CS203098B2 - Fungicide and agent for growth plants regulator and process for preparing efective compound - 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 invention relates to a novel fungicidal composition and to a plant growth regulating composition and to a process for the preparation of the active ingredient of the aforementioned composition. The compositions of the present invention have significant antibacterial and fungicidal properties.

In the prior art, a large number of triazole derivatives can be found here, some of which are described as fungicidal or growth-regulating agents.

1- (3-aryl) ethyl-imidazole ketals which exhibit antibacterial and fungicidal properties are described in U.S. Patent No. 3,575,999.

The closest prior art with respect to these triazole derivatives are the following references: Netherlands Patent Application No. 69 13 028, and France 2 200 012 - Derwent Week V 25 - Pharm. p. 7.

The compounds of the above. The invention differs from the prior art triazole derivatives, inter alia, by the nature and nature of the side chain attached to the triazole nitrogen atom.

The fungicidal and plant growth regulating agents according to the invention are characterized in that they contain an inert carrier material and contain, as active ingredient, 1-j + aryl] ethyl-1H-1,2,4-triazolketal of the formula I

I / J in which it means

Z alkylene comprising the groups —CH2 —CH2—, —CH2 —CH2 —CH2 — —CH (CH3J — C'H (CH3) - and —CH2 —CH (alkyl) -, wherein said alkyl contains 1 to 10 carbon atoms, and

Ar is a radical selected from the group consisting of phenyl, thienyl, halothienyl, naphthyl, fluorenyl, and substituted phenyl, wherein the substituted phenyl is a phenyl radical having 1 to 3 substituents independently selected from the group consisting of halogen, a straight or branched alkyl group containing 1 to 3 C 1 -C 6 alkoxy, cyano and nitro, or an acid addition salt thereof.

In a preferred embodiment, the fungicidal agent and the plant growth regulating agent according to the invention comprise as active substance 1- [β-aryl] ethyl 1-1H-1,2,4-triazoketal of the general formula Ia

1- (2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole or an acid addition salt of this compound,

1- [2- (2,4-dichlorophenyl) -4-pentyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole or an acid addition salt thereof.

SUMMARY OF THE INVENTION A process for the preparation of 1- (4-aryl) ethyl-1H-1,2,4-itriazoketal of the general formula I as defined above, in which Z and Ar have the same meaning as above, or acid addition salts thereof According to the invention, the metal salt of the compound of formula II is reacted

(ia) with a compound of formula (III) ## STR4 ## in which it represents

From alkyleii consisting of -CH-CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -СН (СНз) -CH (СНз) - or -CH ₂ -CH (methyl) -, and

Ar is phenyl, thienyl, halothienyl, naphth. or substituted phenyl, which refers to a phenyl radical having 1 to 3 substituents selected independently from the group consisting of halogen, alkyl of 1 to 6 carbon atoms, alkyloxy of 1 to 6 carbon atoms, cyano or nitro, or addition groups an acid salt thereof.

According to further preferred embodiments of the present invention, the fungicidal composition and the plant growth regulating composition comprise:

1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole or an acid addition salt thereof,

1- [2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole or an acid addition salt thereof,

1- (2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole or an acid addition salt of this compound,

(lil) in which it means

Y halogen, a

Ar and Z have the same meaning as above, preferably in a suitable polar organic solvent which is inert to the refluxing reaction, and further optionally separating and isolating the stereochemical optical isomers of the compounds thus obtained in a conventional manner, and further optionally converting these compounds to acid addition salts.

In a preferred embodiment of the process of the invention, a compound of formula (Ia) as defined above, in which Z and Ar have the same meaning, or acid addition salts thereof as the active ingredient, is prepared by reacting a metal salt of the compound of formula II with a compound of the formula III in which Y, Ar and Z are as defined above, preferably in a polar organic solvent which is inert to the reaction to be carried out at reflux, followed by optionally preparing an acid addition salt from said product.

In further preferred embodiments, the following compounds are reacted to prepare the resulting compound (I) of the present invention:

1H-1,2,4-triazole is reacted with 2- [bromomethyl] -2- [2,4-dichlorophenyl] -1,3-dioxolane followed by, optionally, preparation of an acid addition salt, 1H-1,2,4- triazole is reacted with 2- [bromomethyl] -2- [2,4-dichlorophenyl] -4-methyl-1,3-dioxolane, followed optionally by preparation of an acid addition salt, 1H-1,2,4-triazole reacts with 2- [bromomethyl] -2- [2,4-dichlorophenyl] -4-ethylbenzo-3-dioxolan and optionally followed by the preparation of an acid addition salt, 1H-1,2,4-triazole is reacted with 2 - [bromomethyl] -2- [2,4-dichlorophenyl] -4-propyl-1,3-dioxolane followed, optionally, by preparation of an acid addition salt of this compound, 1H-1,2,4-triazole reacted with 2- [bromomethyl] -2- [2,4-dichlorophenyl] -4-pentyl-1,3-dioxolane, optionally followed by preparation of the acid addition salt of this compound.

The compounds of the formula I and their acid addition salts are useful as active agents in combating fungi and bacteria. The compounds of the present invention are also valuable in the treatment of plants, animals and humans, i.e., organisms that suffer from pathogenic microorganisms, and are useful in combating microorganisms that attack various materials.

The compounds of the present invention are very effective fungicidal agents which can be used in agriculture. These compounds are very effective against various species of fungi, such as powdery mildew on different plant species, such as e.g.

Erysiphe graminis, Erysiphe polygoni, Erysiphe cichoracearum, Erysiphe polyphaga, Podosphaera leuchotricha, Sphaerotheca pannosa, Sphaerotheca morsuvae, Uncinula necator, etc., and other other fungi such as e.g.

