DE2551560B2 - triazole ketals and their salts, processes for their preparation and fungicidal agents and agents regulating plant growth - Google Patents

Description

15th

in the Z the group

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -,
- (CH (CH ₃ J-CH (CH ₃ ) -

25th

or

-CH ₂ -CH (alkyl) -

denotes where alkyl is a straight or branched alkyl radical having 1 to 10 carbon atoms represents, and their salts with acids.

2. Process for the preparation of the compounds according to claim 1, characterized in that one

a metal salt of 1 H-1,2,4-triazole of the formula U

-N

with a compound of the general formula III
Cl

in which Y represents a halogen atom and Z has the meaning given in claim 1, reacts and optionally the resulting mixture of the optical isomers cleaves and / or optionally the obtained compound converted into a salt with an acid.

3. Fungicidal agents, consisting of at least one compound according to claim 1 and usual Carriers and / or diluents and / or auxiliaries.

4. Plant growth regulating agents, consisting of at least one compound according to claim 1 and customary carriers and / or diluents and / or auxiliaries.

From US-PS 35 75 999 certain l- (jS-aryl) -äthylimidazolkctale are known that are effective against bacteria and fungi. Also are different Triazole derivatives known which have fungicidal or plant growth-regulating properties.

The compounds of the invention differ from the corresponding known compounds inter alia through the side chain attached to one of the nitrogen atoms of the triazole ring. Similar Triazole derivatives are also from Dutch patent application 69 13 028 and from FR-PS 22 00 012. Derwent Week V25, Pharm., P. 7.

The invention is based on the object of certain l - [/ 3- (2,4-dich! Orphenyl)] - ethyl-lH-1,2,4-triazole ketals
to make available, which are characterized by good fungicidal and plant growth-regulating effect. The solution to this problem is characterized in the claims.

Specific examples of straight or branched Alkylrestc with 1 to 10 carbon atoms are methyl, ethyl, 1-methylethyl, propyl, U-dimethylethyl. Butyl, pentyl, hexyl, hepiyl, oil and Decyl group.

The compounds of the invention are easily converted from I H-1.2.4-triazole of the formula II hi'wxtellt. this is first converted into a metal salt by reaction with, for example, an alkali metal alkoxide, preferably with sodium methoxide. This metal salt is then reacted with a halide of the general formula ¹ IH, in which Y preferably represents a bromine atom and Ar represents the 2,4-dichlorophenyl group. The reaction of the 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. If Y in the general formula III is a bromine or chlorine atom, the addition of an alkali metal iodide, in particular sodium or potassium iodide, is preferred to carry out the reaction. 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 from the reaction mixture in a customary manner and optionally purified in a customary manner, for example by crystallization, extraction, digestion or Chromatograph.

The aforementioned implementation is explained by the following equation:

Y-CH ₂ -C-Ar

O O (UI)

Η NaO CH ₃ , Z ^

H
(Π)

DMF.NaJ

Y and Ar have the above meanings.

The compounds of the general formula I can be converted into the corresponding salts with an acid are, for example, by reacting 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,

Λ-hydroxypropionic acid,

2-oxopropionic acid,

Oxalic acid, propanedicarboxylic acid, 1,4-butanedicarboxylic acid,

Z-2-butenedicarboxylic acid,

E-2-butenedicarboxylic acid,

2-hydroxy-1,4-butanedicarboxylic acid, 2,3-dihydroxy-1,4-butanedicarboxylic acid, 2-hydroxy-1,2,3-propane tricarboxylic acid, benzoic acid, 3-phenyl propenecarboxylic acid, Λ-hydroxybenzene acetic acid,

Methanesulfonic acid,

Ethanesulfonic acid,

Hydroxyethanesulfonic acid,

4-methylbenzenesulfonic acid,

Λ-hydroxybenzoic acid,

4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid and

2-acetyloxybenzoic acid.

The salts obtained with acids can in a customary manner by reacting with a free base, for example with sodium or potassium hydroxide, can be converted into the corresponding free bases.

The starting compounds of the general formula IH are known in various ways and can per se be produced in a known manner. Such compounds in which Z is the group

-CH ₂ -CH ₂ -, -CH (CH ₃ J-CH ₂ -, - CH (CH ₁ ) -CH (CH ₃ ) or-CH ₂ -CH ₂ -CH ₂ -

significant, as well as their production are described in US-PS 75,999. In general, the Compounds of the general formula III by coalizing a corresponding ketone of the general Formula IV

Ar-C-CH ₂ Y

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

HO-Z-OH

in which Z has the above meaning, the reaction being carried out in the customary manner (cf. Synthesis, Vol. 1 [1974], p. 23).
The ketones of the general formula IV are known

j »and can be produced by known processes will.

