HU177329B - Fungicide,bactericide or plant-growth regulating compositions containing triasole derivatives,and process for producing the active agents - Google Patents

Abstract

Novel 1-(ss-aryl)-ethyl-1H-1,2,4-triazol ketals of the formula <IMAGE> in which Z and Ar are as defined in Claim 1, are obtained by reacting a metal salt of 1H-1,2,4-triazol with a halide carrying the radical <IMAGE> The novel compounds are used as fungicides.

Description

The present invention relates to novel fungicidal, bactericidal or plant growth regulating compositions and to the preparation of new 1- (p-aryl) ethyl-1H-1,2,4-triazole ketal derivatives as active ingredients thereof.

U.S. Pat. No. 3,575,999 discloses bacterial and fungicidal 1- (P-aryl) ethylimidazole ketal derivatives.

Triazole derivatives are also known in the art (see, for example, Dutch Patent Publication No. 69.13.028; French Patent Publication No. 2,200,012, which is described in Derwent Week V25 - Pharm., P. 7). , which are fungicidal or plant growth regulating. However, the novel 1- (P-aryl) ethyl-1H-1,2,4-triazole ketal derivatives differ from the known triazole derivatives in the nature of the side chain attached to the nitrogen atom of the triazole.

Thus, it has been found that the new I- (p-aryl) ethyl-1H-1,2,4-triazole ketal derivatives of formula I wherein Z is -CH, -CH ₂ -, -CH, CH, CH, -.

-CH (CH ₃ ) -CH (CH 1) - or -CH ₂ -CH (alkyl) - 20 and in the latter group the alkyl group contains from 1 to 10 carbon atoms and

Ar is naphthyl, fluorenyl, thienyl optionally substituted by halogen, or phenyl optionally substituted by 1 to 3 halogens, alkyl of 1 to 4 carbon atoms, C1 to C4 alkoxy, cyano or nitro, and their acid addition salts. fii ^ ic | d ^ W ^ er $ id and regulate plant growth. 30

Within the meaning of Z, alkyl may be straight or branched chain and may be, for example, methyl, ethyl. 1-methylethyl. propyl. Acetyl, 1,1-dimethyl. hutil-. pentyl. hexyl, heptyl. octyl or decyl. In the meaning of Ar (winter C 1-4 alkyl may be straight or branched chain and may be, for example, methyl, ethyl, propyl, 1-methylethyl, hutyl or 1,1-dimethylethyl). halogen may be any halogen atom of less than 127, i.e. fluorine, chlorine, bromine or iodine.

The ketals of formula (I) according to the invention are prepared by the reaction of the alkali metal salt. preferably with an alkali metal alcoholate. especially preferably by treatment with sodium methyl, by treatment with sodium methyl, the 1 Hl.2.4-triazole of formula (II) with a ketal derivative of formula (II) - wherein Ar and Z are represented by Y in halo, preferably bromine means react. The reaction is depicted in Scheme Λ, where / Ar and Y are as previously defined. NaOMe sodium ethyl acetate. DMF dimethylformamide and Na! sodium iodide »means. The reaction of the metal salt of the Η-1.2.4-triazole of formula (11) with the ketal derivative of formula (III) is preferably carried out in a polar inert organic solvent such as N, N-dimethylformamide. N, N-dimethylacetamide. acetonitrile or benzonitrile. These solvents may also be used in combination with other inorganic organic solvents such as benzene, methylbenzene or dimethylbenzene. When Y in the formula (III) is bromo or chloro, it is preferable that the reactant177329 is an alkali metal iodide. For example, the addition of sodium or potassium iodide. It is also desirable to use excessively elevated temperatures to enhance the reaction rate, and particularly preferred is the reaction at the boiling point of the reaction mixture. 5

The resulting ketals of formula I can be isolated from the reaction mixture in a known manner and, if desired, further purified. Isolation and purification can be carried out, for example, by crystallization, extraction, trituration and chromatography.

The free base ketals of formula (I) can be converted, if desired, into their acid addition salts, such as inorganic acids such as hydrochloric acid, hydrobromic acid, hydrogen iodide, sulfuric acid, nitric acid, and the like. thiocyanic or phosphoric acids, and organic acids such as acetic acid, propionic acid, 1,4-butanedioic acid, (Z) -2-butenoic acid, (E) -2-butenoic acid, 2-hydroxy-1,4-butane-20-dicarboxylic acid With 2,3-dihydroxy-1,4-butanedicarboxylic acid,

2-hydroxy-1,2,3-propane tricarboxylic acid, hydroxyacetic acid, α-hydroxypropionic acid, 2-oxopropionic acid, ethanedioic acid. propane dicarboxylic acid, benzoic acid, 3-phenylpropenoic acid, α-hydroxybenzene acetic acid, methanesulfonic acid, ethanesulfonic acid, hydroxy-cyanosulfonic acid. 4-methylbenzenesulfonic acid, a-hydroxybenzoic acid,

By reaction with 4-amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid or 2-acetyloxybenzoic acid.

The free bases of the acid addition salts may be liberated by treatment in a conventional manner, such as treatment with an alkali metal hydroxide such as sodium or potassium hydroxide.

The starting compounds of the formula (III), some of which are known compounds, may be prepared in known manner. For example, Z is -CH ₂ -CH ₂ -, -CHICHJ-CH _? -, -CH (CH,) - CH (CH ₃ ) -, and -CH, -CH, -CH, - and their preparation are known in U.S. Pat. No. 3,575,999. in U.S. Pat. Compounds of formula (III) may generally be prepared by ketaling a ketone derivative of formula (IV) wherein Ar and Y are as defined above with a diol of formula (V) wherein Z is as defined above. for example, one of the ketalization methods described in Synthesis, 1, 23 (1974).

For example, the preparation of compounds of formula (111) is preferably carried out by refluxing the two reactants for several hours (while separating the water as an azeotropic mixture) in a suitable organic solvent, preferably a simple alcohol such as ethanol. in propanol, butanol or pentanol in the presence of a suitable strong acid such as 4-methylbenzenesulfonic acid. Other suitable organic solvents for the reaction include aromatic hydrocarbons such as benzene, methylbenzene or dimethylbenzene and saturated hydrocarbons such as cyclohexane.

