CH625103A5 - Fungicide - Google Patents

Abstract

The fungicide contains, as at least one active ingredient, a novel compound of the formula <IMAGE> in which Ar and Z are as defined in Claim 1, or salts of this compound. A process for the preparation of the composition is described.

Description

The invention relates to a fungicidal agent, which is characterized in that it is a new compound of the formula

10th

N

N I

CH

N

J1

(I)

• Ar

/ \

O O

V

in which Z denotes the group -CH2-CH2-, -CH2-CH2-CH2-, -CH (CH3) -CH (ch3) - or -CH2-CH (alkyl) -, where alkyl is a unbranched or branched alkyl radical with 1 represents up to 10 carbon atoms, and Ar is a phenyl group which is optionally substituted by 1 to 3 halogen atoms, alkyl radicals having 1 to 6 carbon atoms, alkoxy radicals having 1 to 6 carbon atoms, cyano or nitro groups, a thienyl, halothienyl, naphthyl or fluorenyl group, or contains their salts with acids as at least one active component.

US Pat. No. 3,575,999 discloses l- (β-aryl) ethyimidazole ketals which are active against bacteria and fungi. Various triazole derivatives are also known which have fun-gicidal or plant growth-regulating properties.

The new triazole derivatives mentioned above differ from the corresponding known compounds, inter alia, by the side chain bonded to one of the nitrogen atoms of the triazole ring. Similar triazole derivatives are also known from Dutch patent application 6 912 028 and from FR 2 200 012, Derwent Week V25, Pharm., P. 7.

Specific examples of unbranched or branched alkyl radicals having 1 to 10 carbon atoms are the methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, butyl, pentyl, hexyl, heptyl, octyl and Decyl group.

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

Halogen atoms are the fluorine, chlorine, bromine or iodine atom.

The new ketals of the general formula I can easily be prepared from 1H-1,2,4-triazole of the formula II below, which is first converted into a metal salt by reaction with, for example, an alkali metal alkoxide, preferably with sodium methoxide. This metal salt can then be reacted with a halide of the general formula III, in which Y is preferably a bromine atom. The reaction of the 1H-1,2,4-triazoIs with a halide of the general formula III is preferably carried out in an organic inert polar solvent, such as N, N-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, then the To is to carry out the reaction

3rd

625 103

an alkali metal iodide, in particular sodium or potassium iodide, would be preferred. The reaction is preferably carried out at a higher temperature, in particular at the reflux temperature of the reaction mixture.

The ketal of general formula I obtained can be isolated in a conventional manner from the reaction mixture and given NaO. CH3

if cleaned in the usual way, for example by crystallization, extraction, digesting or chromatography.

The above implementation is explained by the following equation:

Y-CH-C-Ar

2 / \

° \ / °

e.g.

5>.

DMF, Nal

N.

H

-N

J!

(II)

(HI) (I)

The compound of general formula I obtained can be converted into the corresponding salt with an acid, 20 for example by reaction with an inorganic acid, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, thiocyanic acid or phosphoric acid, or an organic acid, such as acetic acid, Propionic acid, hydroxyacetic acid, a-hydroxypropionic acid, 2-oxopro-25 pionic acid, oxalic acid, propanedicarboxylic acid, 1,4-butanedicarboxylic acid, Z-2-butenedicarboxylic acid, E-2-butenedicarboxylic acid, 2-hydroxy-l, 4-butanedicarboxylic acid, 2 , 3-Dihydroxy-l, 4-bu-tandicarboxylic acid, 2-hydroxy-l, 2,3-propanetricarboxylic acid, benzoic acid, 3-phenylpropenecarboxylic acid, a-hydroxybenzene-30 acetic acid, methanesulfonic acid, ethanesulfonic acid, hydroxy-ethanesulfonic acid, 4-methylbenzenesulfonic acid, a-Hydroxybenzoic acid, 4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid and 2-acetyloxybenzoic acid. The salts obtained with acids can be converted into the corresponding free bases in a conventional manner by reaction with a free base, for example with sodium or potassium hydroxide.

The starting compounds of the general formula III are known in various ways and can be prepared in a manner known per se. Compounds of this type in which 40 Z denotes the group -CH2-CH2-, -CH (CH3) -CH2-, -CH (CH3) -CH (CH3) - or -CH2-CH2-CH2 ~,

and their manufacture are described in U.S. Patent No. 3,575,999. In general, the compounds of the general

Formula III by ketalizing a corresponding ketone of the general formula IV

O

II

Ar-C-CH2Y (IV)

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

HO-Z-OH (V)

in which Z has the meaning given above, the implementation taking place in the customary manner [cf. Synthesis, Vol. 1 (1974), p. 23].