Venturia inaequalis, Colletotrichum lindemuthianum, Fusarium Oxysporum, Alternaria tenuis,

Thielaviopsis basicola, Helminthosporium gramineum, Penicillium digitatum, etc.

These compounds are particularly useful for their prophylactic effects as well as for their healing and systemic action. Their effective fungicidal action against phytopathogenic fungi will be illustrated in more detail by the results obtained by the following experiments.

As used herein, the term "alkyl ¹ *" refers to a straight or branched chain hydrocarbon radical containing from 1 to 10 carbon atoms, such as methyl, ethyl, 1-methylethyl, propyl, 1-dimethylethyl, butyl, pentyl, hexyl, heptyl, octyl. decyl and the like. The term "lower alkyl" refers to a straight or branched chain saturated hydrocarbon radical having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl,

By 1,1-dimethylethyl, pentyl, hexyl and the like, and the above halogen is meant a halogen atom having an atomic mass of less than 127, i.e. fluorine, chlorine, bromine and iodine.

The reaction of 1H-1,2,4-triazole with structural formula II with a compound of structural formula III is preferably carried out in a suitable polar organic solvent which is inert under reaction conditions such as Ν, Ν-dimethylformamide, N, N- dimethylacetamide, acetonitrile, benzonitrile and the like. These solvents may be used in combination with other organic solvents that are inert under the reaction conditions, such as benzene, methylbenzene, dimethylbenzene, and the like. When Y is bromine or chlorine, it is appropriate to add an alkali metal iodide such as sodium iodide or potassium iodide. In order to increase the reaction rate, it is convenient to carry out the reaction at a somewhat elevated temperature, with the reaction at the boiling point of the reaction mixture being most preferred.

The resulting ketal of structural formula I may then be isolated from the reaction mixture by conventional means and, if necessary, purified by conventional purification procedures such as crystallization, extraction, trituration, chromatography, etc.

The above procedure can be illustrated by the following scheme:

->

Y-CH-C ~ Ar

About (!!!)

DMF

N & 1 (I)

In this way, a compound of formula (I), which is in the form of a base, is obtained, which base can be converted into an acid addition salt by reaction with a suitable acid, such as an inorganic acid such as hydrohalic acid, e.g.

hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfuric acid, nitric acid or thiocyanic acid and phosphoric acid; organic acids include acetic acid, propionic acid, hydroxyacetic acid, α-hydroxypropionic acid, 2-oxopropionic acid, ethanedioic acid, propanedioic acid, 1,4-butanedioic acid, (Z) -2-butenedioic acid, (E) -2-butenedioic acid, 2-hydroxy-1,4-butanedioic acid, 2,3-dihydroxy-1,4- butanedioic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, benzoic acid, 3-phenylpropionic acid, α-hydroxybenzeneacetic acid, methanesulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid, 4-methylbenzenesulfonic acid, α-hydroxybenzoic acid, amino-2-hydroxybenzoic acid, 2-phenoxybenzoic acid or 2-acetyloxybenzoic acid.

Conversely, these acid addition salts can be converted to the corresponding bases by conventional processing, such as, for example, RG-C-CH2Y + HO-Z-OH-II.

(IV)

In (III).

The ketones of structural formula IV are well known and can be prepared by methods well known to those skilled in the art.

It can be seen from structural formula I that some of the compounds of the present invention may have an asymmetric carbon atom in this structure and consequently may exist in different stereochemical, optical, isomeric forms. In particular, when the alkyl group is a coupling with an alkali hydroxide such as sodium or potassium hydroxide.

The starting compounds of formula III, many of which are considered to be well known compounds, can be prepared by known methods. These compounds wherein Z is selected from the group consisting of:

—CH'2 — CH2—, —СН (СНз) —CH2, —СН (СНз) - СН (СНз) - and —СНг — СНг — СНг, and methods for preparing these compounds, are described in U.S. Patent No. 5,201,549. In general, compounds of formula III can be prepared by ketalizing a suitable ketone of formula IV, wherein the Ar and Y residues have been previously defined, with a suitable diol of structural formula V, followed by a ketalization reaction which is sufficiently well known and described in the literature (see, for example, Synthesis, 1974, (L), 23).

In a preferred embodiment of the process, the two reactants are heated together under reflux for several hours, with azeotropic removal of water, in a suitable organic solvent, preferably in the presence of a normal alcohol such as ethanol, propanol, butanol, pentanol and the like. , and in the presence of a suitable strong acid, such as 4-methylbenzenesulfonic acid. A suitable organic solvent for use herein is, for example, an aromatic hydrocarbon such as benzene, methylbenzene, dimethylbenzene and the like, and saturated hydrocarbons such as cyclohexane. The above scheme can be illustrated as follows:

Acid

4-Methylbenzenesulfonic butanol benzenonium in position 4 of the dioxolane core, then the carbon atom to which it is attached and the carbon atom in position 2 of the dioxolane core is asymmetric. The stereochemical, optical isomers of the compounds of structural formula I can be separated and isolated by known methods commonly used by those skilled in the art. These isomers are within the scope of the present invention.

The fungicidal effect of the compounds according to the invention on phytopathogenic fungi will be illustrated in more detail by the results obtained by the following experiments.

In these experiments, the compound 1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, of structural formula Ia, was used in several cases, as a representative member of compounds of structural formula I.

In «(I *)

It goes without saying that the compounds for which the results of the experimental tests have been presented do not in any way limit the scope of the invention, but serve as examples of the compounds of structural formula I which show the strong fungicidal activity of these compounds.

AND.

Prophylactic action of compounds of structural formula I against Erysiphe cichoracearum 'in cucumbers in leaf treatment.