From the general formula I it can be seen that the compounds prepared according to the invention are asymmetric Have carbon atom and therefore in

v, in the form of stereochemically different optical isomers. If, for example, there is an alkyl radical in the 4-position of the dioxolane structure, the carbon atom to which the alkyl radical is bonded and the carbon atom in the 2-position of the dioxolane structure are

Ai) arms asymmetrically. The optical isomers obtained by the process according to the invention can be isolated in a customary manner.

The compounds of general formula I prepared according to the invention and their salts with acids are

4 ^r > valuable for combating certain fungi and bacteria. These compounds can be used for the treatment of plants, animals and humans, each of which is affected by the action of pathogenic microorganisms.

jo The compounds prepared according to the invention represent valuable fungicides for use in the Agriculture. They are very effective against a variety of fungi, for example against such mushrooms, which are used in different types of plants

Vi lead to the formation of powdery mold, such as Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pannosa, Sphaerotheca mors-uvae and Unicinula necator, as well as other mushroom eggs, such as

M) Venturia inaequalis, Colletotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenuis, Thielaviopsis basicola, Helminthosporium gramineum and Penicillium digitatum.

The compounds prepared according to the invention

οι are both prophylactic as well as aucn valuable for their therapeutic effect. The effect of these compounds on phytopathogenic fungi is explained by the following experiments.

In several of these experiments 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethy!] - 1H-1,2,4-triazole of formula I-a

(I-a)

used.

A. Prophylactic effect of the compounds

the general formula I opposite

Erysiphe cichoracearum on cucumber

by treating the leaves.

10-day-old cucumber plants are each with 250, 100 or 10 ppm of the aqueous solution containing the compound to be investigated is sprayed. For comparison some of these plants remain untreated. After drying the plants are done on them light rubbing with a leaf heavily infected with Erysiphe cichoracearum will transfer spores of this fungus. 15 days after this artificial infection, the degree becomes of fungus formation assessed by counting the number of spots per plant. The results are in Table I. summarized, the stated values each being the mean values of two plants.

Table I.

Connections used:

π ^N

"Il N YY

CH ₂ Ar

ο ο

(Ua)

R. Base or salt judgement 100 ppm lOppm Ar 250 ppm 0 0 H base - - - 2,4- (CI) ₂ -C ₆ H ₃ CHj ENT ₃ 0 0 0 2,4- (CDj-C ₆ Hj C ₂ H ₅ ENT ₃ - 0 ü 2,4- (CI) ₂ -CH ₃ nCjH ₇ ENT ₃ - 2 - 2,4- (CDj-C ₆ H, nQH, l '/ ₂ (COOH) _: - 0 0 2,4- (CI) ₂ -C ₆ Hj nCjH ,, ENT - - - 2,4- (Ci) ₂ -C ₆ Hj nC ₆ H, ₃ ENT ₃ 0 2 - 2,4- (CI) ₂ -C ₆ Hj nC ₇ H _l5 ENT ₃ - - - 2,4- (CI) ₂ -C ₆ H ₃ nC ₈ H, _7th ENT ₃ 0 2,4- (CI) ₂ -C ₆ H, 0 = no stretching per plant. 1 = 1 to 5 spots per plant. 2 = 6 to 10 spots per plant. 3 = over 10 spots per plant.

A '. Prophylactic effect

opposite Erysiphe polyphaga on cucumbers

by treating the leaves

Young cucumber plants in the single-leaf stage are sprayed with 500, 250 and 125 ppm, respectively, of the aqueous solution containing the compound Ia. As a control, some plants remain 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 8th day after the treatment with the compound Ia. On the 18th and on the 34th day after this treatment with the compound, the percentage of the leaf surface area attacked by the fungus b ^r > is determined both in the infected leaves and in the newly developed leaves. The results, which each represent the mean values of 5 plants, are summarized in Table Γ.