In a preferred embodiment of the process described above, 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 such as cyclohexane and in the presence of a strong acid such as 4-methylbenzenesulfonic acid, heated under reflux. In order to separate the water formed azeotropically, a further organic solvent, preferably a simple alcohol, such as ethanol, propanol, butanol and pentanol, is preferably additionally used. The implementation is explained by the following equation:

O

II 4-Msthvlbonzolsulfonsaure s / - r- \ Ar.é.CH2Y + HO-Z-OH * <HU

(IV) (V)

benzene

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

It can be seen from general formula I that the new 55 active compounds have an asymmetric carbon atom and are therefore in the form of stereochemically different optical isomers. For example, if there is an alkyl radical in the 4-position of the dioxolane skeleton, the carbon atom to which the alkyl radical is attached and the carbon atom in the 2-position of the dioxolane skeleton are asymmetrical. The optical isomers obtained can be isolated in a conventional manner.

The new active compounds of the general formula 65 I and their salts with acids are valuable for combating certain fungi and bacteria. These compounds can be used to treat plants, animals and humans, each of which is affected by the action of pathogenic microorganisms.

The compounds mentioned are valuable fungicides for use in agriculture. They are very effective against a large number of fungi, for example against those fungi which lead to the formation of powdery mold in various types of plants, such as Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pan- nosa, Sphaerotheca mors-uvae and Uncinula necator, as well as to other fungi such as Venturia inaequalis, Colletotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenu-is, Thielaviopsis basicola, Helminthosporium gramineum and Penicillium digitatum.

The new compounds are both prophylactic and therapeutic

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precious. The effect of these compounds against phyto-pathogenic fungi is illustrated by the following experiments.

In several of these experiments, l- [2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-l, 2,4-triazole of the formula I-a s is used.

A. Prophylactic action of the compounds of the general formula I against Erysiphe cichoracearum on cucumbers by treating the leaves

10 day old cucumber plants are sprayed with 250, 100 or 10 ppm of the aqueous solution containing the compound to be examined. For comparison, some of these plants remain untreated. After the plants have dried, spores of this fungus are transferred to them by lightly rubbing them with a leaf heavily infected with Erysiphe cichoracearum. 15 days after this artificial infection, the degree of fungal formation is assessed by counting the number of hedge per plant. The results are summarized in Table I, the values given in each case representing mean values of two plants.

(I-a)

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15

Connections used:

Table I

(IIa)

