compound Ia contains. 28 days after the treatment, the growth of the plants is assessed by determining their length and weight. The results, each mean values from 5 plants are summarized in Table IX.

Table IX Weight of
Plants, % 100 Yes,
mg per plant Length of
Plants, % 118 without 100 134 10 1.14 116 1 127 0.1 122

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"I.

J. Growth regulating effect in barley by treating the leaves

Young barley plants at the 3 ™ Ms 4-leaf stage become with the solutions containing the compound Ia, which have the concentrations given below, sprayed. 24 days after the treatment is done by determining the weight of the plants assessed the effect on their growth. The results, which each represent the mean values of 10 plants, are summarized in Table X.

Table X

Concentration of
Connection Ia in
the Te f; ti ö sun ff Weight of plants,
ti no
125
60 100
126
116

K. Growth regulating effect on saplings of tobacco plants

Tobacco plants of the "Xanthi" variety are grown in the greenhouse and pruned in the early bud stage. After 5 days, the leaves are sprayed with an aqueous suspension of the compound Ia in an amount of 3 or 1.5 kg of the compound per hectare. Each treatment is repeated three times. Twelve days after the end of the treatment, the subsequent growth of the shoots is assessed and compared with the growth of untreated tobacco plants. The reduction in the growth of the pelvic

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linge is 100 % when treated with 3.0 kg of the compound per ha and 90 ⁱ / a at 1.5 kg per ha.

L. Growth retardation in soybean plants.

Soybean plants of the "Hark" variety are exposed to radiation in the greenhouse at a temperature of £ 3 ° C
20,000 lux and a day length of 14 hours in pots. After the third 3-leaved leaf has unfolded, the plants are sprayed with aqueous suspensions of the compound Ia at concentrations of 1000, 500, 100 or 50 ppm. After 14 days, the growth inhibition of the treated plants is assessed in comparison with untreated plants. The results are summarized in Table XI.

Table XI

concentration
binding Ia in
pension, ppm control the
the Ver
Sus- Vachsturnsver
hesitation,
% 1000 70 500 40 100 25th 50 0 0

At a concentration of 1000 ppm, it becomes more intense
green color of the leaves observed.

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The compounds of general formula I or their salts with Acids can be used in appropriate means with antifungal, antibacterial and wax turas-regulating effects will. For this purpose, these compounds can be mixed with a solvent or a solid, semi-solid or liquid diluent or carrier material can be combined. When using appropriate solvents or diluents, emulsions, Received suspensions or ointments. Soaps, surface-active compounds and special dispersants can also be used are, the compounds prepared according to the invention also together with other compounds with arachnicidal, Insecticidal, ovicidal, fung.lp.id and / or bactericidal effects as well as can be used with inactive help guides .

Solid carriers that are used in the manufacture of the appropriate means Can be used in powder form, for example, various inert, porous and powdery inorganic or organic substances such as tricalcium phosphate, calcium carbonate (in the form of further treated lime or limestone), kaolin, clay, bentonite, talc, kieselguhr, boric acid, in powder form Cork and wood flour, as well as finely powdered substances of vegetable origin.

The compounds of the general formula I v / ground with the aforementioned Mixed carriers, for example, the 'components are ground together or the carrier with a solution of the active ingredient in a volatile solution

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solvent is added and then the solvent removed by heating or suction. If wettable and / or dispersing substances are added, the resulting can Powdery equipment lightly moistened with water and converted into suspensions.

If inert solvents are used to produce a liquid agent, these solvents should be difficult to separate, as odorless as possible and non-toxic to humans, mammals and plants. Appropriate solvents are high-boiling oils, for example vegetable oils, and low-boiling solvents with a flash point of at least 30 ⁰ C, such as polyethylene glycol, isopropanol, dimethyl sulfoxide and ₅ hydrogenated and alkylated naphthalene derivatives. Mixtures of solvents can also be used. The solutions are prepared in the usual way, optionally in the presence of solubilizers. Other liquid forms of the agents containing the compounds mentioned are emulsions or suspensions of the active ingredient in water or a corresponding solvent, or else concentrates of the active ingredient for producing such emulsions, which can then be adjusted to the desired concentration. For this purpose, for example, the active ingredient is mixed with a dispersant or emulsifier. The active ingredient can also be dissolved or dispersed in a corresponding inert solvent and mixed simultaneously or subsequently with a dispersing or emulsifying agent.