Young cucumber plants, about 10 days old, were sprayed with an aqueous solution containing 250, 100 and 10 ppm of the compound, which was tested while the control plants were untreated. After the leaves had dried, the leaves were artificially infected with spores of Erysiphe cichoracearum, which was done by weakly brushing the plants with a heavily infected leaf. After day 15 after artificial infection, the degree of fungal infestation was evaluated by adding up the number of spots per plant. The results are shown in Table 1 below, showing the mean values for the two plants and the fungicidal effect is expressed by the following recording system:

= 0 spots per plant = 1 to 5 spots per plant = 6 to 10 spots per plant = more than 10 spots per plant.

Table I

Prophylactic action of compounds of structural formula I against Erysiphe cichoracearum on cucumber plants in leaf treatment.

ArR

2.4- (Cl) 2 -C 6 H 3 H

CeH 5 H

4-NO 2 -C 6 H 4 H

3- Cl-C6H4H

2-C 1 -C 6 H 4 H

4- Br-C 6 H 4 H

2- Br-C6H4H

3- OCH 3 -C 6 H 4 H

2-CH 3 -C 6 H 4 H

4-F-C6H4H

4-CH 3 -C 6 H 4 H

4-Cl-C6H4H

2-naphthylH

2.5- (Clj ₂ -C ₆ H ₃ H

4-CN-C6H4H

3.4- (Cl) 2 -C 6 H 3 H

2-OCH 3 -C 6 H 4 H

2-thienylH

2-fluorenylH

5-Cl-2-thienylH

3-Br, 4-CH 3 -C 6 H 3 H

2-CH3 4-Br-CeH3H

2- CH 3, 4-C 1 -C 6 H 3 H

3- Br-CeH 4h

4- I-C6H41

3.5- (C1-12-C6H3H

WC1J2H3H

3-NO 2 -C 6 H 4 H

М - [ВГ] 2-СбШH

2.4.5- (C1-3-C6H2H

2-Cl, 4-OCH3-C6-C6H3H

2.42 (Cl) 2 < 6HH2OCH3

Base or salt 250 Fungicidal record ppm 100 ppm 10 ppm base - 0 0 base - 3 - base 0 - - base - 2 - (COOHJ2 - 0 - base 0 - - (COOHJ2 - 2 - (COOH) 2 1 - - (COOHJ2 0 - - (COOHJ2 0 - - (COOH) 2 0 - - (COOH) 2. H20 - 0 - (COOHJ2 0 - - (COOH)? - 0 - (COOHJ2 0 - - (COOHJ2 - 3 - (COOHJ2 1 - - (COOHJ2 - 2 - base 0 - - base  - 2 - base 0 - - base - 2 - base 0 - - base 2 - - (COOHJ2 0 - - (COOHJ2 - 2 - (C00HJ2 0 - - base 1 - - (C00HJ2 - 1 - (COOHJ2 0 - - (COOHJ2 - 2 - HNC3 0 - -

Ar R Base or salt 250 Fungicidal record ppm 100 ppm 10 ppm 24- (С1) 2-Сб C2H5 HN03 - 0 0 2,4- (С1) 2-Сб ПСЗН7 HN03 - 0 0 2,4- (С1) ₂ -СбНз ПС4Н9 11/2 (COOH) 2 - 2 - 2,4- (Cl) 2-N-N ПС5Н11 HNO3 - 0 0 2,4- (Cl) 2-Saline ПСВН15 HNO3 0 - - 2,4- (Cl) ₂ -СбНз ПС7Н15 HNO3 - 2 - 2,4- (Cl) 2-Saline nCeHie HNO3 0 - -

A.l

Prophylactic action against Erysiphe polyphaga on cucumbers in leaf treatment.

The young cucumber plants, at the time of the first leaf formation, were sprayed with an aqueous solution containing 500, 250 and 125 ppm of the compound of Structural Formula Ia, leaving the control plants untreated. Artificial infection was performed by Erysiphe polyphaga spores, so that the plants were lightly smeared with a heavily infected leaf on the 4th, 6th and 8th days after treatment. On the 18th and 34th days after treatment, the percentage of leaf surface affected by the fungus was determined, as determined for infected leaves and newly formed leaves. The results are shown in Table 1.1, which shows the mean values for 5 plants, the results being expressed as a percentage of attack compared to untreated areas.

Table 1.1

Prophylactic action of compounds of structural formula I-a against Erysiphe polyphaga on cucumbers in leaf treatment.

Evaluation date 18 days after treatment 34 days after treatment

Infection day after treatment Infected leaves (a) or emerging leaves (b) Concentration of compound I-a in spray solution Untreated

500 ppm

250 ppm

125 ppm

100 100 .100 100

100 100 o o o o o o

100 100 o o o o o o

100 100 100 100

0 0 0

0 0 0

0 0 0

Prophylactic action against Erysiphe graminis on barley, soil treatment.

Barley plants were treated by spraying with an aqueous solution containing 1000, 100 and 10 ppm of the compound of Structural Formula Ia, each containing 100 ml of this solution. Control samples were sprayed with an equal volume of solution but not containing the compound of Structural Formula Ia. In this case, natural infection occurs in the usual way when the plants are grown in a greenhouse adjacent to the infected plants. On the 16th day after treatment, the spots on the leaves were counted. In this case, values from five plants were used, and the results are shown in Table II, which shows the mean values expressed as percentage of attack and compared to the control samples.

Table II

Prophylactic action of a compound of structural formula Ia on Erysiphe graminis on barley in soil treatment.

Dose of compound Ia% attack in mg, per plant relative to control plant

Kontrolní100

100 mg0 mg0 mg53

C.

Protective action against Erysiphe graminis on barley, in the treatment of leaves.

Barley plants attacked by Erysiphe graminis were treated by spraying with an aqueous solution containing a compound of formula Ia at the indicated concentrations. On day 16 after treatment, the number of spots on each plant was determined. Values from five plants were used, and the results are shown in Table III, which shows the mean values in terms of percentage of challenge compared to the controls.