0 = no stain per plant

1 = 1 to 5 spots per plant

2 = 6 to 10 spots per plant

3 = over 10 spots per plant

Ar

R

Base or salt

Assessment 250 ppm

100 ppm

10th

2,4- (Cl) 2-C6H3

H

base

_

0

0

c6h5

H

base

-

3rd

-

4-N02-C6H4

H

base

0

-

-

3-Cl-C6H4

H

base

-

2nd

-

2-Cl-C6H4

H

(COOH) 2

-

0

-

4-Br-C6H4

H

base

0

-

-

2-Br-C6H4

H

(COOH) 2

2nd

-

3-OCH3-C6H4

H

(COOH) 2

i

-

-

2-CH3-QH4

H-

(COOH) 2

0

-

-

4-F-C6H4

H

(COOH) 2

0

-

-

4-CH3-C5H4

H

(COOH) 2

0

-

-

4-Cl-C6H4

H

(C00H) 2H20

-

0

-

2-naphthyl

H

(COOH) 2

0

-

-

2,5- (Cl) 2-C6H3

H

(COOH) 2

-

0

-

4-CN-C6H4

H

(COOH) 2

0

-

-

3,4- (Cl) 2-C6H4

H

(COOH) 2

-

3rd

-

2-OCH3-C6H4

H

(COOH) 2

1

-

-

2-thienyl

H

(COOH) 2

2nd

-

2-fluorenyl

H

base

0

-

-

5-Cl-2-thienyl

H

base

-

2nd

-

3-Br, 4-CH3-C6H3

H

base

0

-

-

2-CH3, 4-Br-C6H3

H

base

-

2nd

-

2-CH3,4-Cl-C6H3

H

base

0

-

-

3-Br-C6H4

H

base

2nd

-

-

4-I-C6H4

H

(COOH) 2

0

-

-

3,5- (Cl) 2-C6H3

H

(COOH) 2

-

2nd

-

2,3- (Cl) 2-C6H3

H

(COOH) 2

0

-

-

3-N02-C6H4

H

base

1

-

-

2,4- (Br) 2-C6H3

H

(COOH) 2

-

1

-

2,4,5- (Cl) 3-C6H2

H

(COOH) 2

0

-

-

2-a, 4-OCH3-C6H3

H

(COOH) 2

-

2nd

-

2,4- (Cl) 2-C6H3

ch3

hno3

0

-

-

2,4- (Cl) 2-C6H3

c2hs hno3

-

0

0

2,4- (Cl) 2-C6H3

nC3H7

hno3

-

0

0

2,4- (Cl) 2-C6H3

nC4H9

IV2 (COOH) 2

-

2nd

-

2,4- (Q) 2-C6H3

ncshu hno3

-

0

0

2,4- (Cl) 2-C6H3

nC6H13

hno3

0

-

-

2,4- (Cl) 2-C6H3

nC7H15

hno3

-

2nd

-

2,4- (Cl) 2-C6H3

nC8H] 7

hno3

0

-

-

5

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A '. Prophylactic effect against 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 I-a 5. As a control, some plants remain untreated. Spores of this fungus are transferred to these plants by lightly rubbing with a leaf heavily infected with Erysiphe polyphaga, this artificial infection occurring on the 4th, 6th or 8th day after treatment with the compound I-a. 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 each represent mean values of 5 plants, are summarized in Table I '.

Table I '

Assessment 18 days after treatment with 34 days after treatment with

Compound Ia Compound Ia

Infected after days 4 6 8 4 6 8

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

Concentration of compound Ia in the spray solution untreated

100

100

100

100

100

100

100

100

100

100

100

100

500 ppm

0

0

0

0

0

0

0

0

0

0

0

0

250 ppm

0

0

0

0

0

0

0

0

0

0

0

0

135 ppm

0

0

0

0

0

0

0

0

0

0

0

0

B. Prophylactic effect against 25

Erysiphe graminis on barley by treating the soil

Barley plants are watered by watering each with 100 ml / plant of an aqueous solution of the compound I-a, which is present in a concentration of 1000, 100 or 10 ppm 30. As a control, the same plants are watered with the same amount of water. A natural infection of these plants is caused, which usually happens

if these plants are kept in a glass house next to infected plants. 16 days after treatment with 35 of the aforementioned solution, the number of spots on the leaves of the plants is determined. The results, which each represent mean values of 5 plants, are summarized in Table II.

Table II

Compound Ia, mg / plant% infestation

Control 100

100 mg 0

10 mg 0

1 mg 53

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

Barley plants infested with Erysiphe graminis are sprayed with an aqueous solution of compound I-a in the concentrations indicated below. 16 days 55 after the treatment, the number of spots per plant is determined. The results, which each represent mean values of 5 plants, are summarized in Table III.

Table III 60

Concentration of the compound Ia% infestation in the spray solution

0 100 65

1000 ppm 0

100 ppm 1.5

10 ppm 25

D. Prophylactic Effect against Podosphaera leuchotricha on Apple Seedlings by Spraying One-year-old apple seedlings are sprayed with an aqueous solution of the compound I-a in the concentrations given below. The plants are artificially infected 1 day after treatment with spores of Podosphaera leuchotricha and incubated for 36 hours. 25 days after the treatment with the compound I-a, the fungal attack is assessed by determining the number of spots. The results, which each represent mean values of 2 plants, are summarized in Table IV.

Table IV

Concentration of the compound Ia% infestation in the spray solution

0 100

100 ppm 0

10 ppm 6

E. Effect on Thielaviopsis sp.

5 mm thick potato and leek slices are each immersed in an aqueous solution of the compound I-a in the concentrations given below. The discs are then placed in a large plastic bowl on a filter paper and the bowl is covered with a glass lid. On the same day that said disks are treated with compound Ia, they are sprayed with a concentrated suspension of Thielaviopsis sp. artificially infected and then incubated at room temperature. Six days later, the fungal growth on the slices is assessed by estimating the surface affected by the fungus. The results are summarized in Table V.

Table V

Concentration of compound Ia in the test solution, ppm

% Infestation "potato

leek

0

100

100

1000

0

0

100

0

0

10th

0

42.8

1

11

100

45

625 103

6

The compounds of the general formula I are also active against fungi which have pathogenic properties in humans and animals. For example, these compounds are active against fungi such as Microsporum canis, Trichophyton mentagrophytes, Trichophyton rubrum, Aspergillus fumigatus, Phialophora verucosa, Cryptococcus neoformans, Candida albicans and Candida tropicalis.