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Semi-solid carriers with ointment-like, paste-like or v / axis-like · Consistency can be used in which the active ingredient is incorporated is, optionally in the presence of solubilizers and / or emulsifiers. A specific example of such carrier is petroleum jelly.

The compounds of general formula I can also be used in corresponding Agents transferred in the form of an aerosol. For this purpose, the active ingredient is dissolved or dispersed, if necessary in the presence of an inert solvent, such as difluorodichloro · methane, as a liquid carrier, which at ambient pressure at boils at a temperature below room temperature. In this preparation, solutions are obtained under pressure that when Spraying aerosols and used to fight fungi and bacteria, for example in closed chambers and storage rooms, as well as for prophylactic and therapeutic treatment of plants are particularly suitable.

The agents obtained in one of the above ways can, for example, by atomizing, sprinkling, spraying, brushing, Dipping, brushing or impregnating applied. The active ingredients are also very effective in high dilution. For example are still concentrations of the active ingredient from 0.1 to 10 percent by weight, based on the weight of the agent, effective in combating fungi or bacteria. However, higher concentrations can also be used.

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- - 24 - ^Π

The examples illustrate the invention / parts refer on weight, unless otherwise stated.

example 1

A cooled to a temperature of 0 ⁰ C mixture of 30 parts of 1- (4 ~ amino "2 ~ methoxypheiryl) -ethanone in 360 parts of concentrated hydrochloric acid, 75 parts WassW and 30 parts of acetic acid is added under stirring with a solution of 17.25 parts of sodium nitrate diazotized in 200 parts of water. After 30minütigera stirring at said temperature the reaction mixture with stirring in a solution of 30 parts of copper (I) chloride is poured into 240 parts of concentrated hydrochloric acid. the resulting mixture is heated for 1 hour at 60 ⁰ C. After After cooling to room temperature, the mixture is extracted twice with 2,2'-oxybispropane. The combined extracts are washed in sequence with water, a dilute sodium hydroxide solution and again twice with water, then dried, filtered and evaporated. Yield 28 parts (76 % d.Th.) 1- (4-chloro-2 ~ methoxyphenyl) -ethanone from the F. 55 ⁰ C.

Example 2

A mixture of 78.8 parts of 2-bromo-1- (4-bromo-2- methylphenyl) -1-ethanone and 200 parts of butanol are mixed with 3 parts of 4-methylbenzenesulfonic acid and 225 parts of benzene with stirring. Afterward 33 »5 parts of 1,2-ethanediol are added dropwise. To complete the reaction, the mixture is refluxed for 16 to 18 hours using a water separator heated. Then the reaction mixture

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^r -2S-

evaporated. The residue is dissolved in 2.2 ^f- oxybispropane, and the resulting solution is stirred with 15 parts of concentrated sodium hydroxide solution. After separating the layers formed, the aqueous layer is extracted with 2,2 '^ - oxyhispropane. The combined organic layers are washed with water to neutralize the reaction, then dried, filtered and evaporated. The solid residue is recrystallized from methanol. Yield 30> 5 parts of 2 ~ (BromomGthyl) -2- (4 · - brorn ~ 2-methylphenyl) -1,3-dioxolane with a melting point of 86 C.

Example 3

According to Example 2, but using an equivalent amount of the corresponding 1-aryl-2-bromo-1-ethanone instead of 2-bromo ~ 1- (4-bi "Om« 2-methylphenyl) "1-ethanone, are the following Get connections.

4- / 2- (bromomethyl) -1,3-dioxolan-2 ~ yl / -benzonitrile, · 92.4 ⁰ C; 2- (bromomethyl) -2- (2-naphthalenyl) -1,3-dioxolane; F. 64 ⁰ C.