Table Γ

judgement

Days after treatment
with connection Ia

34 days after treatment
with connection Ia

Infected after days

Infected leaves (a) or
newly developed leaves (b)

Concentration of the compound Ia
in the spray solution

untreated
500 ppm
250 ppm
125 ppm

100 100 100 100 100 100 100 100 100 100 100

00000000000

00000000000

00000000000

B. Prophylactic effect

against Erysiphe graminis on barley

by treating the soil

Barley plants are made by watering with 100 ml / plant of an aqueous solution of the compound l-a watered, which is present in a concentration of 1000, 100 or 10 ppm. The same will be used for control purposes Water the plants with the same amount of water. A natural infection of these plants is caused, which usually happens when these plants are kept in a glass house next to infected plants will. 16 days after treatment with the aforementioned solution, the number of stains on the Leaves of the plants determined. The results, which in each case represent the mean values of 5 plants, are in 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

opposite Erysiphe graminis on barley

by treating the leaves

Barley plants infested by Erysiphe graminis are each with an aqueous solution of the Compound I-a sprayed in the concentrations given below. 16 days after treatment the number of spots per plant is determined The results, the mean values of 5 plants are summarized in Table III.

20th

25th

3 (1

D. Prophylactic effect
opposite Podosphaera leuchotricha
on apple seedlings by spraying

One year old apple seedlings are each given one sprayed aqueous solution of the compound I-a in the concentrations given below. the Plants are artificially infected 1 day after treatment with Podosphaera leuchotricha spores and 36 Incubated for hours. 25 days after 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 shown in FIG Table IV summarized.

Table IV

Concentration of the compound Ia
in the spray solution

% Infestation

100 ppm
10 ppm

100
0
6th

E. Action against Thielaviopsis sp.

5 mm thick potato and leek slices are each in an aqueous solution of the compound I-a in

immersed in the concentrations given below. Then the slices are in a large plastic dish is placed on a filter paper, and the dish is covered with a glass lid. At the same day of treatment of the mentioned slices

with the compound I-a these are by spraying with a concentrated suspension of spores of Thielaviopsis sp. artificially infected and then incubated at room temperature. 6 days later that will Fungal growth on the discs by estimating the

assessed by the fungus-infested surface. The results are summarized in Table V.

% Infestation Table V % Infestation leek Table III 100
0
1.5
25th 60 Concentration of the Ver potato Concentration of the compound Ia
in the spray solution binding Ia in the test
solution, ppm 100
0
0
0
11th 100
0
0
42.8
100 0
65 1000
100
10
1 0
1000 ppm
100 ppm
10 ppm

The compounds of general formula I are also effective against fungi, against Humans and animals have pathogenic properties. For example, these connections are opposite Fungi such as Microsporum canis, Trichophyton menta-

10

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

F. Effect of compound la against candidiasis in goiter of turkeys

14 day old turkeys are artificially infected by administering a suspension containing 4 χ ΙΟ ⁶ CFU (Colony Forming Units) of Candida albicans and inserted into the crop using a probe. The animals then receive either their normal feed (control) or a medicinal feed containing 125 ppm of the compound la. Two weeks later, all turkeys are killed and cultures are set on each of the turnips. The number of Candida colonies per gram of goiter is recorded. The results are summarized in Table VI.

Table VI

number
of animals number of Candida colonies per g des
Goiter

control

3 520000

848 700

3132000

1909000

Ia, 125 ppm

247 200
6742

From Table VI it can be seen that the compound Ia at a dose of 125 ppm compared to a corresponding blind test is very effective.

G. Effectiveness of compound la against candidiasis in the vagina of rats

Female rats weighing approximately 100 g each are ovariectomized and hysterectomized. 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 5} CFU of Candida albicans. Groups of 4 rats each are then treated orally for 14 consecutive days either with polyethylene glycol 200 (PEG 200) or with the compound la. 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 medium containing 20 μ / ml penicillin and 40 μg / ml streptomycin. The number of Candida colonies is then counted. The results are summarized in Table VI.

Table VII Number of animals Days after the
treatment Assessment of the
0 1 2 0 0 Culture*)
3 4th 200 4 14th 0 1 0 1 3 PEG 4th 14th 3 0 0 Yes = no growth.
= 1-25 colonies.
= 26-100 colonies.
=> 100 colonies.
= countless colonies. *) 0 =
1 =
2 =
3 =
4 =

ti

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

H. Effectiveness of Compound Ia
against systemic candidiasis in guinea pigs

Adult male guinea pigs are infected intravenously with Candida albicans, which is a induce general systemic candidiasis. Then each group of 7 of the Guinea pigs for 14 consecutive days either polyethylene glycol 200 (PEG 200) or the Compound Ia administered orally. 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 cultivated according to G. The number of isolated Candida colonies per g of kidney is then counted. the Results are summarized in Table VIII.