Thus, the compounds of formula (III) may be prepared, for example, as shown in Scheme B. In Scheme B, Ar, Y and Z are as previously defined.

The ketone derivatives of formula (IV) are generally known compounds and may be prepared in a manner known to those skilled in the art of organic chemistry.

It will be understood by those skilled in the art from formula (1) that many of the compounds of formula (I) contain asymmetric carbon atoms in their molecules and may thus exist in the form of optical isomers of different stereochemistry. In particular, when the dioxolane ring has an alkyl group at the 4-position, the carbon atom to which the alkyl group is attached and the carbon at the 2-position of the dioxolane ring are asymmetric. The stereochemically optical isomers of the compounds of formula (I) may be separated and separated from each other in a manner known per se. Of course, the various optical isomers are also included within the scope of the invention.

As mentioned above, the compounds of formula I and their acid addition salts can be used for controlling fungi and bacteria. Thus, these compounds are useful for treating plants suffering from diseases caused by pathogenic microorganisms and for killing microorganisms on various materials.

The compounds of formula I are thus highly potent agricultural fungicides. They are extremely effective against a variety of fungal species, including fungi that cause powdery mildew on various plants, such as Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga. Podosphaera leuchotricha, Sphaerotheca pannosa, Sphareotheca mors-uvae and Uncinula necator species, as well as other fungi such as Venturia inaequalis, Colietotrichum lindemuthianum, Fusarium oxysporum, Alternaria tenuis, Thielaviopsis basicola, Helminthosporium gramineum.

The compounds of the formula I are particularly useful for their prophylactic, curative and systemic activity. We wish to demonstrate their fungicidal activity against phytopathogenic fungi by the results of the following experiments.

In many of the experiments described below, 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H, which is a compound of formula I, -1,2,4-triazole is used as the test compound, but this does not mean that the invention is intended to be limited to this compound.

A) Prophylactic activity of compounds of formula I against cucumber Erysiphe cichoracearum by foliar treatment.

For almost 10 days, cucumber seedlings are sprayed with an aqueous solution of 250,100 or 10 µg of the test compound. p. m. concentration. However, control plants are left untreated. After drying, the plants are infected with the spores of Erysiphe cychoracearum by weakly rubbing the plants with a highly infected leaf. 15 days after the artificial infection, the extent of the disease is determined by counting the spots on the plants. The values in Table I below are to the mean of two plants calculated according to the following scoring system.

- no spot is detected for the plant = 1-5 spots can be observed on the plant = 6-10 spots can be observed on the plant ~ more than 10 spots can be observed for the plant

Table I Compounds of formula Ib

Ar R Free base Fungicidal effect

or salt 250 p.p.m 100 p.p.m 10 p.j. 2,4- (Cl) ₂ -C ₆ H ₃ H base 0 0 c ₆ h ₅ H base - 3 - 4 — NO ₂ —C ₆ H ₄ H base 0 - - 30 0 -C ₆ H ₄ H base - 2 2 — Cl — C ₆ H ₄ H Exalt - 0 - 4 — Br — C ₆ H ₄ H base 0 - - 2 — Br C ₆ H ₄ H oxalate - 2 - 3-OCH-C ₆ H ₄ H oxalate 1 - - 2-CH-C ₆ H ₄ H oxalate 0 - - H oxalate 0 - - 4 —CH, —C ₆ H ₄ H oxalate 0 - - 4 — Cl — C ₆ H ₄ H oxalate monohydrate - • 0 - 2-naphthyl H oxalate 0 - - 2.5- (Cl) ₂ -C ₆ H ₃ H oxalate - 0 - 4 — CH — C ₆ H ₄ H oxalate 0 - - 3,4- (Cl) ₂ -C ₆ H ₃ H oxalate - 3 - 2 — OCH, —C ₆ H ₄ H oxalate 1 - - 2-thienyl H oxalate - 2 - 2-fluorenyl H base 0 - - 5-Cl-2-thienyl H base - 2 - 3-Br-4-CH ₃ -C ₆ H ₃ H base 0 - - 2 CH _} —4 — Br — C ₆ H, H base - 2 - 2- C'H. 4 — O C, .H. H base 0 - 3-Br-OH. H base 2 - - 4-IC ₆ H ₄ H oxalate 0 - - 3,5- (Cl) ₂ -C ₆ H ₃ H oxalate - 2 - 2,3- (C 1) ₂ C ₆ H ₃ H oxalate 0 - - 3 — NO ₂ —C ₆ H ₄ H base 1 - - 2.4- (Br) ₂ -C _(f) H ₃ H oxalate - I - 2,4,5- (Cl) -C ₆ H ₂ H oxalate 0 - - 2-Cl-4-OCH-C ₆ H, H oxalate - 2 - 2,4- (Cl) ₂ -C ₆ H ₃ CH ₃ nitrate 0 - 0 2,4- (Cl) ₂ -C ₆ H ₃ c ₂ h ₅ nitrate - 0 2,4- (Cl) ₂ -C <, H ₃ n-C ₃ H ₇ nitrate - 0 0 2,4— (Ojj — C $ H ₃ n-C ₄ H ₉ '/ 2 oxalate - 2 - 2,4 - (Cl) ₂ - n CjHn nitrate - 0 0 2,4 (0) ^ - ^ 3 n-guild nitrate 0 - - 2,4- (0) 2-0 ^ 3 n-C ₇ H _{) 5} nitrate - 2 - 2,4- (0) 2-C \ H ₃ n-CgH ₁₇ nitrate 0 -

A. L. Prophylactic effect against Erysiphe polyphaga in cucumber foliage.

Young single-leaf cucumber seedlings are sprayed with an aqueous solution of 500, 250 or 125 µg of the compound (Ia). p. m. concentration. However, control plants are left untreated. Artificial infection with the spores of Eiysiphe polyphaga is carried out by lightly rubbing the plants with a heavily infected leaf on the 4th, 6th or 8th day after spraying. On the 18th and 34th days after treatment, the percentage of fungal infestation on the leaves was determined separately for the initially infected leaves and the newly developed leaves. The following section 1.1. The values in Table 1 are the mean values of 5 plants and the percentages relative to the untreated control.

B) Prophylactic effect of the compound of formula (Ia) against Erysiphe graminis in barley soil treatment.