Example 4

57 parts of 1- (5 ~ chloro-2-thienyl) -1-ethanone are dissolved at a temperature of 50 ⁰ C in 220 parts of 1,2-ethanediol. 64 parts of bromine are added dropwise to the solution over a period of 1 hour while stirring, without external heating. After stirring for one hour at room temperature, 4 parts of 4-methylbenzenesulfonic acid and 360 parts of benzene are added. The entire mixture is stirred and refluxed for 16-18 hours using a water separator. Then the reaction

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tion mixture evaporated. The residue is taken up in 2.2'-OXyMspropane. The solution obtained is washed in sequence once with dilute sodium hydroxide solution and three times with water, then dried, filtered, evaporated and distilled. Yield 73.3 parts (64.5 % of theory) 2- (bromomethyl) 2- (5 »chloro-2-thienyl) -1,3-dioxolane with a boiling point of 125 Ms 127 ° C / 0.1 Torr .

Example 5

According to Example 4, but using an equivalent quantity

"from ge of the corresponding 1-aryl-i-ethanone instead of / 1- (5-chloro-2-thienyl) ~ 1-ethanone _> the following compounds are obtained:

2 »(bromomethyl) -2- (9H-luoren-2-yl) -1,3-dioxolane; M.p. 90 ⁰ C; 2 ~ (bromomethyl) -2 ~ (3-bromo-4 ~ iriethylphenyl) -1,3-dioxolane, b.p. 126 to 130 ⁰ C / 0.1 Torr.

2- (Bromomethyl) -2- (4-iodophenyl) -1,3-dioxolane, 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; F. 96 ⁰ C.

Example 6

A. A solution of 2.3 parts of sodium in 120 parts of methanol is mixed with 6.9 parts of a mixture of 1H-1,2,4-triazole and ISO parts of dimethylformamide. The methanol is then distilled off at ambient pressure reaches 13O ⁰ C until the temperature of the mixture. Then 25 parts of 2- (bromine-

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Γ-. 2.7 - ^Π

ethyl) -2- (2,4-di-chlorophynyl) -1,3-clioxolane was added. The mixture is stirred, refluxed for 3 hours, cooled to room temperature and poured into water. The precipitated product is filtered off and, after treatment with activated charcoal, recrystallized from diisopropyl ether. Yield 12 parts of 1- / 2- (2, A-dichlorophenyl) -1,3-dioxolan-2 ~ ylmethyl7-1H-1,2,4-triazole, mp 109.9 ⁰ C.

B. 6 parts of the compound obtained according to A v / ground in 2,2'-oxy mspropane as a solvent in the corresponding nitrate. After the mixture has cooled down, the salt is filtered off and recrystallized twice from 2-propanone. Yield 3 parts of the corresponding nitrate, mp 172.7 ⁰ C.

C. 6 parts of the compound obtained according to A are dissolved in 2,2'-oxybispropane converted as a solvent into the corresponding sulfate. The sulfate formed is filtered off and extracted from 2-propanol recrystallized. The product obtained is filtered off, recrystallized from ethanol after treatment with activated charcoal and dried. Yield 6 'parts of the corresponding sulfate from

F. 207.1 ⁰ C.

Example 7

A solution of 2.3 parts of sodium in 80 parts of methanol is treated with stirring with 6.9 parts of 1H-1,2,4-triazole and a mixture of 2 parts of sodium iodide and 100 parts of Ν, Ν-dimethylformamide. The methanol is distilled off under atmospheric pressure, achieved .to the temperature of the reaction mixture 130 ⁰ C. then

L -. -J

■ 609821/1003

^Γ - 28 - ^Π

34.4 parts of 2- (bromomethyl) -2- (2,4-dichloropbenyl) -4-methyl-1,3-dioxolane are added and the mixture is stirred under reflux for 3 hours. The reaction mixture is then poured into water and the resulting mixture is extracted twice with diisopropyl ether. The extract is washed with water and then mixed with an excess of concentrated nitric acid. The crude nitrate is filtered off and recrystallized from a mixture of 2-propanol and diisopropyl ether. Yield 15 parts of 1- / 2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole nitrate with a melting point of 137-8 ° C.