Table III

Table IV

Protective action of the compound of structural formula Ia against Erysiphe gra mlnis on barley, in the treatment of leaves.

Concentration of compound Ia in the spray solution% attack compared to the control

1000 ppm 100 ppm 10 ppm

100 0

1.5

D.

Prophylactic action of a compound of structural formula Ia against Podosphaera leuchotricha on apple seedlings by spraying.

Apple seedlings, one year old, were sprayed with an aqueous solution containing a compound of structural formula Ia at the indicated concentrations. These plants were artificially infected in the same way as in the "A" test of Podosphaera leuchotricha spores 1 day after treatment and incubated for 36 hours. The degree of fungal infestation was determined 25 days after treatment by counting the number of spots. In this case, values from two plants were used and the results are shown in Table IV, which shows the mean values expressed as percentage of attack compared to the control.

Prophylactic action of a compound of structural formula Ia against Podosphaera leucotricha on apple seedlings by spraying.

Concentration of compound Ia in the% attack solution compared to the control

0100

100 ppm0 ppm6

E.

Activity against Thielaviopsis sp.

Slices of tomato and leek, 5 mm thick, were immersed in an aqueous solution containing a compound of structural formula Ia at the indicated concentrations. After soaking, the slices were placed on filter paper on a large plastic dish and the dish was sealed with a glass lid. Thereafter, the slices were artificially infected on the very day they were treated by spraying with a concentrated suspension of spores of the species Thielaviopsis sp. and the slides were incubated at room temperature.

Mold formation on these slices was detected 6 days after treatment, and the area of fungal infestation was estimated. The results are shown in Table V, showing the percentage of challenge compared to the control.

Table V

Activity of a compound of structural formula Ia against Thielaviopsit sp.

Concentration of Compound Ia% Infection Compared to Control in Tomato Test Solution. Leek in ppm

0 100 ALIGN! 100 ALIGN! 1000 0 0 100 ALIGN! 0 0 10 0 42.8 1 11 100 ALIGN!

The compounds of formula (I) are also very active against a variety of fungi which are pathogenic to human organisms and animals. For example, these compounds are very active against fungi such as

Microsporum canis,

Trichophyton mentagrophytes,

Trichophyton rubrum,

Aspergillus fumigatus,

Phislophora verucosa,

Craptococcus neoformans,

Candida albicans,

Candida tropicalis, etc.

Exceptional activity against Candida albicans is further demonstrated by the results obtained as follows. trying.

F.

Activity of a compound of formula (Ia) against candidose in a turkey volley.

This test was performed. artificially infecting young turkeys (14 days old) into the oxen, with a suspension containing 4.106

C.F.U. (which is the number of colonies created;

the number of elements in the homogenised culture capable of forming colonies when

IS that they are further bred in a suitable environment, this dimension will be used in the following text), Candida albicans.

Following infection, the animals received either a normal diet (control group) or a treated diet containing the compound of formula Ia in an amount

125 ppm. After two weeks, all the turkeys were sacrificed, the cultures formed were removed from the bull and the number of colonies of Candida per gram of bull was determined.

The results obtained are shown in Table VI.

Table VI

You select the number of colonies of Candida albicans per gram in turkeys that have been treated with Compound 1a at 125 ppm or in untreated control turkeys.

Treatment Number of animals Number of colonies of Candida per gram vol Control animals 1 3,520,000 2 848 700 3 3 132000 ..........................- 4 1 909 000 Animals treated with compound 1a 1 0 in an amount of 125 ppm 2 247 200. 3 6 742

As can be seen from the results shown in Table VI, the compound of Structural Formula Ia is highly potent against candidose in volunteers in turkeys, as compared to the corresponding control experiments.

G.

Activity of a compound of Formula Ia for vaginal candidose in rats.

Female rats weighing 100 grams were ovariectomized and hysterectomized. After a further about three weeks, all animals received subcutaneous injections of estradiolundecylate at a dose of 100 milligrams, and then the animals were infected intravaginally with a suspension containing 8.10 ⁵ CFU (see above) of Candida albicans.

The group of four rats was then orally treated for 14 consecutive days with either PEG 200 (a polyethylene glycol having an average molecular weight of about 200) or a compound of Formula Ia. The doses administered were 40 mg / kg, meaning the amount of compound per kilogram of body weight. At the end of the treatment, vaginal samples (i.e., after 14 days) were taken from all animals and then cultured in Sabouraud agar medium containing 20 IU / ml Penicillin (International Units, one IU equivalent to 0.6 µg). benzylpenicillin sodium) and Streptomycin (40 (Ug / ml)), and then the sum of colonies of Candida species were summed.

Table VII summarizes the results obtained with the compound of formula (Ia) against vaginal candidose in rats.

Table VII

Number of animals and recorded culture

Treatment Number of animals The day after treatment Recording of created culture 0 1 2 3 4 Control substances PEG 200 4 14 0 0 0 1 3 Compound Ia 40 mg / kg, orally administered 4 14 3 1 0 0 0 * Record created culture 0 = 'no occurrence

= 1-2 colonies = 26-100 colonies - more than 100 colonies = countless colonies

From the results shown in Table VII, it is apparent that the compound of Structural Formula Ia is very effective against vaginal cadidosis in rats.

H.

Activity of a compound of structural formula Ia against systemic candidacy in guinea pigs.

In this case, increased males were guinea pigs infected intravenously with Candida albicans _of which induces a general, systemic candidiasis.

Thereafter, groups of 7 guinea pigs were orally treated for the next 14 days with either a solvent (PEG 200) or a compound of structural formula Ia The doses used were 40 mg / kg animal weight.