In addition to their antimicrobial properties, the compounds of general formula I have valuable plant growth-regulating properties. Depending on the type of plants treated and the dose administered, growth can be stimulated or delayed. These compounds are particularly suitable for delaying the growth of plants, particularly the growth of shoots, for example in tobacco plants. Under these circumstances, however, these compounds also stimulate plant growth.

The compounds of general formula I or their salts with acids can be converted into corresponding agents with an antifungal effect. For this purpose, these compounds can be combined with a solvent or a solid, semi-solid or liquid diluent or carrier. When using appropriate solvents or diluents, e.g. Receive emulsions, suspensions or ointments. Soaps, surface-active compounds and special dispersants can also be used, and the new compounds can also be used together with other active compounds.

Solid carriers which can be used in powder form for the preparation of corresponding agents are, for example, various inert, porous and powdery inorganic or organic substances, such as tricalcium phosphate, calcium carbonate (in the form of treated lime or limestone), kaolin, clay, bentonite, talcum, kieselguhr , Boric acid, powdered cork and wood flour, as well as fine powdered substances of vegetable origin.

The compounds of general formula I are usually mixed with the aforementioned carriers, for example the components are ground together or the carrier is mixed with a solution of the active ingredient in a volatile solvent and then the solvent is removed by heating or suction. If wettable and / or dispersing substances are added, the resulting powdery mixtures can easily be wetted with water and converted into suspensions.

E.g. 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. Corresponding solvents are high-boiling oils, for example vegetable oils, and low-boiling solvents with a flash point of at least 30 ° C., such as polyethylene glycol, isopropanol, dimethyl sulfoxide and hydrogenated and alkylated naphthalene derivatives. Mixtures of solvents can also be used. The solutions are usually prepared in a customary manner, if appropriate in the presence of solubilizers. Other liquid forms of the compositions 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.

The compounds of the general formula I can also be converted into corresponding agents in the form of an aerosol. For this purpose, the active ingredient is e.g. dissolved or dispersed, optionally in the presence of an inert solvent, such as difluorodichloromethane, as a liquid carrier which boils at ambient pressure at a temperature below room temperature. In this preparation, pressurized solutions are obtained which give aerosols when sprayed and which are particularly suitable for combating fungi and bacteria, for example in closed chambers and storage rooms, and for the prophylactic and therapeutic treatment of plants.

The agents obtained in one of the above ways can be applied, for example, by spraying, sprinkling, spraying, brushing, dipping, brushing or impregnating. 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 composition, are still effective in combating fungi. However, higher concentrations can also be used.

The examples illustrate the invention. Parts refer to weight unless otherwise stated.

example 1

A mixture of 30 parts of l- (4-amino-2-methoxyphenyl) ethanol in 360 parts of concentrated hydrochloric acid, 75 parts of water and 30 parts of acetic acid, cooled to a temperature of 0 ° C., is stirred with a solution of 17.25 parts Sodium nitrite diazotized in 200 parts of water. After stirring for 30 minutes at the temperature mentioned, the reaction mixture is poured with stirring into a solution of 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid. The resulting mixture is heated to 60 ° C for 1 hour. After cooling to room temperature, the mixture is extracted twice with 2,2'-oxybispropane. The combined extracts are washed in turn with water, a dilute sodium hydroxide solution and again twice with water, then dried, filtered and evaporated. Yield 28 parts (76% of theory) of 1- (4-chloro-2-methoxyphenyl) ethanol of melting point 55 ° C.

Example 2

A mixture of 78.8 parts of 2-bromo-l- (4-bromo-2-methylphenyl) -l-ethanol and 200 parts of butanol is mixed with 3 parts of 4-methylbenzenesulfonic acid and 225 parts of benzene with stirring. Then 33.5 parts of 1,2-ethanediol are added dropwise. To complete the reaction, the mixture is heated under reflux for 16 to 18 hours using a water separator. The reaction mixture is then evaporated. The residue is dissolved in 2,2'-oxybispropane and the solution obtained is stirred with 15 parts of concentrated sodium hydroxide solution. After separating the resulting layers, the aqueous layer is extracted with 2,2'-oxybispropane. The combined organic layers are washed with water until neutral, then dried, filtered and evaporated. The solid residue is recrystallized from methanol. Yield 30.5 parts of 2- (bromomethyl) -2- (4-bromo-2-methylphenyl) -l, 3-dioxolane, mp 86 ° C.

Example 3

According to Example 2, but using an equivalent amount of the corresponding l-aryl-2-bromo-l-ethanol instead of 2-bromo-1- (4-bromo-2-methylphenyl) -l-ethanol, the following compounds are obtained .