Barley plants are treated with irrigation at 100, 1000, 100 or 10 p. p. m. An aqueous solution containing a compound of formula (Ia) is irrigated. Control plants were watered with an equal volume of solution but not containing the compound of formula (Ia). Plants are kept in the vicinity of the greenhouse infected plants to induce natural infection, and on the 16th day after treatment, the degree of infection is evaluated by counting the spots on the leaves. Five plants were used to evaluate each concentration, and the mean values for the five plants as percentage of the control65 are shown in Table II below. table.

1.1. [Prophylactic effect of the compound of formula (Ia) against Erysiphe polyphaga in cucumber foliage treatment]

The day of evaluation

Day 18 after treatment

Day 34 after treatment

After treatment on the specified day 4 6 8 4 6 8 tőzve Infected leaves (a) or newly grown b a b a b a b a b a b

leaves (b) the concentration of the compound of formula (Ia) in the spray liquid

control

500 p. p. m.

250 p. p. m.

125 p. p. m.

100 100 100 100 100 100 100 100 100 100 100 100

II. [Prophylactic effect of the compound of formula (Ia) against Erysiphe graminis by barley soil treatment)

Dose per plant expressed as mg of compound of formula (Ia) Percentage relative to control control 100 100 mg 0 10 mg 0 1 mg 53

C) Healing effect against Erysiphe graminis by treatment of barley foliage.

Barley plants attacked by Erysiphe graminis are sprayed with aqueous solutions containing the indicated concentration of compound (Ia). On the 16th day after treatment, the number of spots per plant was determined. Five plants are used to evaluate each concentration. Below

III. The values in Table 1 are mean values and percentages relative to the control.

III. [The curative effect of the compound of formula (Ia) against Erysiphe graminis in barley foliage treatment]

The compound of formula (Ia) Compared to control concentration measurable in the spray liquid percentage 0 100 1000 p. p. m. 0 100 p. p. m. 1.5 10 p.m. p. m. 25

At day 3, the degree of fungal infection is evaluated by determining the number of spots. Two seedlings were used for each concentration. The average results obtained are shown in Table IV below. table. Values are percentages measured relative to the control.

ARC. [Prophylactic effect of the compound of formula (Ia) against Podosphaera leucotricha by spraying on apple seedlings]

30 Concentration of the compound of formula Ia in the spray liquid Percentage relative to control 0 100 35 100 p. p. m. 0 10 p.m. p. m. 6

E) Thielaviopsis sp. effect.

mm thick potato and onion slices were immersed in aqueous solutions containing the compound of formula Ia at the following concentrations of ⁴⁰ k. After dipping, place the slices in a large plastic bowl on filter paper and cover the bowl with glass. Artificial infection was performed on the day of treatment with slices of ⁴ Thielaviopsis sp. sprayed with a concentrated suspension of its spores and incubated at room temperature. On day 6 after treatment, the growth of the fungus is evaluated by examining the surface of the slices. The values shown in Table V below are percent values relative to the control.

Table V [Activity of the compound of formula (Ia) in Thielaviopsis sp. against]

-------------------------------------------------- ---------- Concentration of Percent Contamination of Compound of Formula (Ia) in Control Solution in Ppm Potato Onion

-------------------------------------------------- -------

0 100 100 1000 0 0 100 0 0 10 0 42.8 1 11 100

D) Prophylactic effect of compound (Ia) against Podosphaera leuchotricha by spraying on apple seedlings.

One-year-old apple tree seedlings are sprayed with aqueous solutions containing the compound of formula Ia at the indicated concentration. One day after treatment, seedlings are infected with spores of Podosphaera leuchotricha as indicated in Experiment A and incubated for 36 hours. After treatment 25.

In addition to their antimicrobial activity, the compounds of formula I have valuable plant growth regulating activity. The regulatory effect may be growth-promoting or growth-inhibiting, depending on various factors such as the type of plant treated and the concentration of active ingredient used. Thus, the compounds of formula (I) may be used alone to control plant growth. In particular, most of the compounds of the formula I are used for growth inhibition, particularly for example for the inhibition of shoot growth in tobacco. However, under certain circumstances, they can also be used to stimulate plant growth.

To illustrate the plant growth regulating activity of the compounds of formula (I), the following experiments are carried out with the compound of formula (Ia).

I. Plant growth regulating effect on tomatoes by soil treatment.

We plant young tomato plants 3.5 to 4 cm high in pots. In each pot, the soil is irrigated with experimental solutions containing the compound of formula Ia below. At day 28 post-treatment, growth is assessed by determining the length and weight of the plants. The results obtained are shown in Table IX below. table. Values given are mean values for five plants and percent values relative to control.

VI. [Plant growth regulating effect of a compound of formula (Ia) on tomato by soil treatment]

The dose of the compound of formula (Ia) is expressed in mg / plant unit Plants length in percent relative to control Plants weight as a percentage of control 0 100 100 10 114 18th 1 127 134 0.1 122 116

VII. [Plant growth regulating effect of compound (Ia) on barley foliage treatment]

The compound of formula (Ia) p. p. m in the test solution Average weight of plants as a percentage of control 0 100 I25 126 60 116

J) Plant growth regulating effect on barley by foliar treatment.

Young barley plants with 3-4 leaves are sprayed with test solutions containing the compound of formula la at the indicated concentrations. Twenty-four days after treatment, the growth of the plants is evaluated by determining their weight. The resulting and the following VII. The results in Table 1 are the mean values for ten plants and the percent values relative to the control.

K) Growth inhibitory effect on shoots in tobacco plants.

"Xanthi" tobacco plants are grown in a greenhouse and cut off at their early buds. On the 5th day after slaughter, the leaves of the plants are sprayed with an aqueous suspension of a compound of formula (Ia) at a concentration of 3 kg / ha or

Application rate of 1.5 kg / ha. Each treatment is repeated three times. Twelve days after treatment, post-treatment shoot growth is evaluated relative to apex depleted and untreated control plants.

Shoots increase at 3 kg / ha application rate

It is reduced by 100% and by 90% at 1.5 k & Twkar.

L) Growth inhibitory effect on soybeans.