Four days after the last day of treatment, all animals were killed, their kidneys were removed, the sections were cultured in Sabouraud agar medium containing Penicillin (20 IU / ml) and streptomycin (40 _l / ml), and finally to determine the number of isolated colonies of Candida albicans per gram of kidney.

Table VIII shows the results obtained from compound Ia against systemic mycosis in guinea pigs.

Table VIII

Type of treatment

Number of animals

Number of colonies of Candida per gram of kidney

Control solution (PEG 200)

182

2 838

25 220

Compound Ia (40 mg / kg, oral)

385

800

113

345

From the results shown in Table VIII, it is evident that the compound of structural formula Ia is highly effective against systemic deep mycosis in guinea pigs.

In addition to the antimicrobial effects of the compounds of structural formula I, they exhibit valuable plant growth-regulating properties. Depending on various factors, such as the species of the plant, the method of treatment and the dose of the active compound, this effect may be both growth stimulation and growth inhibition. In this way, the compounds of the invention can be used as plant growth regulators. In particular, the compounds may serve as plant growth inhibitors or as retardants, especially as shoot growth inhibitors, for example tobacco plants. Under certain conditions, these compounds can serve as plant growth promoters.

The ability of these compounds of structural formula I to control the growth of plants within the scope of the present invention will be further illustrated in the results obtained in the following experiments, using the compound of structural formula Ia as a representative member of the compounds of the invention. The results obtained with compound Ia serve only as an example of the ability to control the growth of plants of the compounds of structural formula I and are not to be construed as limiting the scope of the invention to this type of compound Ia.

I. Regulatory effect on the growth of tomato plants in soil treatment.

In this test, young tomato plants, about 3.5 to 4 cm high, were grown in separate containers. Each vessel was watered with a test solution containing a compound of Structural Formula Ia. Growth effects were assessed by determining the length and weight of the plants 28 days after treatment.

The results are shown in the table

IX, which shows the mean values of five plants as compared to control plants, expressed as a percentage.

Table IX

Regulatory effect of compounds of structural formula Ia on the growth of tomato plants in soil treatment.

Dose of compound Ia in mg / plant Height -plants % in comparison with control Weight of plants in% compared to control none 100 ALIGN! 100 ALIGN! 10 114 118 1 127 134 0.1 122 116

J.

Regulatory effect on barley growth in leaf treatment.

Young barley plants in the 3 to 4 leaf stage were sprayed with a test solution containing a compound of structural formula Ia at the indicated concentrations. The effect on plant growth was determined 24 days after treatment by determining the weight of the plants.

The results are shown in taib. X, where the mean values for ten plants are expressed as a percentage relative to control plants.

Table X

Regulatory effect of compound of structural formula Ia on barley growth in leaf treatment.

Compound concentration Average weight Ia 'in test plant as a percentage of solution [ppm] compared to control no100

125126

60116. K. - ..

Control effect on shoot growth of tobacco plants.

Tobacco plants of the "Xanthi" species were grown in the greenhouse and, at an early stage, when they were about the size of a button, they cut off the tops.

Over the next 5 days, the leaves were sprayed with an aqueous solution · a suspension containing a compound of structural formula Ia in an amount equivalent to up to 15 grams and i (m ² ) abbreviation a. · I. below).

Each treatment was repeated three times. After 12 days, the growth of the shoots was estimated in comparison with the cut and untreated control plants.

In these experiments, a reduced shoot growth of 100% at 30 g / m ² and 90% at 15 g / m ² was observed.

L.

Inhibition of soybean growth.

Hark soybean plants were grown in containers that were placed in a 23 ° C and 20,000 lux chamber for 14 hours a day.

After the third triple leaf had unfolded, the plants were sprayed with an aqueous solution containing a compound of structural formula Ia at a concentration of 1000, 500, 100 and 50 ppm of the active ingredient.

Growth inhibition of treated plants in% relative to control plants was estimated after 14 days.

The following results were obtained:

Treatment. Growth inhibition

..... in O /)

Compound Ia

1000 ppm · a.i. 70%

500 ppm a.i. 40%

100 ppm · a.i. 25% ppm · a.i. 0% · ·

Control sample 0%

Comparison of the efficacy of the compounds of the present invention with those of the prior art.

Compounds of the invention:

Compound number

Cl

according to the invention according to the invention according to the invention

Cl

I — J—

Cl

Cl

Cl

_L_Lch ^ _{c 3} according to the invention invention according to the invention according to Example 1 of U.S. patent

No. 3,575,999

Compounds of the prior art

_сн ъ CH ₃ Example 6 of U.S patent no. 3,755,349 hydrochloride

Testing methods

1. Effect on Puccinia triticina in wheat plants (residual protective effect).

Wheat plants of six days old were sprayed by dropwise wetting with a nutrient slurry (600, 200, 60 and 20 ppm active ingredient concentration) prepared from a wettable powder of the active ingredient. After 24 hours, the treated plants were evenly infected with the uredospore suspension of said fungus. After incubation for 48 hours at 95-100% RH and about 20 ° C, the infected plants were placed in a greenhouse heated to 22 ° C. The number and size of infected sites served as a criterion for evaluating the efficacy of the test compound. Wheatgrass treated with compounds 1-7 was shorter than those treated with compounds A and B and untreated control plants.

2. Effect on Venturia inaequalis in apple clippings (residual protective action)

Apple shavings that had new shoots of 10-20 cm in length were sprayed with an emulsion (active ingredient concentration of 600, 200 and 60 ppm) prepared from a wettable powder of the active ingredient. After 24 hours, the treated plants were infected with a conidiospore suspension of the fungus. These plants were then incubated for 5 days in an environment with 90-100% humidity, and were kept in a greenhouse at 20-24 ° C for an additional 10 days. Assessment of scab infestation was performed 15 days after infection of the plants.