Examples

A solution of sodium methoxide obtained from 2.8 parts of sodium and 48 parts of methanol is admixed with 8.3 parts of 1H-1,2,4-triazole while stirring. After 30 minutes of stirring at room temperature, 135 parts of N, N-dimethylformamide are added. After the methanol has been distilled off from the mixture, a mixture of 24.3 parts of 2- (bromomethyl) -2.-phenyl-1,3-dioxolane and 3 parts of potassium iodide is added and the mixture is then stirred under reflux for 3 hours. After the reaction mixture has cooled to room temperature, it is poured into water. A product precipitates when the inner wall of the vessel is rubbed. This is filtered off with suction, washed with water, dried and ^{recrystallized from a mixture of ethanol and 2.2 f-} oxybispropane (1: 5 parts by volume). Yield 10.9 parts (43.7 % of theory) 1- (2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, melting point 127.3 ⁰ C

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^Γ - 29 - "

Example 9

According to Example 8, but using an equivalent amount of the corresponding 2-aryl ~ 2- (bromoethyl) -1,3-clio3; olane an-

from

place / 2- (bromomethyl) »2 ~ phcnyl-1,3-dioxolane, the following Get connections :,

1- / 2- (4-IJi trophenyl) -1,3-dioxolan-2-ylmethyl7-1H-1,2,4-triazole,

F. 160.1 ⁰ C;

1- / 2- (3-chlorophenyl) -1,3-dioxolan-2 ~ ylmethyl / -1H ~ 1,2,4-triazole,

113.9 ° C;

1_ / 2- (4-broriphenyl) -1,3-dioxolan-2-ylmethyl / -1H-1,2,4-triaü.ol,

135.9 ° C;

1- / 2- (3-methylphonyl) -1,3-dioxolan-2-ylmethyl] J-1H-1,2,4-triazole

F. 105.4 ⁰ C;

1- / 2- (3-bromophenyl) -1,3-dioxolan-2 ~ ylmethyl7-1H-1,2,4-triazole,

115.4 ° C;

1- / 2- (3-nitrophenyl) -1,3-dioxolan-2-ylmethyl7-1H-1,2,4-triazole,

F. 154.1 ⁰ C.

Example 10

A solution of sodium methoxide obtained from 1.6 parts of sodium and 48 parts of methanol is admixed with 4.9 parts of 1H-1,2,4-triazole with stirring. After stirring for 1 hour at room temperature, 135 parts of N, N-dimethylformamide are added to the mixture. The methanol is distilled off at ambient pressure reaches 130 ⁰ C until the temperature of the reaction mixture. Then the mixture is gradually added with 17.4 parts of 2- (bromomethyl) -2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide

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added and stirred under reflux for 16 "to 18 hours. After cooling to room temperature, the reaction mixture is poured into water. When rubbing the inner wall of the vessel, a product precipitates which is filtered off and washed with water. The product is dissolved in trichloromethane and chromatographically purified on a column filled with silica gel using trichloromethane containing 5% methanol as the eluent. The pure fractions are collected and the eluent is distilled off. The residue is isolated from a mixture of 2,2'-oxybispropane and methanol (9: 1 Yield 9.3 parts (55.5 % of theory ) 1- / 2- (2,3,4-tri-chlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H-1 , 2,4-triazole, mp 181.4 ° C.