Table VIII Number of animals Number of candida Colonies per gram of kidney PEU 200 1 182 2 2838 3 25220 4th 385 5 19800 6th 113 7th 345 Ia 1 0 2 18th 3 0 4th 0 5 0 6th 53 7th 0

Poured test solution which contains the amount of compound Ia indicated below. 28 days after the Treatment is to assess the growth of plants by determining their length and weight. The results, which in each case represent mean values from 5 plants, are summarized in Table IX.

From Table VIII it can be seen that the compound Ia against a strong systemic mycosis is very effective in guinea pigs.

In addition to their antimicrobial properties, the compounds of general formula I have valuable plant growth regulating properties. Depending on the type of plant and the administered dose stimulates or retards growth. In particular these compounds are suitable for retarding plant growth, especially the growth of Shoots, for example in tobacco plants. Under these circumstances, however, these connections excite in in other cases also plant growth.

The plant growth-regulating properties of the compounds of general formula I are given below explained using the example of compound Ia

I. Growth regulating effect on
Tomato plants by treating the soil

Young tomato plants 3.5 to 4 cm high are grown in planted in separate pots. Each pot comes with one

Table IX Length of
Plants, % Weight of
Plants, % la
mg per plant 100
114
127
122 100
118
134
116 Without
10
1
0.1

J. Growth regulating effect in barley
by treating the leaves

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

Table X

Concentration of the compound Ia weight of the

in the test solution, ppm plants,%

Not 100

125 126

60 116

K. Growth regulating effect
on saplings of tobacco plants

Tobacco plants of the »Xanthi« variety are grown in the greenhouse and in the early bud stage trimmed. After 5 days, the leaves are treated with an aqueous suspension of the compound la in an amount sprayed from 3 or 1.5 kg of the compound per hectare. Each treatment is repeated three times. 12 days after At the end of the treatment, the subsequent growth of the shoots is assessed and with the Growth of untreated tobacco plants compared. The reduction in the growth of the saplings is 100% when treated with 3.0 kg of the compound per hectare and 90% when treated with 1.5 kg per hectare.

L Soybean plant growth retardation

Soybean plants of the »Hark« variety are grown in the greenhouse at a temperature of 23 ° C, an irradiation with 20,000 lux and a day length of 14 hours in pots. After the third 3-leaved leaf has unfolded, the plants are treated with aqueous suspensions of the compound Ia

Concentrations of 1000, 500, 100 or 50 ppm - sprayed. After 14 days, growth inhibition no.

of treated plants compared to untreated

th plants assessed. The results are summarized in Table XI. >

Table XI

Concentration of the compound la growth

in suspension, ppm delay,%

14th

C ₃ H ₇ Cn)

100
50
control

70

40

25th

20th

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

M. For the following comparison tests the:> compounds listed below are used:

1. Compounds according to the invention investigated

η N ^{J (1}

N
CH ₂ -R

No. R

Cl

2 -C 1-4 Cl

O O

-CH ₃

7th
40 / \ ^x
OO -CH -Cl II ρ I n ₃ * _ 45 II. Known connections γ-ϊ 50 ΐ X- CH ₂ -C ^^ Cl 3575999 55 / \
OO
II

b0

b5

C ₄ H ₉ (Ii)

C (C ₆ Hs) ₂ -CH

/ \
OO

CH, PH,

U.S. PS
3755349, example 6

(Hydrochloride)

III. Test methods

1. Effect against

Puccinia triticina in wheat plants

(Residual protective effect)

6-day-old grass plants are sprayed to runoff with a broth prepared from a wettable powder of the active ingredient (600, 200, 60 and 20 ppm active ingredient). 24 hours later, the treated plants are infected uniformly with a uredospore suspension of the fungus. After a 48 hour incubation, at a relative humidity of 95 to 100% and a temperature of about 20 ⁰ C, the infected plants are placed in a greenhouse with a temperature of 22 ° C. The number and size of the infected areas are used as a measure of the effectiveness of the test compound. The wheat plants treated with the compounds 1 to 7 are slightly shorter than the plants treated with the comparison compounds A and B and the untreated plants.