3. Effect on Cercospora arachidicola in peanuts (residual protective action)

Peanuts of 10 to 15 cm in size were sprayed with a nutrient slurry (containing 200, 60, 20 and 6 ppm of the active ingredient), prepared from a wettable powder of the active ingredient, and infected after 48 hours with a conidia suspension of the fungus. These infected plants were incubated for 24 hours at about -21 ° C and high humidity, and then placed in a greenhouse until typical spots appeared on the leaves. Assessment of the fungicidal effect, based on the number and size of said spots, was performed 12 days after infection.

4. Effect on Erysiphe graminis in barley plants (residual protective effect)

The barley size of about 8 cm was sprayed with an emulsion (active ingredient concentration of 200, 60, 20, 6 and 2 ppm) prepared from a wettable powder of the active ingredient. After 48 hours, the treated plants were dusted with conidiospores of the fungus. The infected barley plants were then stored in a greenhouse at a temperature of about 22 ° C, and the fungal infestation was assessed after 10 days.

5. Effect on Puccinia triticna in wheat plants [tyslemic effect]

Wheat plants 5 days old were sprayed with a thin nutrient slurry (60, 20 and 6 ppm active ingredient), prepared from a wettable powder of the active ingredient. Care was taken when spraying. . that the nutrient slurry does not come into contact with the above-ground part of the plants. After 48 hours, the treated plants were evenly infected with the uredospore suspension of said fungus. After incubation for 48 hours at 95-100% RH and about 20 ° C, the infected plants were placed in a greenhouse heated to 22 ° C. The number and size of the infected sites served as a criterion for assessing the efficacy of the test compounds. Rose's wheat treated with compounds 1 to 7 - was a little bit -. shorter than the plants treated with Comparative Compounds A and B and untreated plants.

24

6. Effect on Erysiphe graminis in barley (systemic action)

Barley Rossi, about 8 cm in size, were sprayed with a thin nutrient slurry (active ingredient concentration of 60, 20, 6 and 2 ppm), prepared from a wettable powder of the active ingredient. After 48 hours, the treated plants were dusted with conidospore of said fungi. The infected barley plants were then stored in a greenhouse at a temperature of about 22 ° C, and the fungal infestation was evaluated after 10 days.

Test results

The concentration of the active ingredient was reported in ppm (with 600 ppm = 0.06% active ingredient) - in tests 1 to 4, residual activity relative to the test nutrient tested, - in tests 5 'and 6, systemic activity was observed relative to soil volume .

Activity was expressed as percent attack compared to untreated control plants (which were 100%). The percentage of fungal infestation was evaluated using the following 4 levels:

= '0-5% attack = 5-20% attack = 20-50% attack 3' = '50 -100% attack (the compound was considered inactive)

Each test was performed twice. The results are shown in the following table.

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Combines - Puccinia Venturia Cercospora Erysiphe nina residual. ac. residual account. ac. residual. ac

No. 600 200 60 20 600 200 60 200 60 '20 6 200 Ref

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Combining Puccinia nina Systemic Effect No. 60 20 6

Erysiphe systemic effect 60 20 6 2

1 0 2 3 0 2 3 2 0 0 1 0 0 2 3 1 2 3 2 2 3 4 0 0 1 0 0 2 5 0 0 0 0 1 1 6 0 0 1 0 0 1 7 0 0 0 0 0 0 AND 0 3 3 1 3 3 В 1 1 3 1 2 3

0 0 1 2 0 0 1 3 0 1 1 2 0 1 1 2 0 1 1 2 0 1 2 3 0 0 1 1 0 0 1 1 0 0 1 2 0 0 1 2 0 1 2 3 0 1 2 3 0 0 1 1 0 0 1 2 0 1 2 3 0 1 2 3 2 3 3 3 2 3 3 3

The results show that the compounds of the present invention have a much broader spectrum of activity than the two prior art imidazolyl compounds A and B. This is particularly noticeable for compound B. For example, in the Erysiphe test, residual Compounds 1 to 7 are potent even at very low doses, with a degree of attack of 1 or 2, at doses of 6 ppm and even 2 ppm. Even at concentrations as low as 2 ppm, the compounds of the present invention exhibit potent activity. On the contrary, at a concentration of 2 ppm, the prior art compounds show almost inactivity, which results in a degree of attack of "3".

Other results also show much better properties of the compounds of the present invention relative to the prior art compounds. The degree of efficacy is higher in each test and, in addition, the triazole compounds of the invention are effective at low doses.

At a concentration of 1000 ppm, a more intense green foliage was observed.

In view of the aforementioned fungicidal, antibacterial and growth-regulating activity of the compounds of the present invention, it is an important feature of the present invention to provide valuable compositions containing the ketals of formula I or their acid addition salts as active ingredient in a solvent or solid, a semi-solid or liquid diluent or carrier, and the invention further provides an effective control of fungi or bacterial growth using an effective fungicidal or antibacterial amount of the ketals of formula (I) or salts thereof. The compounds of the invention may be used in dissolved form in various solvents or diluents, in the form of emulsions, suspensions, dispersions or pastes on suitable solid or semi-solid carriers as such or mixed in surfactants, detergents or dispersion media, and they may be used in conjunction with compounds having arachnicidal, insecticidal, ovicidal, fungicidal and / or bactericidal effects, or may be mixed with inactive agents.

Solid carriers which are suitable for the preparation of powdered formulations include various inert porous and powdered materials of an inorganic or organic nature, such as normal calcium phosphate, chalk carbonate or ground lime, kaolin, red clay, bentonite, talc, diatomaceous earth and boric acid, and also suitable carriers are powdered cork, sawdust and other fine powders of a natural nature.

The active ingredient is admixed with these carriers, for example by grinding them, and the like may be impregnated with a solution containing the active agent in a suitable volatile solvent, the solvent being removed by heating or filtration using suction under reduced pressure. When wetting and / or dispersing agents are added to these powder formulations, it is possible to make the substance readily wettable with water so that a suspension can be prepared.