Example 11

According to Example 10, but using an equivalent amount of the corresponding starting compounds v / ground the following. the following connections:

1- / 2- (9H-fluoren-2 ~ yl) -1,3-dioxolan-2-ylmethyl7-1H-1,2,4-triazole, mp 186.8 ⁰ C;

1- / 2- (5-chloro-2-thienyl) -1,3-dioxolan-2-ylmethyl / ~ -1H-1,2,4-triazole, mp 117.4 ⁰ C;

1 - / 2L (3-bromo-4-methylphenyl) -1,3-dioxolan -2-ylmethyl7-1 H-1,2,4-triazole, mp 120.7 ⁰ C;

1- / 2- (4-bromo-2-methylphenyl) -1,3-dioxolan-2 ~ ylmethyl7-1H-1,2,4-triazole, mp 148.1 ⁰ C;

1- / 2- (4-chloro-2-methylphenyl) -1,3-dioxolan-2-ylmethyl_7-1H-1,2,4-l-triazole, P. 147.9 ⁰ C._J

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Example 12

A solution of sodium carbonate oxide obtained from 2.8 parts of sodium and 56 parts of methanol is mixed, with stirring, with a mixture of 8.3 parts of 1II-1,2,4-triazole and 135 parts of N, N-dimethylformamide. The methanol is abdestilliertj reaches 130 ⁰ C under atmospheric pressure until the temperature of the reaction mixture. Then 27.8 parts of 2- (Broir: methyl) 2- (2-chlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are added to the mixture. After stirring for about half an hour under reflux, the roaction will be happy! sch cooled to room temperature, poured into water and extracted three times with 1,1 '-Cbrybisäthan. The combined extracts were washed twice with Y / Hsser, dried, filtered and evaporated. The residue is converted into the corresponding oxalate in 4-methyl-2-pentanone. The oxalate is filtered off and recrystallized from 4-methyl-2-pentanone. Yield 16 parts of 1- / 2- (2-chlorophenyl) -1,3 ~ dioxolan-2-ylmethyl / ~ -1H-1,2,4 triazoloxalat, mp 156.5 ⁰ C.

Example 13

According to Example 12, but using an equivalent amount of the corresponding starting compounds, the following Oxalates of the 1,2,4-triazole derivatives given below obtain:

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CH.

Ar

ι I

Ar

salt

2-Br-C ₆ H ₄ (COOH) ₂ 172.1 ° C. 3-OCH ₃ -C ₆ H ₄ (COOH) ₂ 155.6 ° C. 2-CH ₃ -C ₆ H ₄ (COOH) ₂ 177.1 ° C. 4-FC ₆ H ₄ (COOH) ₂ 185.5 ° C, 4-CH ₃ -C ₆ H ₄ (COOH) ₂ 151.2 ° C. 4-Cl-C ₆ H ₄ (COOH) ₂ . H ₂ O 169.1 ° C. 4-OCH ₃ -C ₆ H ₄ (COOH) ₂ 187.1 ° C. 2-naphthalenyl (COOH) ₂ 175 ⁰ C 2, 5- (Cl) ₂ -C ₆ H ₃ (COOH) ₂ 173.7 ° C. 4-CN-C ₆ H ₄ (COOH) ₂ 186.3 ° C. 3,4- (Cl) ₂ -C ₆ H ₃ (COOH) ₂ 182.2 ° C. 2-thienyl (COOH) ₂ 144. 5 ° C. 2,4- (Br) -C ₆ H ₃ (COOH) ₂ 190.3 ° C.

Example 14

One obtained from 2.3 parts of sodium and 48 parts of methanol Solution of sodium methoxide is mixed with 6.9 parts of 1H ~ 1,2,4-triazole with stirring. After stirring for about 50 minutes at room temperature 135 parts of N, N-dimethylformamide are added to the mixture given. Then the methanol is distilled off under ambient pressure, until the temperature of the mixture reaches 130 ° C. At-

. then gradually adding 3 parts of potassium iodide to the mixture and 16.4 parts 2- (bromomethyl) ~ 2 ~ (o ~ methoxyphenyl) -1,3-

L -I

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added dioxolane and stirred under reflux for 18 hours. After cooling to room temperature, the reaction mixture is poured into water and the resulting solution is extracted three times with trichloromethane. The combined extracts are washed four times with water, then dried, filtered and evaporated. The residue is purified by chromatography on a column loaded with silica gel using Tr: L-chloromethane containing 5% methanol as the mobile phase. The pure fractions are collected and the eluent is distilled off. The residue is converted into the corresponding oxalate in 4-methyl-2-pentanone. The oxalate is filtered off and made from a mixture of 2-propanone and 2.2 ^! -0xybi3propane (2; 1 parts by volume) recrystallized. Yield 5.5 parts (26 ¹ A of theory ) 1 - ^ - (2 ~ H8thoxyphonyl) -1,3- (iioxolan-2-ylmethyl7-1H-1,2,4-triazole oxalate from F. 166.4 ° C.