Hark soybean plants are grown in pots in a climate chamber with a temperature of 23 ° C, illumination of 20000 Lux and illumination for 14 hours per day.

After the third leaf from the cotyledons has developed, the plants are sprayed with 1000, 500, 100 or 50 µl of the compound of formula (Ia). p. m. aqueous suspensions. On the 14th day after treatment, the percentage increase in the treated plants relative to the control was determined. The results obtained are shown in Table VIII below. table.

VIII. spreadsheet

Treatment Percentage growth inhibition From the compound of formula (Ia): 1000 p. p. m. 70% 500 p. p. m. 40% 100 p. p. m. 25% 50 p. p. m. 0% control 0%

II

1000 ρ. ρ. m. at active concentration the foliage color is more intensely green.

For their fungicidal, bactericidal and plant growth regulating effects described above, the compounds of the formula I or their acid addition salts may be advantageously used in the form of compositions which contain, in addition to the active ingredient, a solvent or solid, supple or liquid diluent or carrier. optionally containing a surfactant. Ready-to-use formulations include emulsions, suspensions, and dispersions which, in addition to carrier materials of appropriate consistency, contain natural or artificial soaps, other detergents and, if desired, other non-biologically active additives such as acaricides, insecticides, and / or bactericidal compounds known per se.

Solid carriers for powder formulations include various inorganic, porous and powdered materials of inorganic or organic origin, such as tricalcium phosphate, calcium carbonate (in the form of ground limestone or synthetic product), kaolin, paint, bentonite, silica gel, like powdered cork or sawdust.

The active ingredient is admixed with these carriers by, for example, grinding with them. Alternatively, the inert carrier material may be impregnated with a solution of the active ingredient in a volatile solvent and the solvent removed by heating or vacuum filtration. When wetting agents and / or dispersing agents are added, these compositions can be made wettable with water to form suspensions in use.

Inert solvents used in liquid preparations should, as far as possible, be highly flammable, odorless and non-toxic to warm-blooded animals or plants. Examples of such solvents are high-temperature oils of vegetable origin and solvents having a flash point of at least 30 ° C, such as polyethylene glycol. isopropanol, dimethyl sulfoxide, hydrogenated naphthalenes and alkylated naphthalenes. Of course, solvent mixtures may also be used. Solutions may be prepared in conventional manner, optionally using solubilizers. Other liquid forms which may be employed are emulsions or suspensions of the active ingredient in water or other suitable inert solvent, and concentrates for the preparation of such emulsions or suspensions, which may be adjusted directly to the desired concentration. For this purpose, the active ingredient is admixed, for example, with a dispersant or emulsifier. However, the active ingredient may also be directly dissolved or dispersed in an inert solvent and may be mixed with, or at the same time as, a dispersant 55 or emulsifier.

The active ingredient may also be used in the form of an aerosol. For this purpose, the active ingredient is dissolved or dispersed under atmospheric pressure at temperatures below room temperature in hot solvents or liquid carriers such as difluorodichloromethane or other volatile solvents. This gives a pressurized solution which, when sprayed, gives an aerosol. These aerosols are particularly effective for controlling fungi and bacteria, for example, in closed chambers and storage rooms, or 65 for aerosol treatment of plants to kill or prevent infections caused by bacteria or fungi.

The compounds of formula (I) or compositions containing them are used conventionally. For example, a fungal or bacterial culture, or material attacked or attacked by a fungus or bacterium, may be sprayed, sprayed, impregnated, or dipped in the compositions.

When used in combination with suitable carriers, such as solutions, suspensions, dusts, wettable powders, or emulsions, the compounds of Formula I are also effective at very high dilution concentrations. For example, from 0.1 to 90% by weight of the composition employed, the active ingredient is effective in controlling fungi or bacteria.

The following examples illustrate the invention.

Example 1 Weight of 1- (4-amino-2-methoxyphenyl) ethanone. A stirred solution of 360 parts by weight of concentrated hydrochloric acid, 75 parts by weight of water and 30 parts by weight of acetic acid, cooled to 0 ° C, is treated with 17.25 parts by weight of sodium nitrite in 200 parts by weight of water. After stirring at 0 ° C for 30 minutes, the solution was poured into 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid with stirring. The reaction mixture was then heated at 60 ° C for 1 hour, cooled to room temperature and extracted twice with 2.2'-oxybispropane. The combined extracts were washed with water, dilute sodium hydroxide solution and water twice more, dried, filtered and evaporated. There was thus obtained 1- (4-chloro-2-methoxyphenyl) ethanone (28% by weight, 76%), m.p.

Example 2

To a mixture of 78.8 parts by weight of 2-bromo-1- (4-bromo-2-methylphenyl) -1-ethanone and 200 parts by weight of butanol, 3 parts by weight of 4-methylbenzenesulfonic acid and 225 parts by weight of benzene are added followed by 33.5 drops. 1 g of 1,2-ethanediol is added. After the addition was complete, the reaction mixture was refluxed overnight under stirring with a water separator, evaporated and the resulting residue was dissolved in 2,2'-oxybispropane. The resulting solution was stirred with 15 parts by weight of concentrated sodium hydroxide solution, the layers were separated and the aqueous layer was extracted with 2,2-oxybispropane. The combined organic layers were washed with water until neutral, then dried, filtered and evaporated. The solid residue was crystallized from methanol. 30.5 parts by weight of 2-bromomethyl-2- (4-bromo-2-methylphenyl) -1,3-dioxolane, m.p.

Example 3

The procedure described in Example 2 was followed, but using 2-bromo-1- (4-bromo-2-methylphenyl) -1-ethanone in an equivalent amount using the appropriate 1-aryl-2-bisphenyl-ethanone as described below aryl-2-bromo-m-1,3-didxoto-8-derivatives can be prepared:

4- (2-bromomethyl-1,3-dioxolan-2-yl) -benzonitrile, m.p. 92.4 ° C; and

2-Bromomethyl-2- (2-naphthyl) -1,3-dioxolane, m.p.