The inert solvents to be used for the preparation of liquid preparations are preferably those which are not readily flammable and must be as odorless as possible and must, as far as possible, not be toxic to warm-blooded animals or plants in which: surroundings are used. High boiling oils such as natural oils and low boiling solvents with a flash point of at least 30 ° C such as polyethylene glycol, isopropa 203098 nol, dimethylsulfoxide, hydrogenated naphthalenes and alkylated naphthalenes are well suited for this purpose. It is also possible to use mixtures of solvents. Solutions can be prepared in conventional manner and if necessary in the presence of promoters. Other liquid forms which may be used are emulsions or suspensions of the active compounds in water or a suitable inert solvent, or else concentrates for preparing these emulsions, which can be directly adjusted to the desired concentration. In this case, for example, the active ingredient is mixed with a dispersing agent or emulsifier. The active ingredient may also be dissolved or dispersed in a suitable inert solvent and mixed simultaneously or sequentially with a dispersing agent or emulsifier.

It is also possible to use semi-solid carriers of a creamy, pasty or waxy nature to which the active ingredient is added and, if necessary, also to use solution promoters and / or emulsifiers. Examples of semi-solid carriers are petrolatum and other creamy materials.

In addition, it is possible to use the active substances in the form of aerosols. For this purpose, the active ingredient is dissolved or dispersed in a suitable inert solvent, which in this case is a carrier liquid, such as difluorodichloromethane, which boils at atmospheric pressure at a temperature below room temperature, or other volatile solvents may be used. solvents. In this way, pressurized solutions can be obtained which, when sprayed, provide aerosols which are particularly suitable for controlling or controlling the growth of molds and bacteria, for example in closed chambers and storage rooms, and for use in controlling or preventing mold development. or bacteria.

Said compounds and mixtures thereof may be used by conventional methods. For example, the growth of fungi or bacteria or the treatment of the material or the protection against fungal or bacterial attack may be stopped or the treatment carried out with the aid of said compounds or mixtures thereof by dusting, spraying, spraying, brushing, soaking, pasting, impregnation or other suitable methods.

When the compounds of the present invention are used together with suitable. carriers in the form of, for example, solutions, suspensions, dusts, powders, pastes, emulsions and other forms, then high activity can be observed even at high dilution. For example, it has been found that an effective amount for controlling fungi or bacteria is in the range of from 0.1 to 10% by weight of the composition used. Of course, higher concentrations may also be used, depending on the situation.

The following examples are intended to further illustrate the invention without limiting it in any way. Unless otherwise stated, all parts are by weight.

Example l

In this example, a stirred and cooled (to 0 ° C) solution consisting of 30 parts of 1-phenylamino-2-methoxyphenyl Jethanone in 360 parts of concentrated hydrochloric acid, and 75 parts of water and 30 parts of acetic acid was diazotized with a solution containing 17.25 parts of sodium nitrite in 200 parts of water. The mixture was stirred for 30 minutes at 0 ° C and the contents were poured into a solution consisting of 30 parts of copper (I) chloride in 240 parts of concentrated hydrochloric acid and further stirred. The mixture was then heated at 60 ° C for 1 hour. Further, the mixture was cooled to room temperature and the product was extracted twice with 2,2'-oxybispiopane. The combined extracts were washed sufficiently with water, then with dilute sodium hydroxide solution and twice more with water to dry, filter and evaporate to give 28 parts (76% yield) of 1- (4-chloro-2-methoxyphenyl) ethanone having mp 55 ° C.

Example 1 and d · 2

In this example, a mixture of 78.8 parts of 2-broirmll (4-broim _l-2- methylphenyl] -l-etlhanonu and 200 parts of butanol, · to which were added 3 parts of 4-methylbenzensulfQnové acid and 225 parts of benzene. Then was lk; mixtures of added dropwise 33.5 parts of ¹ • 1,2-ethanediol. after completion of this addition, stirring was continued overnight at Vairo using a water separator. the reaction was then evaporated and the residue was dissolved in · 2 The resulting solution was stirred together with 15 parts of concentrated sodium hydroxide solution, the layers were separated and the aqueous phase was extracted with 2,2'-oxybispropane, and the resulting organic layers were combined and washed with water (until neutralized), dried, filtered and concentrated. the solid residue was recrystallized from methanol · · result was 30.5 parts of 2-i ^(l thyH bromomethyl) -2- (4-bromo-2-methylphenyl) -1,3-dioxolane, mp thus z plied product was 86 ° C.

Example 3

In this example, the same procedure as in Example 2 was followed, except that an equivalent amount was used instead of 2-broim-1-γ (4-benzo-2-methylphenyl) -1-ethanone used in the foregoing. For example, the corresponding 2-aryl-2-bromo-methyl-1,3-dioxylanes resulted in:

4- (2- (bromo-methyl) -1,3-dioxolan-2-yl) benzinilitrile, m.p. 92.4.0 ^° C;

2- (Biromethyl) -2- [2-naphthalenyl) -1,3-dioxolane having a melting point of 64 ° C.

Example 4

In this example, 57 parts of 1- (5-chloro-2-thienyl) -1-ethanone were dissolved in 220 parts of 1,2-ethanediol at 50 ° C while stirring with the mixture. 64 parts of bromine were added dropwise to the mixture with no external heating, the addition was continued for 1 hour, then the mixture was stirred for an additional 1 hour at room temperature, and 4 parts of 4-methylbenzenesulfonic acid were added. The mixture was stirred and refluxed overnight using a water separator, then the reaction mixture was evaporated and the residue was taken up in 2,2'-oxybispropane and the resulting solution was washed sufficiently, once with dilute. sodium hydroxide solution and three times with water, dried, filtered and evaporated, the residue was distilled off to give 73.3 parts [yield

64.5%) 2- (trimethyl) H 2 - [5-chloro-2-thienyl] -1,3-dioxolane, boiling in the range of 125-127 ° C at 13 Pa.