Example 15

Gam'iss Example 14, but using an equivalent H-ane of the corresponding starting compound, are the following Get salts:

1- / 2- (4-iodophenyl) -1,3-dioxolan-2-ylmethyl7-1H-1,2,4-tria2oloxalat, F. 169.3 ⁰ C;

1- ^ 5- (3,5-dichlorophenyl) -1,3-dioxolan-2-ylraethyl7-1H-1 _t 2,4-triazole oxalate, mp 204.4 ° C;

1 ~ [2 ~ (2,3-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole oxalate, mp 188.4 ° C;

(4-chloro-2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl / ~ 1H _L 1,2,4-triazoloralate, mp 173.2 ° C;

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1- / 2- (2,4,5-Triehlorphenyl) -1,3 - dioxolan-2-ylmethyl7--1H ~ 1,2,4-triazolo; Calat, F. 170.4 ⁰ C;

1- / 2- (2-chloro-4-i.isthoxyphenyl) -1,3-dioxolan-2-ylmethyl7-1H-1,2,4 »triazole oxalate, F. 188, 2 ⁰ C.

Example 16

A mixture of 9.5 parts of 1H-1,2,4-triazole and 225 parts of IJ, N-dimethylformamide is added in portions while stirring with 4.2 parts of a 78% dispersion of matriurahydride. After stirring has been continued until the foam has formed, 16 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) ~ 4-propyl-1,3-dioxolane are added to the mixture. The Gonisch is stirred under reflux for 5 hours, then cooled and poured for 3 seconds. The mixture is extracted three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The ¹ residue is purified by chromatography on a column loaded with silica gel using trichloromethane containing 2% methanol as the mobile phase. The first fraction is collected and its eluent is distilled off. The residue is converted into the corresponding nitrate in 2,2'-oxybispropane. The nitrate is filtered off and recrystallized from a mixture of 2-propanone and petroleum ether. Yield 8.2 parts (45 % of theory ) 1- / 2- (2,4-dichloiphenyl) -4-propyl-1,3-dioxolan-2-ylmethyl7-1H-1,2,4-triazole nitrate vom F. 132.6 ⁰ G.

Example 17

One obtained from 3.8 parts of sodium and 40 parts of methanol Solution of sodium mathoxide is added with stirring with 11.5 parts _j

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1H-1,2,4-triazole and 225 parts of N, N-dimethylformamide were added.

Then the methanol is distilled off from the mixture until the

d it emisehes
Temperature reaches ^ 150 C ♦ After adding 19 parts

2- (Bro.nimethyl) -2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane is stirred for 4 hours under reflux, then cooled and poured into V / a ε s. The genic is extracted three times with 2.2 ^f -Cxybispropane. The combined extracts are washed with water / water, dried, filtered and evaporated. The residue is purified by chromatography on a column charged with silica gel using trichloromethane containing 2% methanol as the mobile phase. The first fraction is collected and its eluent is evaporated. The residue is converted into the corresponding nitrate ^{in 2.2 f-oxybispropane.} The nitrate is filtered off and recrystallized from a mixture of 4-methyl-2-pentanone and 2,2'-oxybispropane. Yield 10.5 parts (49 % of theory ) 1 - / 2 - (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl7-1H-1,2,4 -triasol nitrate from F. 119, O ⁰ C.