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60

65

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4- [2- (bromomethyl) -1, 3-dioxolan-2-yl] benzonitrile,

F. 92.4 ° C;

2- (bromomethyl) -2- (2-napthalenyl) -1, 3-dioxolane,

F. 64 ° C.

Example 4

57 parts of l- (5-chloro-2-thienyl) -l-ethanone are dissolved in 220 parts of 1,2-etanediol at a temperature of 50 ° C. 64 parts of bromine are added dropwise to the solution with stirring over the course of 1 hour without heating from the outside. 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 heated under reflux for 16 to 18 hours using a water separator. The reaction mixture is then evaporated. The residue is taken up in 2,2-oxybispropane. The solution obtained is washed in turn 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) of 2- (bromomethyl) -2- (5-chloro-2-thienyl) -l, 3-dioxolane, b.p. 125 to 127 ° C / 0.1 Torr.

Example 5

According to Example 4, but using an equivalent amount of the corresponding 1-aryl-1-ethanol instead of 1- (5-chloro-2-thienyl) -l-ethanol, the following compounds are obtained:

2- (bromomethyl) -2- (9H-fluorene-2-yl) -1, 3-dioxolane,

F. 90 ° C;

2- (bromomethyl) -2- (3-bromo-4-methylphenyl) -1, 3-dioxolane,

Bp 126-130 ° C / 0.1 Torr; 2- (bromomethyl) -2- (4-iodophenyl) -1, 3-dioxolane, mp 74 ° C 2- (bromomethyl) -2- (4-chloro-2-methoxyphenyl) -l, 3-dioxolane, F 110 ° C;

2- (bromomethyl) -2- (2,4-dibromophenyl) -1, 3-dioxolane,

F. 96 ° C.

Example 6

A. 6.9 parts of a mixture of 1H-1,2,4-triazole and 150 parts of dimethylformamide are added to a solution of 2.3 parts of sodium in 120 parts of methanol. The methanol is then distilled off at ambient pressure until the temperature of the mixture reaches 130 ° C. Then 25 parts of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -1, 3-dioxolane are added. The mixture is stirred, heated under reflux for 3 hours, cooled to room temperature and poured into water. The precipitated product is filtered off and recrystallized from diisopropyl ether after treatment with activated carbon. Yield 12 parts of l- [2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-ylmethyl] -lH-l, 2,4-triazole, mp 109.9 ° C.

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

C. 6 parts of the compound obtained according to A are converted into 2,2'-oxybispropane as solvent in the corresponding sulfate. The sulfate formed is filtered off and recrystallized from 2-propanol. The product obtained is filtered off, uncrystallized from ethanol after treatment with activated carbon and dried. Yield 6 parts of the corresponding sulfate, mp 207.1 ° C.

Example 7

A solution of 2.3 parts of sodium in 80 parts of methanol is mixed 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 N, N-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-1,3-dioxolane are added and the mixture is stirred under reflux for 3 hours. 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 an excess of concentrated nitric acid is added. The crude nitrate is filtered off and recrystallized from a mixture of 2-propanol and diiospropyl ether. Yield 15 parts of l-r2- (2,4-dichlorophenyl) -4-methyl-l, 3-dioxolan-2-ylmethyl] - IH-1,2,4-triazole nitrate, mp 137.8 ° C.

Example 8

A solution of sodium methoxide obtained from 2.8 parts of sodium and 48 parts of methanol is mixed with 8.3 parts of 1H-l, 2,4-triazole with stirring. After stirring for 30 minutes 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-l, 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 falls out by rubbing against the inside of the vessel. This is filtered off, washed with water, dried and recrystallized from a mixture of ethanol and 2,2'-oxybispropane (1: 5 parts by volume). Yield 10.9 parts (43.7% of theory) of l- (2-phenyl-l, 3-dioxolan-2-yImethyl) -lH-l, 2,4-triazole, mp 127.3 ° C . -

Example 9

According to Example 8, but using an equivalent amount of the corresponding 2-aryl-2- (bromomethyl) -l, 3-dioxolane instead of l- (bromomethyl) -2-phenyl-1,3-dioxolane, the following are Obtaining compounds: 1- [2- (4-nitrophenyl) -1,3-dioxolan-2-ylmethyl] - 1H-

1,2,4-triazole, mp 160.1 ° C; l- [2- (3-chlorophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-

1,2,4-triazole, mp 113.9 ° C; l- [2- (4-bromophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-

1,2,4-triazole, mp 135.9 ° C; l- [2- (3-methylphenyl) -1, 3-dioxolan-2-ylmethyl] -1H-

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

1,2,4-triazole, mp 115.4 ° C; l-f2- (3-nitrophenyl) -l, 3-dioxolan-2-ylmethyl] -lH-1,2,4-triazole, mp 154.1 ° C.