Example 4

At C, 220 parts of 1- (5-chloro-2-thienyl) -1-ethanone are dissolved in 220 parts of 1,2-ethanediol, and 64 parts of elemental bromine are added dropwise over 1 hour with stirring. After stirring for one hour at room temperature, 4 parts of 4-methylbenzenesulfonic acid and 360 parts of benzene were added to the reaction mixture, which was then stirred under reflux with water separator overnight, evaporated and the residue was stirred for 2 hours. The resulting solution was washed thoroughly once with dilute sodium hydroxide solution, three times with water, then dried, filtered and evaporated to give a residue which was subjected to fractional distillation (73.3 parts by weight). 64.5%) of 2-bromomethyl-2- (5-chloro-2-thienyl) -1,3-dioxolane (b.p. 125-127 ° C) at 0.1 torr. k.

Example 5

The procedure described in Example 4 was followed, but using 1- (5-chloro-2-thienyl) -1-ethanone in equivalent amounts using the corresponding 1-aryl-1-ethanone, the following 2-aryl-2-bromomethyl- 1,3-dioxolane derivatives: 2-bromomethyl-2- (9H-fluoren-2-yl) -1,3-dioxolane, m.p. 90 ° C;

2-Bromomethyl-2- (3-bromo-4-methyl-phenyl) -1,3-dioxolane, bp 126-130 ° C at 0.1 torr;

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

2-bromomethyl-2- (4-chloro-2-methoxyphenyl) -1,3-dioxolane, m.p. 110 ° C; and 2-bromomethyl-2- (2,4-dibromophenyl) -1,3-dioxolane, m.p. 96 ° C.

Example 6

Step A: To a stirred solution of 2.3 parts of metal sodium in 120 parts of methanol was added 6.9 parts of 1H-1,2,4-triazole in 150 parts of dimethylformamide, and methanol was distilled under normal pressure until the reaction mixture was its temperature reaches 130 ° C. 25 parts of 2-bromomethyl-2- (2,4-dichlorophenyl) -1,3-dioxolane are then added to the reaction mixture and the mixture is refluxed for 3 hours under stirring. The reaction mixture was allowed to cool to room temperature and then poured into water. The precipitated product is filtered off, dissolved in diisopropyl ether, the resulting solution is treated with activated carbon, the carbon is filtered off and the solution is allowed to crystallize. Thus, 12 parts by weight

1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 109.9 ° C.

Step B: 6 parts by weight of the compound obtained in the previous step are converted into its nitrate salt in 2,2'-oxybispropane. After cooling, the salt is filtered off and crystallized twice from 2-propanone. 1- (2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1,1-1,2,4-triazole nitrate is obtained in 3 parts by weight, m.p. 172.7 ° C.

Step C: 6 parts by weight of the compound obtained in Step A are converted to the sulfate salt in 2,2'-oxybispropane, and the sulfate salt formed is filtered off and crystallized from 2-propanol. The precipitated crystals are filtered off and recrystallized from ethanol, even with activated charcoal. After drying the precipitated crystals, 6 parts by weight of 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1,1-1,2,4 m.p. triazole sulfate is obtained.

Example 7

To a stirred solution of 2.3 parts of metal sodium in 80 ml of methanol was added 6.9 parts of a mixture of 1H-1,2,4-triazole and 2 parts of sodium iodide in 100 parts of Ν, Ν-dimethylformamide. The methanol is then distilled under normal pressure until the internal temperature of the mixture reaches 130 ° C. 34.4 parts by weight of 2-bromomethyl-2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolane are added and the reaction mixture is heated under reflux for 3 hours. The reaction mixture was poured into water and the aqueous mixture was extracted twice with diisopropyl ether. The combined extracts were washed with water and excess nitric acid was added. The precipitated crude nitrate salt was filtered off and recrystallized from a mixture of 2-propanol and diisopropyl ether. Thus, 1- (2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl) -1- [1,2,4] m.p. triazole nitrate is obtained.

Example 8

To a stirred solution of 2.8 parts by weight of sodium sodium metal and 48 parts by weight of methanol are added 8.3 parts by weight of 1H-1,2,4-triazole. After stirring at room temperature for 30 minutes, 135 parts by weight of 5 Ν, Ν-dimethylformamide were added and methanol was distilled off. A mixture of 24.3 parts of 2-bromomethyl-2-phenyl-1,3-dioxolane and 3 parts of potassium iodide was then added to the reaction mixture, which was heated under reflux with stirring for 3 hours. The reaction mixture was allowed to cool to room temperature and then poured into water. The product is precipitated from the aqueous mixture by rubbing. The product is then filtered off with suction, washed with water, dried and finally crystallized from ethanol / 2.2'-oxybispropane (1: 5). 1- (2-Phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 127.3 ° C, is obtained in a yield of 10.9 parts by weight (43.7%). .

Example 9> The procedure described in Example 8 was followed, but using 2-aryl-2-bromomethyl-1,3-dioxolane in equivalent amounts instead of 2-bromomethyl-2-phenyl-1,3-dioxolane 1,2,4-triazole derivatives are obtained:

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

- [2- (3-chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1 H -1,2,4-triazole, m.p. 113.9 ° C;

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

11- (2- (3-methylphenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 105.4 ° C;

- [2- (3-Bromophenyl] -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 115.4 ° C; nitro-phenyl) -l, 3-dioxolan-2-ylmethyl] -lH-l, ^{2,4-triazole,} tetrazol, mp 154.1 ° C.

Example 13

Using an equivalent amount of starting materials as in Example 12, Formula Ic

1,2,4-Triazole slides may be prepared in the form of their oxalate salts.

Example 10

To a stirred solution of 1.6 parts by weight of sodium sodium metal and 48 parts by weight of methanol are added 4.9 parts by weight of 1H-1,2,4-triazole. After stirring at room temperature for 1 hour, 135 parts by weight of Ν, Ν-dimethylformamide are added and the methanol is distilled under normal pressure until the internal temperature of the reaction mixture reaches 130 ° C. 17.4 parts of 2-bromomethyl-2- (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide are then added to the reaction mixture. The reaction mixture was then refluxed with stirring overnight, then cooled to room temperature and poured into water. The product is precipitated from the aqueous mixture by rubbing. The precipitate was filtered off, washed with water and dissolved in trichloromethane. The resulting solution was purified by column chromatography over silica gel using a mixture of trichloromethane and 5% aqueous methanol as eluent. The pure fractions were combined and evaporated. The resulting residue was crystallized from a 9: 1 by volume mixture of 2,2'-oxybispropane and methanol. Thus, 9.3 parts (55.5%) of 1- [2- (2,3,4-trichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1 ú melting point 181.4 ° C. -1,2,4-triazole is obtained.