Example 18

According to Example 17, but using the equivalent amounts the starting compounds are given the following salts;

1 - / 4 ~ butyl-2- (2,4-dichlorophenyl) -1, 3-DIØ3: olan-2-ylmethyl7 ~ 1H-1,2,4 ~ triazolsesquioxalat, F. 111.6 ⁰ C;

I- / 2- (2,4-dichlorophenyl) -4-pentyl-1,3 ~ dioxolan-2 ~ ylmothyl7- " 1H-1,2,4-triazole nitrate, mp 130.3 ° C;

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^Γ -36- 255156ο " ¹

1- / 2- (2,4-Dichlo-rphenyl) -4-hexyl-1,3-dioxolan-2-yl-methyl / -1H-1,2,4-triazolnrfcrat _f P. 106.2 ⁰ C;

1 - / 2- (2,4-dichlorophenyl) -4-heptyl-1,3-dioxolan-2-yl-methyl7-1H-1,2,4-triazole nitrate, m.p. 96, S ⁰ C;

1 - / 2- (2,4-dichlorophenyl) -4-octyl-1,3-dioxolan-2-yl-methyl7-1H-1,2,4-triazolnitrat, F. 110.6 ⁰ C.

Example 19

According to Example 6A, but using an equivalent amount of the corresponding 2 ~ (bromomethyl) -2-aryl-1,3-dioxolane an-

place / 2- (bromomethyl) -2- (2,4 ~ dichlorophenyl) -1,3-dioxolane get the following connections: ■

1 - / 2- (2, A , 6-trichlorophenyl) -1, 3 ~ dioxolan-2-ylmethyl7 ~ 1H-1,2,4-triazole;

1- / 2- (2,6 ~ dichlorophenyl) -1,3-dioxolan-2-ylmethyi7-1H-1,2,4-

triazole; ·

1 ~ / 2- ■ (2-chloro-4-methylphenyl) -1,3-0110X01311-2 - ^^ 6 ^ 1 / -1H-1,2,4-triazole.

B e i s ρ i e 1 20

According to Example 7, compounds of the general formula I can be prepared in which Z denotes the group -CH ₂ -CH (CH ^) - or -CH (CH ^) - CH (GHj) -. Vv-earth by using the corresponding 2-aryl-2- (bromomethyl) -4-methyl-1,3-dioxolane or 2-aryl-2- (broramethyl) -4,5-diß9thyl - 1- , 3-dioxolane, the naclifol- "ing compounds obtained in the form of their nitrates;

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1 _ (4-methyl-2-phenyl-1,3-dioxolan-2-ylmothyl) -1H-1,2,4-triazole; 1- / 2- (4-ChIoI ¹ PJIeHyI) -4-methyl-1,3-dioxolan-2-ylmethyl7-1H-1, 2,4-triazole;

1- / 2- (2-chlorophanyl) -4-methyl-1,3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole;

1/2 _f _Hsthyl-2- (4-methylphenyl) -1,3-dioxolan-2-ylraethyl / ~ 1H-1,2,4-triazole

1- / 2- (4-methoxyphenyl) -4-methyl-1,3-dioxolan-2-ylmethyl7-1H-1,2,4-triazole;

1 - / 4, 5-bimethyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / -1H -1 , .2,4-triazole;

1- (4,5-dimethyl-2- phenyl-1,3-dioxolan-2-ylaethyl) -1H-1,2,4-triazole;

1- / 2- (4-chlorophenyl) -4,5-dimethyl-1,3-dioxolan-2-ylmethyl / ~ 1H-1,2,4-triazole.

Example 21

According to Example 6A, compounds of the general formula I can be prepared in which Z denotes the group -CHp-CH ₉ -GHp-. If an equivalent amount of the corresponding 2-aryl-2- (bronmethyl) -1,3-dioxane is used as the starting compound, the following compounds are obtained:

1- (2-phenyl-1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole; 1 ~ / 2- (2,4-dichlorophenyl) -1 ^ -dioxane ^ -ylmeth ^ oZ-iH-i, 2,4- ' triazole; ·

1- / 2- (4-chlorophenyl) -1,3-dioxan-2-ylmethyl / -1II-1,2,4-triazole;

1 - / 2- (4-M3thy! Phenyl) -1, 3-dioxan-2-ylmethyl7-1H-1,2,4-triazole; L ¹ - / 2- (4-methoxyphenyl) -1,3-dio3-: an-2-ylniethyl7-1H-1,2,4-triazolu

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1- / 2- (2-thienyl) -1,3-dioxan-2-ylmethyl / -1H-1,2,4-triazole; 1 - [Z- (2-naphthyl) -1,3-dioxan-2-ylmethyl / -1H-1,2,4-triazole.