Example 10

A solution of sodium methoxide obtained from 1.6 parts of sodium and 48 parts of methanol is mixed 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 until the temperature of the reaction mixture reaches 130 ° C. Then 17.4 parts of 2- (bromomethyl) -2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are added to the mixture in stages and the mixture is stirred under reflux for 16 to 18 hours. After cooling to room temperature, the reaction mixture is poured into water. When rubbing against the inside 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 loaded with silica gel using trichloromethane containing 5% methanol as the eluent. The pure fractions are collected and the eluent is distilled off. The backlog becomes one

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Mixture of 2,2'-oxybispropane and methanol (9: 1 parts by volume) recrystallized. Yield 9.3 parts (55.5% of theory) of l- [2- (2,3,4-trichlorophenyl) -1, 3-dioxolan-2-ylmethyl] -lH-

1,2,4-triazole, mp 181.4 ° C.

Example 11

According to Example 10, but using an equivalent amount of the corresponding starting compounds, the following compounds are obtained: l- [2- (9H-fluoren-2-yl) -l, 3-dioxolan-2-ylmethyl] -lH-

1,2,4-triazole, mp 186.8 ° C; l- [2- (5-chloro-2-thienyl) -1, 3-dioxolan-2-ylmethyl] -lH-

1,2,4-triazole, mp 117.4 ° C; 1- [2- (3-bromo-4-methylphenyl) -1, 3-dioxolan-2-ylmethyl] -

1H-1,2,4-triazole, mp 120.7 ° C; 1 - [2- (4-bromo-2-methylpehnyl) -1,3-dioxolan-2-ylmethyl] -

1H-1,2,4-triazole, mp 148.1 ° C; 1- [2- (4-chloro-2-methylphenyl) -1, 3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, mp 147.9 ° C.

Example 12

A solution of sodium methoxide obtained from 2.8 parts of sodium and 56 parts of methanol is mixed with stirring with a mixture of 8.3 parts of 1H-1, 2,4-triazole and 135 parts of N, N-dimethylformamide. The methanol is distilled off under ambient pressure until the temperature of the reaction mixture reaches 130 ° C. Then 27.8 parts of 2- (bromomethyl) -2- (2-chlorophenyl) -1, 3-dioxolane and 3 parts of potassium iodide are added to the mixture. After stirring under reflux for 6 hours, the reaction mixture is cooled to room temperature, poured into water and extracted three times with 1,1'-oxybisethane. The combined extracts are washed twice with water, dried, filtered and evaporated. The residue is converted into the corresponding oxalate in 4-methyl-2-pentanone. The oxalate is filtered off and recrystallized from 4-methyl-2-pentanone. Yield 16 parts of l- [2- (2-chlorophenyl) -l, 3-dioxolan-2-ylmethyl] -lH-l, 2,4-tri-

azole oxalate, mp 156.5 ° 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 indicated below are obtained:

v

I I

Ar

salt

F.

2-Br-C6H4

(COOH) 2

172.1 ° C

3-OCH3-C6H4

(COOH) 2

155.6 ° C

2-CH3-C6H4

(COOH) 2

177.1 ° C

4-F-C6H4

(COOH) 2

185.5 ° C

4-CH3-C6H4

(COOH) 2

151.2 ° C

4-Cl-C6H4

(C00H) 2H20

169.1 ° C

4-OCH3-C6H4

(COOH) 2

187.1 ° C

2-naphthalenyl

(COOH) 2

175 ° C

2,5- (Cl) 2-C6H3

(COOH) 2

173.7 ° C

4-CN-C6H4

(COOH) 2

186.3 ° C

3,4- (Cl) 2-C6H3

(COOH) 2

182.2 ° C

2-thienyl

(COOH) 2

144.5 ° C

2,4- (Br) 2-C6H3

(COOH) 2

190.3 ° C

Example 14

A solution of sodium methoxide obtained from 2.3 parts of sodium and 48 parts of methanol is mixed with 6.9 parts of 1H-l, 2,4-triazole with stirring. After stirring for 30 minutes at room temperature, 135 parts of N, N-dimethylformamide are added to the mixture. Then the methanol is distilled off under ambient pressure until the temperature of the mixture reaches 130 ° C. The mixture is then gradually added 3 parts of potassium iodide and 16.4 parts of 2- (bromomethyl) -2- (o-methoxyphenyl) -1, 3-dioxolane and stirred under reflux for 18 hours. After cooling to room temperature, the reaction mixture is poured into water and the solution obtained 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 trichloromethane containing 5% methanol as the eluent. 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 recrystallized from a mixture of 2-propanone and 2,2'-oxybispropane (2: 1 parts by volume). Yield 5.5 parts (26% of theory)

1 - [2- (2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] - IH-1,2,4-

triazole oxalate, mp 166.4 ° C.