Example 11

The procedure described in Example 10 was followed using an equivalent amount of starting materials to give the following 1.2.4-triazole derivatives:

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

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

l- [2- (3-bromo-4-methylphenyl) -l, 3-dioxolan-2-ylmethyl] -lH-1,2,4-triazole. 120.7 ° C:

1- [2- (4-Bromo-2-methyl-phenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 148.1 C; and

(2- (4-chloro-2-methylphenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 147.9 ° C.

Example 12

To a stirred solution of 2.8 parts by weight of sodium methylate in metal and 56 parts by weight of methanol are added 8.3 parts by weight of a mixture of 1H-1,2,4-triazole and 135 parts by weight of N, N-dimethylformamide and methanol is distilled under normal pressure. while the internal temperature of the reaction mixture reaches 130 ° C. Then to the reaction mixture

27.8 parts by weight of a mixture of 2-bromomethyl-2- (2-chlorophenyl) -1,3-dioxolane and 3 parts by weight of potassium iodide are added and the mixture is heated under reflux for 6 hours. The reaction mixture was allowed to cool to room temperature, poured into water and extracted with 3 x Γ-oxybisethane (3x). The combined extracts were washed twice with water, dried, filtered and evaporated. The resulting residue is converted into the oxalate salt in 4-methyl-2-pentanone. The salt was filtered off and crystallized from 4-methyl-2-pentanone. Thus, 16 parts by weight

1- [2- (2-Chlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate salt, m.p. 156.5 ° C.

Price Compounds of formula Ic salt mp (° C) 2 — Br — C ₆ H ₄ oxalate 172.1 3 — OCH ₃ —C ₆ H ₄ oxalate 155.6 2 — CHj — C ₆ H ₄ oxalate 177.1 4 — F — C ₆ H ₄ oxalate 185.5 4 — CHj — C ₆ H ₄ oxalate 151.2 4 — Cl — C ₆ H ₄ oxalátmonohidrát 169.1 4 — OCHj — C ₆ H ₄ oxalate 187.1 2-naphthyl oxalate 175 2.5- (Cl) ₂ -C ₆ H ₃ oxalate 173.7 4 — CN — C ₆ H ₄ - oxalate 186.3 3,4- (Cl) ₂ -C ₆ Hj oxalate 182.2 2-thienyl oxalate 144.5 2,4- (Br) -C ₆ H ₃ oxalate 190.3

Example 14

To a solution of 2.3 parts by weight of sodium sodium metal and 48 parts by weight of methanol is added 6.9 parts by weight of 1H-1,2,4-triazole with stirring. After stirring at room temperature for 30 minutes, 135 parts by weight of Ν, Ν-dimethylformamide are added and the methanol is distilled at normal pressure until the internal temperature of the reaction mixture reaches 130 ° C. 3 parts by weight of potassium iodide and 16.4 parts by weight of 2-bromomethyl-2- (2-methoxyphenyl) -1,3-dioxolane are then added. The reaction mixture was then refluxed with stirring for 18 hours, cooled to room temperature and poured into water. The aqueous solution was extracted three times with trichloromethane and the combined extracts were washed four times with water, dried, filtered and evaporated. The residue was purified by column chromatography on silica gel using a mixture of trichloromethane and 5% aqueous methanol as eluent. The pure fractions were combined and evaporated. The residue is converted into its oxalate salt in 4-methyl-2-pentanone, and the salt is filtered off and then crystallized from a 2: 1 mixture of 2-propanone and 2,2'-oxybispropane. 5.5 (26%) of 1- (2- (2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl) -1 5 -1,2,4- m.p. triazole oxalate is obtained.

Example 15

Using an equivalent amount of starting materials as in Example 14, the following 1,2,4-fisoloxalate salts were obtained:

- [2- (4-iodophenyl) -1,3-dioxolan-2-yl] ethyl] -1H-1,2,4-triazole oxalate, m.p. 169.8 ° C;

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

dichlorophenyl-1,1-hydroxy-2-yl-2-methyl-3H- ¹ H, ¹ H, ² H

-triazole oxalate, m.p. 188.4 ° (%)

- [2- (4-chloro-2-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2.4-triazole oxalate, m.p. 173.2 ° C;

- [2- (2,4,5-Trifluorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole oxalate, m.p. C; and 1- [2- (2-Chloro-4-methoxyphenyl) -1,3-dioxolan-2-ylmethyl] -1H-5 -1,2,4-triazole oxalate, m.p. 188.2 ° C.

Example 16

To a stirred mixture of 9.5 parts by weight of 1H-1,2,4-triazole and 225 parts by weight of N, N-dimethylformamide are added 4.2 parts by weight of 78% sodium hydride dispersion in small portions. The reaction mixture was then stirred until the foaming ceased, and 16 parts by weight of 2-bromomethyl-2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolane were added and the reaction mixture was stirred at room temperature for 15 minutes. while stirring under reflux for 5 hours. The reaction mixture was cooled and poured into water, and the aqueous mixture was extracted three times with 2,2'-oxybispropane. The combined extracts were washed with water, dried, filtered and evaporated. The residue was purified by column chromatography over silica gel (eluent: trichloromethane / 2% methanol). The first fraction was separated and evaporated. The residue is converted into its nitrate salt in 2,2'-bisoxypropane, the salt is filtered off and finally crystallized from a mixture of 2-propanone and 25 petroleum ether. Thus, 1- (2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl) -1H, 8.2 parts (45%), m.p. 2,4-Triazole nitrate is obtained.

Example 17

To a stirred solution of 3.8 parts by weight of sodium methylate in metal and 40 parts by weight of methanol are added 11.5 parts by weight of 1H-1,2,4-triazole and 225 parts by weight of N, N-dimethylformamide and the methanol is distilled off. under normal pressure until the internal temperature of the reaction mixture reaches 150 ° C. To the reaction mixture was then added 19 parts by weight of 2-bromomethyl-2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane and the resulting mixture was heated under reflux for 4 hours. The reaction mixture was cooled and poured into water, and the aqueous mixture was extracted three times with 2,2'-oxybispropane. The combined extracts were washed with water, dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of trichloromethane and 2% aqueous methanol as eluent. The first fraction was separated and evaporated. The residue was converted to its nitrate salt in 2,2'-oxybispropane, filtered off and finally recrystallized from a mixture of 4-methyl-2-pentanone and 2,2'-oxybispropane. Thus, 10.5 parts by weight (49%)

1- [2- (2,4-Dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole nitrate, m.p. 119.8 ° C we get.