2. Effect against

Venturia inaequalis in apple tree cuttings

(Residual protective effect)

Apple tree cuttings with new shoots 10 to 20 cm long are sprayed with an emulsion (600, 200 and 60 ppm of active ingredient) prepared from a wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a conidiospore suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90 to 100%. The plants are then left to stand in a greenhouse at a temperature of 20 to 24 ^° C. for 10 days. 15 days after infection, the plants are assessed for scab infestation.

3. Effect against

Cercospora arachidicola on peanut plants
(Residual protective effect)

Peanut plants 10 to 15 cm high are sprayed with a broth (200, 60, 20 and 6 ppm of active ingredient) prepared from a wettable powder of the active ingredient. 48 hours later, the plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 24 hours at a temperature of about 21 ^° C. and high atmospheric humidity and then left to stand in a greenhouse until the typical leaf spots appear. Twelve days after infection, the evaluation of the fungicidal effect is made on the basis of the number and size of the spots.

4. Effect against

Erysiphe graminis in barley plants

(Residual protective effect)

Barley plants about 8 cm high are sprayed with an emulsion (200, 60, 20, 6 and 2 ppm of active ingredient) prepared from a pinprn wettable powder of the active ingredient. After 48 hours, the treated plants are dusted with conidiospores of the fungus left to stand in a greenhouse at a temperature of about 22 ^° C. After 10 days, the fungal attack is assessed.

ι ο 5. Effect against

Puccinia triticina in wheat plants
(systemic effect)

5 day old wheat plants are grown with one

is watered broth (60, 20 and 6 ppm active ingredient) made from a wettable powder of the active ingredient. Care is taken that the broth does not come into contact with the above-ground parts of the plants. After 48 hours, the treated plants are infected uniformly with a uredospore suspension of the fungus. After incubation for 48 hours at a relative humidity of 95 to 100% and a temperature of about 20 ⁰ C, the plants are in a greenhouse at a temperature of about

left to stand at 22 ° C. The number and size of the infected areas serve as a measure of assessing the effectiveness of the test compound. The ones with the Compounds 1 to 7 treated wheat plants are slightly shorter than those with the comparison compounds

3 plants treated with A and B and the untreated plants Plants.

6. Effect against

Erysiphe graminis in mixed plants

(systemic effect)

Barley plants 8 cm high are watered with a broth made from a wettable powder of the active ingredient (60, 20, 6 and 2 ppm active ingredient). After 48 hours, the treated plants are dusted with conidiospores of the fungus. The infected barley plants are then allowed to stand in a greenhouse at a temperature of about 22 ⁰ C. The fungal attack is assessed after 10 days.

IV. Test Results

The concentrations of the active ingredients are given in ppm (600 ppm = 0.06% active ingredient). Both Test methods 1 to 4 (residual protective effect) refers to the concentration of the active ingredient on the one used Broth of the active ingredient, in test methods 5 and 6 (systemic effect on the volume of the soil).

The effect is expressed as a percentage compared to untreated control plants (= 100%). The percentage found falls into one of the following four areas:

0 = 0-5% infestation

1 = 5-20% infestation

2 = 20-50% infestation

3 «= 50-100% infestation (connection ineffective)