Example 15

According to Example 14, but using an equivalent amount of the corresponding starting compound, the following salts are obtained: 1- [2- (4-iodophenyl) -1, 3-dioxolan-2-yImethyl] -

lH-l, 2,4-triazole oxolate, mp 169.8 ° C; l- [2- (3,5-dichlorophenyl) -1, 3-dioxolan-2-ylmethyI] -

1H-1, 2,4-triazole oxolate, mp 204.4 ° C; 1 - [2- (2,3-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -

1H-1, 2,4-triazole oxolate, mp 188.4 ° C; 1- [2- (4-chloro-2-methoxyphenyl) -1, 3-dioxolan-2-ylmethyl] -

1H-1,2,4-triazole oxolate, mp 173.2 ° C; 1- [2- (2,4,5-trichlorophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-l, 2,4-triazoloxolate, mp 178.4 ° C;

1- [2- (2-chloro-4-methoxyphenyl) -1, 3-dioxolan-2-ylmethyl] -1 H-1,2,4-triazoloxolate, mp 188.2 ° C.

Example 16

A mixture of 9.5 parts of 1H-1, 2,4-triazole and 225 parts of N, N-dimethylformamide is mixed in portions with 4.2 parts of a 78 percent dispersion of sodium hydride. After stirring is continued until foaming stops, 16 parts become the mixture

Given 2- (bromomethyl) -2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolane. The mixture is stirred under reflux for 5 hours, then cooled and poured into water. The mixture is extracted three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by chromatography on a column loaded with silica gel using trichloromethane containing 2% methanol as the eluent. The first fraction is collected and its eluent is distilled off. The residue is converted into the corresponding nitrate in 2,2'-oxy-bispropane. The nitrate is filtered off and recrystallized from a mixture of 2-propane and petroleum ether. Yield 8.2 parts (45% of theory) l- [2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-yImethyl] -

1H-1,2,4-triazole nitrate, mp 132.6 ° C.

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Example 17

A solution of sodium methoxide obtained from 3.8 parts of sodium and 40 parts of methanol is mixed with stirring with 11.5 parts of 1H-1, 2,4-triazole and 225 parts of N, N-dimethylformamide. Then the methanol is distilled off from the mixture until the temperature of the mixture reaches 150 ° C. After adding 19 parts

2- (Bromomethyl) -2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane, the mixture is stirred under reflux for 4 hours, then cooled and poured into water. The mixture is extracted three times with 2,2'-oxybispropane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by chromatography on a column loaded with silica gel using trichloromethane containing 2% methanol as the eluent. The first fraction is collected and its eluent is evaporated. The residue is converted into the corresponding nitrate in 2,2'-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)

l- [2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-ylmethyl] -

1H-1,2,4-triazole nitrate, mp 119.8 ° C.

Example 18

According to Example 17, but using the equivalent amounts of the starting compounds, the following salts are obtained:

1 - [4-butyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl-

methyl] -IH-l, 2,4-triazole sesquioxalate, mp 111.6 ° C; l- [2- (2,4-dichlorophenyl) -4-pentyl-l, 3-dioxolan-2-yl-

methyl] -IH-l, 2,4-triazole nitrate, mp 130.3 ° C; l- [2- (2,4-dichlorophenyl) -4-hexyl-l, 3-dioxolan-2-yl-

methyl] -IH-l, 2,4-triazole nitrate, mp 106.2 ° C; 1 - [2- (2,4-dichlorophenyI) -4-heptyI- l, 3-dioxolan-2-yl-

methyl] -IH-l, 2,4-triazole nitrate, mp 96.8 ° C; 1- [2- (2,4-dichlorophenyl) -4-octyl-l, 3-dioxolan-2-ylmethyl] -IH-l, 2,4-triazole nitrate, mp 110.6 ° C.