Example 18 55

In the same manner as in Example 17, the following 1,2,4-triazole derivatives can be prepared from equivalent amounts of the starting materials in the form of acid addition salts:

1- [4-Butyl-2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H-60

-1,2,4-triazole sesquioxalate, m.p. 111.6 ° C;

- [2- (2,4-Dichlorophenyl) -4-pentyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole nitrate, m.p. 130.3 ° C;

1- (2- (2,4-dichlorophenyl) -4-hexyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole nitrate, m.p. 2C; 65

1- (2- (2,4-Dichlorophenyl) -4-heptyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole nitrate, m.p. 96.8 ° C ; and

- (2- (2,4-Dichlorophenyl) -4-octyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole nitrate, m.p. 110.6 ° C.

Example 19

The compounds of formula (I) wherein Z is -CH, -CH ₃ -CH, - can also be prepared as described in Example 6, Step A. Thus, starting from an equivalent amount of the corresponding 2-aryl-2-bromomethyl-1,3-dioxane, 1- [2- (2,4-dichlorophenyl) -1,3-dioxane-2] is obtained. -ylmethyl] -1H-1,2.4-triazole, m.p. 113.9-117.8 ° C and its nitrate melting point 143.1 ° C.

Also in Example 6 illítható prepared as described in Step A and B, the melting point 125 1- (2- ^{(2,4-dichloro-1} phenyl) -4,5-dimethyl-1,3-dioxan-2-yl -methyl] -1? -1,2,4-triazole mononitrate.

2C. example

Compositions comprising the compounds of formula (I) obtainable by the process of the invention may be used for the control of fungi or bacteria as ready-to-use agents. For example, it may be formulated as a suspension, dustable composition or solution. The following are examples of ready-to-use agents:

(a) Suspension

component

- Polyethylene sorbitan monolaurate containing 2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole technical grade xylene mole clylene oxylol

Quantity in kg

I

350 ml

1- (2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole forms a stable aqueous suspension when dissolved in xylene followed by surfactant. emulsify.

(b) Dusting powder part 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole with 360 parts by weight of talc in a ball mill and 8 parts by weight of olein and the mixing is continued, and finally 4 parts by weight of lime milk are added to the mixture.The resulting powder is highly dispersible and has good adhesion.

(c) Solution parts by weight of 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole are dissolved in 95 parts by weight of 1-methylnaphthalene, and the resulting solution is sprayed to treat fungi-infected individuals and may be used to treat walls, corridors, or other objects to prevent fungal infection.

(d) Particulate matter by weight of 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole is homogenized with 99 parts by weight of highly dispersed silica. a porous composition containing by weight of active ingredient which can be used directly for plant protection purposes.

(e) Wettable Powder Formulation, Part by weight of 1- [2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl] -1H, 2,4-triazole, 5 parts by weight of sodium salt of lignin sulfonic acid, 1 part by weight of dibutylnaphthalenesulfonic acid and homogenizing with 4 parts by weight of silica to give a wettable powder formulation containing 90 parts by weight of the active ingredient. This formulation is readily dispersible in water and can be applied by spraying.

Example 21

In the following, comparative experiments and their results will be described.

On the one hand, the following compounds of formula I are used in comparative experiments.

Ar Z The compound number of the example

2,4-dichloro-

-phenyl-CH ₂ -CH ₂ -1

2,4-dichloro-

-phenyl-CH ₂ -CH (CH ₂ ) -2

2,4-dichloro-

-phenyl-CH ₂ -CH (n-C 4 H 9) -3

2,4-dichloro-

-phenyl-CH ₂ -C (n-CU 17) -4

2,4-dichloro-

phenyl-CH, CH, CH, -5

2,4-dichloro-

-phenyl - CH, -CH (C, H ₅ ) -6

2,4-dichloro-

-phenyl-CH (CH ₃ ) -CH (CH}) 7

On the other hand, 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl] imidazole (Compound A in the example) disclosed in U.S. Patent 3,575,999, and 1- [2,2-Dimethoxy-1,1-diphenyl-1-ethyl] -imidazole (Compound B in the Example), as disclosed in U.S. Patent No. 3,755,349.

The experimental methods are described below.

(a) Effect on wheat against Puecinia triticina (residual protective effect)

Six-day wheat seedlings were sprayed with cauliflower at 600.200.60 and 20 p.p.m. Concentrated in a nasal suspension prepared by diluting the wettable powder composition with water to the following composition:

part by weight of active ingredient part by weight of lignin sulphonic acid sodium salt part by weight dibutylnaphthalenesulphonic acid sodium part by weight silicic acid (Note that the wettable powder formulations mentioned below have the same composition.)

After incubation at 95% to 100% humidity for 48 hours at about 20 ° C, the plants are placed in a greenhouse near 22 ° C. To evaluate the effect of the test compounds, the number and extent of infected areas were determined. 1-7. wheat seedlings treated with compounds A are slightly shorter than taste A and

Plants treated with Compound B and untreated control plants.

(b) Effect on apple cuttings against Venturia inaequalis (residual protective effect)

10 to 20 cm long apple cuttings containing new sprouts are sprayed with 600,200 and 60 p.p.m. of a suspension prepared from a wettable powder formulation containing the active ingredient by dilution with water. After 24 hours, the treated cuttings are inoculated with a suspension of fungal conidiospores. The plants were then incubated for 5 days at 90-100% humidity and kept in a greenhouse at 20-24 ° C for 10 days. 15 days after infection, the extent of scabs is evaluated.