rort ...; ... i ■

I \ -3l VT Il VJ I

030 131/211

link Puccinia 200 60 20th Venturia 200 60 Cercospora 60 20th 6th Erysiphe 60 2Ü 6th 2 Puccinia 20th 6th Erysiphe 20th 6th 2 N) **. (Residual protection) 1 0 0 (Resl protection) 1 3 (Residual protection) 2 3 2 (Residual protection) 0 1 2 3 (systemic) 2 3 (systemic) 0 1 2 Ui OO 600 1 I. 0 600 1 3 200 2 3 2 200 0 1 2 3 60 2 3 60 0 1 3 Oi 1 0 0 0 1 0 0 0 0 0 0 2 0 0 1 1 2 0 0 1 0 1 1 2 1 * ■ » 0 0 0 1 1 0 1 0 0 0 2 0 0 1 1 2 0 0 2 0 1 1 2 Wl
(J) 2 0 0 0 0 0 0 1 0 0 0 1 0 0 0 0 1 0 2 3 0 1 1 2 O 0 0 0 1 0 0 2 0 0 0 1 0 0 0 0 1 0 2 3 0 1 2 3 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ] 1 1 0 1 0 0 1 1 0 0 0 0 0 0 1 0 0 0 0 0 0 1 1 1 2 0 2 0 ö 1 1 4th 0 0 2 3 0 0 2 0 0 0 0 0 0 0 1 2 0 0 0 0 0 1 2 0 1 2 3 0 0 2 0 0 ] 0 0 0 0 1 2 0 1 1 0 0 1 2 5 0 1 1 0 0 0 0 0 0 0 0 0 0 0 1 2 0 0 1 0 1 2 3 0 2 1 0 0 0 1 0 0 0 0 0 0 0 1 2 0 0 1 0 1 2 3 6th 0 0 0 0 0 0 0 0 0 0 1 0 0 0 1 1 0 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 1 0 0 0 1 1 0 0 0 0 0 1 2 7th 0 2 2 1 0 1 3 0 1 2 1 0 0 1 2 3 0 3 3 0 1 2 3 0 2 3 2 0 3 0 1 2 1 0 0 1 2 3 0 3 3 0 1 2 3 A. 1 1 2 3 1 3 3 1 3 3 2 0 1 1 2 3 0 1 3 0 3 3 3 2 2 2 3 1 3 3 1 3 3 2 0 1 1 2 3 1 2 3 0 3 3 3 B. 1 3 2 0 1 2 1 3 2 0 1 2

From the table it can be seen that the compounds of the invention have a broader spectrum of activity than the known imidazolyl compounds A and B. This is especially true for connection B.

For example, for the series of experiments "Erysiphe (residual protection)" in the table, the compounds 1 to 7 are still very effective at a very low dose, as they have a rating at a dose of 6 and even 2 ppm usually result in 1 or 2. In contrast, the comparative compounds A and B show at a dose of 2 ppm only a rating of 3 which means these compounds are useful at this concentration are ineffective.

The other values given in the table above also show similarly good results. In order to it can be seen that the compounds according to the invention in contrast to the known compounds a unexpectedly have higher effectiveness and thus used in a significantly lower concentration can be.

The compounds of the invention or their salts with acids can be used to form corresponding agents with fungicides and growth-regulating effects. To do this, these connections can be made with a solvent or a solid, semi-solid or liquid diluent or carrier will. When using appropriate solvents or diluents, be Obtain emulsions, suspensions or ointments. It can also use soaps, surface-active compounds and special dispersants are used, the compounds of the invention also being used together with other compounds with acaricidal, insecticidal, ovicidal, fungicidal and / or bactericidal effects as well as can be used with inactive auxiliaries.

The means can for example by atomizing, sprinkling, spraying, brushing, dipping, brushing or Impregnation can be applied. The active ingredients are also very effective in high dilution. For example, concentrations of the active ingredient from 0.1 to 10 percent by weight, based on the Weight of the product, effective in combating fungi or bacteria. However, it can also be higher Concentrations are used.

The examples illustrate the invention. Unless otherwise stated, parts are based on weight is.

example 1

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 150 parts of dimethylformamide. The methanol is then distilled off at ambient pressure reaches 130 ⁰ C until the temperature of the mixture. Then 25 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) 1,3-dioxolane are 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

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

B. 6 parts of the compound obtained in A are in 2,2'-oxybispropane as a solvent in the corresponding nitrate transferred. After the mixture has cooled, the salt is filtered off and extracted twice 2-propanone recrystallized. Yield 3 parts of the corresponding nitrate with a mp of 172.7 ° C.

C. 6 parts of the compound obtained according to A are in 2,2'-oxybispropane as a solvent in the corresponding sulfate transferred. The sulfate formed is filtered off and recrystallized from 2-propanol. That The product obtained is filtered off, recrystallized from ethanol after treatment with activated charcoal and dried Yield 6 parts of the corresponding sulfate with a melting point of 207.1 ° C.

Example 2

A solution of 23 parts of sodium in 80 parts of methanol is mixed with stirring with 6.9 parts of 1H-1,2,3-triazole and a mixture of 2 parts of nairium iodide and 100 parts of Ν, Ν-dimethylformamide. The methanol is distilled off under ambient pressure, until the temperature of the reaction mixture reaches 130 ° C. Then 34.4 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-methyl-1 _r 3-dioxolane are added, and the mixture is refluxed for 3 hours touched. The reaction mixture is then poured into water and the mixture obtained is extracted twice with diisopropyl ether. The extract is washed with water and then treated 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] -IH-1,2,4-triazole nitrate with a melting point of 137.8 ° C.