Example 19

According to Example 6A, but using an equivalent amount of the corresponding 2- (bromomethyl) -2-aryl-1,3-dioxolane instead of 2- (bromomethyl) -2- (2,4-dichlorophenyl) -1,3 -dioxolane, the following compounds are obtained:

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

1H-1,2,4-triazole: 1- [2- (2,6-dichlorophenyl) -1, 3-dioxolan-2-yImethyl] -

1H-1,2,4-triazole;

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

Example 20

According to Example 7, compounds of the general formula I can be prepared in which Z denotes the group -CH2CH (CH3) - or -CH (CH3) -CH (CH3) -. By using the corresponding 2-aryl-2- (bromomethyl) -4-methyl-1,3-dioxolane or 2-aryl-2- (bromomethyl) -4,5-dimethyl-1,3-dioxolane receive the following compounds in the form of their nitrates:

l- (4-methyl-2-phenyl-1,3-dioxo] an-2-ylmethyl) -IH-1,2,4-triazole;

1- [2- (4-chlorophenyl) -4-methyl-l, 3-dioxolan-2-ylmethyl] -

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

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

1H-1,2,4-triazole; 1 - [2- (4-methoxyphenyl) -4-methyl-1,3-dioxolan-2-yl-

methyl] - IH-1,2,4-triazole; l- [4,5-Dimethyl-2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-yl-

methyl] -1 H-1,2,4-triazole; l- (4,5-dimethyl-2-phenyl-l, 3-dioxolan-2-ylmethyl) -lH-1,2,4-triazole;

1- [2- (4-chlorophenyl) -4,5-dimethyl-1,3-dioxolan-2-ylmethyl] -1 H-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 -CH2-CH2-CH2-. If an equivalent amount of the corresponding 2-aryl-2- (bromomethyl) -l, 3-di-oxane is used as the starting compound, the following compounds are obtained:

l- (2-phenyl-l, 3-dioxan-2-ylmethyl) -lH-l, 2,4-triazole; l- [2- (2,4-dichlorophenyl) -1, 3-dioxan-2-ylmethyl] -1H-1,2,4-triazole;

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

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

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

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

1- [2- (2-Naphthyl) -1, 3-dioxan-2-ylmethyl] -1H-l, 2,4-triazole.

Example 22

The new compounds are used to produce a suspension, a powder and a solution that are suitable for combating fungi.

A. Suspension 1- [2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-yl-methyl] -1H-l, 2,4-triazole 1 kg

Technical xylene 2 liters of surface-active compound 350 ml

Dilution to the desired concentration of the active ingredient water

B. Dust powder

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

C. Solution

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

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Claims (8)

625 103 2nd PATENT CLAIMS 1. Fungicidal agent, characterized in that it means a new compound of the formula, or its salts with acids, mixed with formulation auxiliaries. N N Ì CH N ß (I) ■ Ar / \ O O V in which Z denotes the group -ch2-ch2-, -CH2-CH2-CH2-, —CH (CH3) -CH (ch3) - or —CH2-CH (alkyl) -, where alkyl is a straight-chain or branched alkyl radical with 1 represents up to 10 carbon atoms, and Ar represents a phenyl group which is optionally substituted by 1 to 3 halogen atoms, alkyl radicals having 1 to 6 carbon atoms, alkoxy radicals having 1 to 6 carbon atoms, cyano or nitro groups, a thienyl, halothienyl, naphthyl or fluorenyl group, or contains their salts with acids as at least one active component. 2. Composition according to claim 1, characterized in that it contains 1- [2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-ylmethyl] -1H-l, 2,4-triazole as the active component. 3. Composition according to claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) -4-methyl-l, 3-dioxolan-2-ylmethyl] -lH-l, 2,4- contains triazole as active component. 4. Composition according to claim 1, characterized in that it is 1- [2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-ylmethyl] -1H, 2,4-triazole as active component contains. 5. Composition according to claim 1, characterized in that it is l- [2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-ylmethyl] -lH-2,4-triazole contains active component. 6. Composition according to claim 1, characterized in that it is l- [2- (2,4-dichlorophenyl) -4-pentyl-l, 3-dioxolan-2-ylmethyl] -lH, 2,4-triazole contains active component. 7. Composition according to claim 1, characterized in that it contains a compound of formula I, which is present as an optical isomer, as an active component. 8. A process for the preparation of the fungicidal composition according to claim 1, characterized in that a compound of the formula (I) 25th 30th 40 55 60 in which Z denotes the group -CH2-CH2-, -CH2-CH2-CH2-, -CH (CH3) -CH (ch3) - or -CH2CH (alkyl) -, where alkyl is an unbranched or branched alkyl radical having 1 to 10 Represents carbon atoms, and Ar is a phenyl group optionally substituted by 1 to 3 halogen atoms, alkyl radicals having 1 to 6 carbon atoms, alkoxy radicals having 1 to 6 carbon atoms, cyano or nitro groups, a thienyl, halothienyl, naphthyl or fluorenyl group