(c) Peanut effect against Cercospora arachidicola (residual protective effect)

Spray 10 to 15 cm tall peanuts at 200, 60, 20, and 6 ppm. p. m. containing a slurry of the active ingredient in aqueous solution prepared by diluting the wettable powder formulation containing the active ingredient with water. 48 hours later, the plants are inoculated with a conidium suspension of the fungus. The infected plants are incubated for 24 hours at 21 ° C and almost 100% humidity and then kept in a greenhouse until characteristic leaf spots appear. Twelve days after infection, an evaluation of the fungicidal effect should be made, taking into account the size and number of spots.

(d) Effect against barley against Erysiphe graminis (residual protective effect)

Barley plants, nearly 8 cm high, are sprayed with 200, 60, 20, 6 and 2 p.p.m. containing a slurry of the active ingredient in a concentrated form prepared by dilution with an aqueous wettable powder formulation containing the active ingredient. After 48 hours, the plants are pollinated with conidiospores of the fungus. The infected plants are kept in a greenhouse at about 22 ° C and the infection is evaluated 10 days after infection.

e) Systemic action on wheat against Puecinia triticina sunflower seedlings at 60, 20 and 6 p.p.m. is prepared by dilution with water of a wettable powder formulation containing the active ingredient. During irrigation, care is taken to prevent the suspension from coming into contact with the above-ground part of the plant. After 48 hours, the treated plants were uniformly infected with a suspension of fungal uredospores. After incubation for 48 hours at 95-100% humidity and near 20 ° C, the plants are kept in a greenhouse at about 22 ° C. The criterion for the efficacy of the test compounds is the number and size of the infected areas. 1-7. Compound treated wheat seedlings are slightly shorter than A- and B-treated plants and untreated control plants.

(f) Systemic action against barley against Erysiphe graminis

Nearly 8 cm high barley plants with the active ingredient 60, 20, 6 and 2 p.p.m. is prepared from a wettable powder formulation containing the active ingredient by dilution with water. After 48 hours, the treated plants are sprayed with the fungal conidiospores. The infected plants are then kept in a greenhouse near 22 ° C and the infection is evaluated after 10 days. 10

The results obtained are shown in Table IX. table. IX. Table a) for experiments a) - d) a

The active ingredient content, expressed in p.p.m., is related to the aqueous suspension used for the treatment, while in experiments e) and f) it is based on the soil volume.

The effect is expressed in terms of the rate of infection (100%) of the fungal infection on the untreated control plant, the percentage of infection being divided into the following four ranges:

= 0-5% infection = 5-20% infection = 20-50% infection = 50-100% infection (compound ineffective) Each experiment is performed in duplicate.

Serial number of compound Puccinia (residual) 600 200 60 20 Venturia (residual) 600 200 60 Cercospora (Residual) 200 60 20 6 Erysiphe (residual) 200 60 20 6 2 Puccinia (systemic) 60 20 6 Erysiphe (Systememiluf I 60 20 6 2 1 0 100 0 1 3 02 3 2 00 123 023 00 12 0 110 I I 3 0 2 3 2 00123 02 3 00 13 2 000 1 000 0002 0 0 112 00 1 0 1 1 ' 00 0 1 0 0 1 0002 0 0 112 00 2 0 112 3 0000 00 1 000 1 0 00 0 1 1 2 3 0 112 000 1 002 000 1 00 0 0 1 22 3 0 12 3 4 00 00 0 0 0 0000 0 00 11 00 1 00 11 0,000 0 0 1 0000 0 0 111 002 00 11 5 00 2 3 0 0 2 0000 0 0 0 12 000 OOI? 0 12 3 0 0 2 0 0 10 0 00 1 2 0 1 1 00 12 6 0 110 0 0 0 0000 000 1 2 00 1 0 12 3 02 10 0 0 1 0,000 000 12 00 1 0 12 3 7 00 0 0 000 0001 0 00 11 000 00 11 00 10 0 00 000 1 0 0011 0 00 00 12 THE 12 2 1 1 1 3 112 1 00 123 0 3 3 0 12 3 22 3 2 1 2 3 112 1 0 0 12 3 1 3 3 0 12 3 B 112 3 3 3 3 2 3 3 2 0 112 3 1 1 3 2 3 3 3 12 2 3 3 3 3 2 3 3 2 0 112 3 1 2 3 2 3 3 3

Patent claims

Claims (4)

Patent claims 1. Fungicide. bactericides or plant growth regulating composition comprising, as active ingredient 0.1 to 90 weight ⁰ / amount of formula (I), triazole derivative of formula - wherein Z is -CH ₂ CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -. -CH (CH ₃ } -CH (CH ₃ ) - or CH ₂ -CH (alkyl) -, the latter group having from 1 to 10 carbon atoms, and Ar is naphthyl, fluorenyl. thienyl optionally substituted with halogen, or optionally substituted with 1 to 3 halogens, C 1-4 alkyl, C 1-4 alkoxy, cyano or nitro substituted phenyl, or an acid addition salt thereof with a total content of 100% in an amount of a carrier, preferably talc or silica, and optionally a surfactant, preferably a wetting or emulsifying agent, provided that the surfactant is present in an amount of up to 20% by weight. (Priority: October 9, 1975) 2. A fungicidal, bactericidal or plant growth regulator composition comprising 0.1 to 90% by weight of a triazole derivative of the formula I as an active ingredient, wherein Z is -CH ₂ -Cl ₁₂ -. -CH ₂ -CH-CH ₂ -. CH (CH) CH (CH?) - or _(H -CH (CH?) - group, and Ar is naphthyl, thienyl optionally substituted with halogen, or allyl containing 1-4 carbon atoms, optionally substituted with 1 to 3 halogens, and 1-4 carbon atoms. cyano or nitro substituted phenyl, or an acid addition salt thereof for agricultural use and a total amount necessary for 100% of a carrier, preferably talc or silicic acid, and optionally a surfactant, preferably a wetting or emulsifying agent, provided that the surfactant is amount of material not exceeding 20% by weight. (Priority: November 18, 1974) Embodiment according to claim 1 or 2, characterized in that the active ingredient is 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl-melyl]. ] -l Hi, 2,4-thiazole or an acid addition salt thereof for agricultural use. (Priority: November 18, 1974) The article of manufacture of claim 1 or claim 2. characterized in that the active ingredient is 1- [2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2.4-triazole or for agricultural use. containing a suitable acid addition salt thereof. (Priority: November 18, 1974)