Example 3

A mixture of 9.5 parts of 1H-1,2,4-triazole and 225 Share Ν, Ν-dimethylformamide with stirring

Ji in portions with 4.2 parts of a 78 percent Dispersion of sodium hydride added after stirring until the foam has formed has continued, the mixture becomes 16 parts 2- (Bromomethyl) -2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolane added. The mixture is taking 5 hours Stirred at reflux, then cooled and poured into water. The mixture is made three times with 2,2'-oxybispropane extracted. The combined extracts are washed with water, dried, filtered and concentrated

4> steams. The residue is on a silica gel charged column using trichloromethane containing 2% methanol as the eluent cleaned The first fraction is collected and its eluent is distilled off. Of the 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-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -lH-

y-> 1,2,4-triazole nitrate from F. 132.6 ⁰ C.

Example 4

A solution of sodium methoxide obtained from 3.8 parts of sodium and 40 parts of methanol is under

Feo stirring with 11.5 parts of 1H-1,2,4-triazole and 225 parts of Ν, Ν-dimethylformamide. Then, the methanol is distilled off from the mixture reaches 15O ⁰ C until the temperature of the mixture. After adding 19 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-ethereal-

ti) 1,3-dioxolane is taking the mixture for 4 hours Stirred at reflux, then cooled and poured into water. The mixture is made three times with 2,2'-oxybispropane extracted. The combined extracts are with

Washed water, dried, filtered and evaporated The residue is deposited on a column loaded with silica gel using 2% methanol chromatographically containing trichloromethane as a lukewarm agent cleaned The first fraction is collected and its eluent is evaporated The residue is converted into the corresponding in 2,2'-oxybispropane Nitrate transferred The nitrate is filtered off and from a mixture of 4-methyl-2-pentanone and 2,2'-OxYbispropane recrystallized, yield 10.5 parts ι ο (49% αTh.) 1- [2- (2,4-Dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-methyl] -1H-1,2,4-triazole nitrate of 119.8 ° C.

Example 5

According to Example 4, but using the equivalent amounts of the starting compounds the following salts are obtained: 1-4-butyl-2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-ylmethyl] -1H-i , 2,4-triazolesesquiox Jat,

111.6 ° C; - "

1- [2- (2,4-dichlorophenyl) -4-pentyl-

1,3-dioxolan-2-ylmethylj-1H-1,2,4-triazole nitrate,

M.p. 130 3 ^° C;
l- [2- (2,4-dichlorophenyl) -4-hexyl-1,3-dioxolane

2-yl-methyl] -lH-l, 2,4-triazole nitrate, ² '

F. 106.2 ⁰ C;
1 - [2- (2,4-dichlorophenyl) -4-heptyl-1.3-dioxo 'ι n-2-yl-methyl] -lH-l, 2,4-triazole nitrate,

F. 96.8 ⁰ C;
1 - [2- (2,4-dichlorophenyl) -4-octy I-1,3-dioxolane ^} "

2-yl-methyl] -lH-l, 2,4-triazole nitrate,

110.6 ° C.

Example 6

With the compound produced according to the invention π A suspension, a dusting powder, a solution and an ointment are produced which are used for Suitable for combating fungi.

A. Suspension

1 - [2- (2,4-dichlorophenyI) -1,3-dioxolan-2-yl-methyl] -1H-U, 4-triazole 1 kg

Technical xylene 2 liters

Surface active compound 350 ml
Dilution up to
desired concentration
of the active ingredient water

B. Dust powder

20 parts of 1- [2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole are ground with 360 parts of talc in a ball mill. The mixture will then mixed with 8 parts of OJein and, after further grinding, with 4 parts of slaked lime. The powder obtained can be easily dusted and has good adhesion properties.

C. Solution

5 parts of 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1 H-1,2,4-triazole are dissolved in 95 parts of alkylated naphthalene.

D. Ointment

10 parts of 1- [2- (2,4-dichloropheny!) -1, 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole is dissolved in a heated liquid mixture of 400 parts of polyethylene glycol 400 and 590 parts of polyethylene glycol 1500. the Solution is stirred until cool, forming an ointment.

Claims (1)

Patent claims: 1. 1- [0- (2,4-dichlorophenyl)] - ethyl-1H-1,2,4-triazole ketals the general formula Cl (D 10