Example 22

Hit the compounds prepared according to the invention, a suspension, a dust powder, a solution and an ointment are prepared, which are suitable for combating fungi or bacteria.

Δ. suspension

1- / 2- (2,4-dichlorophenyl) -1,3-dioxolane-2-

yl-methyl / -1H-1,2,4-triazole 1 kg

Technical xylene 2 liters

surface-active compound 350 ml

Dilution to the desired concentration of the active ingredient 'water

B. Dust powder

20 parts of 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yliaethyl / -1H- 1,2,4-triazole are ground with 360 parts of talc in a ball mill. The mixture is then made with 8 parts of olein and after further grinding, 4 parts of slaked lime are added. The powder obtained can be atomized well and has good properties Adhesion properties.

C. Solution

5 parts 1- / 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl / 1,2,4-triazole are ge in 95 parts of alkylated naphthalene solves.

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D. Ointment

10 'parts of 1- / 2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-ylmethyl / -1H-1,2,4-triazole is in a heated liquid mixture of 400 parts of polyethylene glycol 400 and 590 parts of polyethylene glycol 1500 are dissolved. The solution is stirred until it cools, where an ointment is formed.

609821/1003

Claims (1)

J? "3. £ ,, ^θ , ⁿ , .t. § ,,. ~>. -ß P ₁₁ ^r ^ ^c -h ^e ("j / 1» (D-aryl) -ethyl-1H-1, 2,4-triazole ketals of the general Formula I _VT ■ ■ C- ~ Ar in which Z denotes the group -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH (CH ₃ ) -CH (CH ₇ ) - or -CPIp-CH (alkyl) -, where alkyl represents an unbranched or branched alkyl radical with 1 to 10 carbon atoms, and Ar represents a phenyl group optionally substituted by 1 to 3 halogen atoms, alkyl radicals with 1 to 6 carbon atoms, alkoxy radicals with 1 to 6 carbon atoms, cyano or nitro groups, a thienyl, halothienyl, Means capthyl or fluorenyl group, and their salts with acids. ■ 2. 1- / 2- (2,4-dichlorophenyl) ~ 1,3-dioxolan-2-ylmethyl / ~ 1H- 1,2,4-triazole. ■ ..... ' 3. 1 - / 2 »(2,4-dichlorophenyl) -4-methyl-1,3-dioxolan ~ 2-yl / methyl / -1H-1,2,4-triazole. 4. 1- / 2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmothyl / -1H-1,2,4-tria2ol. L -I 609821/1003 5. 1- / 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylinethyl / -1H-1,2,4-triazole. 6. 1- / 2- (2,4-dichlorophenyl) -4-pentyl-1,3-dioxdlan-2-ylmethyl7-1H-1,2,4-triazole. 7. A process for the preparation of the compounds according to Claim 1, characterized in that a metal salt of 1H-1,2,4-triazole is used of formula II ίΓ KJ (H) with a compound of the general formula III Y-CH ₉ C-Ar ^L ' ^K (in) represents in which Y is a halogen atom / ie Z and Ar is the one specified in claim 1 Have meaning, converts and optionally cleaves the resulting mixture of optical isomers and / or optionally the compound obtained is converted into a salt with an acid. 8. Fungicidal agents consisting of at least one compound according to claim 1 and customary carriers and / or diluents and / or auxiliaries. 609821/1003 9. Fungal disease regulating agents, consisting of at least a compound according to claim 1 and customary carriers and / or diluents and / or auxiliaries. 609821/1003