Example 5

In this example, the same procedure was followed as in Example 4 except that an equivalent amount of the appropriate 1'-1'-ethanol was used instead of 1'-1'-ethanol instead of 1'-1'-ethanol. The compound (2-thienyl) -lithiol which was used in the previous example, resulting in the following 2-aryl-2- (bromomethyl) -1,3-dioxolanes:

- [bromobutyl] -2- (9H-fluoren-2-yl) -1,3-dloixolane, the melting point of which is 90 ° C,

2- (3-bromo-4-methylphenyl) -1,3-dioxolane having a boiling point of from 126 to 130 ° C at a pressure of 13 Pa,

2- (4-iodophenyl) -1,3-dioxolane having a melting point of 74 ° C,

2- (bromoethyl) -2- (4-chloro-2-methoxyphenyl) -1'-dimethyne, m.p. 110 ° C; and

2- (bromoethyl) -2- (N -bromophenyl) -1,3-diolanelane, having a melting point of 96 ° C.

Example 6

A. To a stirred solution containing 2.3 parts of sodium in 120 parts of methanol was added 6.9 parts of 1H-1,2,4-triazole in 150 parts of dimethylformamide. The methanol was then removed under normal pressure at an internal temperature of 130 ° C. Then 25 parts of 2- (O-methylmethyl) -2-i (2,4-dichlorophenyl) -1,3-dioxolane were added to the solution. The reaction mixture was stirred and heated to boiling for 3 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature until the temperature reached ambient temperature and the mixture was poured into water. The precipitated product was filtered off and crystallized from - diisopropyl ether - (activated with charcoal) and yielded 12 parts, 1- (2- / Z, 4-dihydro-phenyl) -1,3-di-oxolan-2-ylmethyl) -1H] 1,2,4-triazole having a melting point of 100.9 ° C.

B. According to this process was- 6 parts 1] (2 - / -, ^4-DL · chlorophenyl / -l, 3-dioxolane --- · methylpent-yl) -lH-l, 2,4-triazole transferred to the nitrate salt in 2,2'-oxybispropane. After cooling the mixture, the salt was filtered off and crystallized twice from 2-propanone, yielding 3 parts of 1 - ((2- (1,4-dimethoxyphenol)) ^. 3-dimethylamino-1H-triazole nitrate, the melting point of the product thus obtained was 172.7 degrees Celsius.

C. According to this procedure, 6 parts of 1- (2- / 2,4-dichlorophenyl) -1,3-diioxolan-2-ylmethyl-1H-1H-triazole were converted to the sulfate salt in 2.2 '-oxyOisproιpanu. The resulting sulfate salt was filtered off and recrystallized from 2-propanol. The product was filtered off and recrystallised from ethanol (which was activated charcoal), and after drying resulted · 6 parts of 1- (2- / 2,2 ·· · di ^Ohto, phenyl / l, 3-dioxolan-2 (methylmethyl) -1H-11,4-triazolysulphate, the melting point of the product thus obtained being 207.1 ° C.

Example 7

The solution was stirred by mixing the solution it contained

2.3 parts of sodium in 0 parts of methanol, and 6.9 parts of 1H-1,2,4-triazole and 2 parts of sodium iodide in 100 parts of Ν, Ν-dimethylformamide were added to this solution. Methanol was then removed using an internal temperature of up to 130 ° C. The solution thus formed was then added

34.4 parts of 2 ((boommethyl-2--2,4-dimethoxyphenyl) -4-methyl-1, 3-dioxolane) and the total volume was stirred and heated to boiling for 3 hours. The reaction mixture was poured into water and the product was extracted twice with diisopropyl ether, the extract was washed with water, and then an excess of concentrated nitric acid was added, and the crude nitrate salt was filtered off and crystallized with a mixture of 2-propanol and diisopropyl ether. - (2- / 2,4-di-chlorophenyl € / -4-methyl-l, 3-dioxolan-2-ylmethyl) -lH-l, i2,4 ^-triazole! herein, wherein the melting point of the thus obtained product features being 137, Low: 14 ° C.

Example 8

In this example, a solution of sodium methoxide prepared from 2.8 parts of sodium in 48 parts of methanol was first mixed, to which 8.3 parts of 1H-1,2,4-triazole were added. The mixture was stirred for 30 minutes at room temperature, then 135 parts of Ν, Ν-dimethylformaimide was added and the methanol was evaporated. To this solution was added a mixture consisting of 24.3 parts of 2i (bromoethyl) -2-phenyl-1,3-dloxolan and 3 parts of potassium iodide, and then the total volume was immersed and heated to boiling for 3 hours. . The reaction mixture was cooled to room temperature and poured into water. After purification, the product precipitated. The precipitate formed was aspirated, washed with water, dried and crystallized from a mixture of ethanol and 2,2'-oxybispropane (1: 5 by volume) to give 10.9 parts (43.7% yield). (2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 127.3 ° C.

Example 9

In this example, the same procedure as described in Example 8 was followed except that an equivalent amount of the appropriate 2-aryl-2- (bromoethyl) -1,3-dioxolane was used instead of 2- (Bramethyl) - Of 2-phenyl-1,3-dioxolane used in the previous example (which gave the following 1,2,4-triazoles:

1- (2- (4-nitrophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, the melting point of the product thus obtained being 160.1 ^and C1.1 (2). - (3-chlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, melting at 113.9 ° C,

1- (2- / 4-Brutyl ⁽ phenyl) -1,3-dloxolan-2-ylmethyl) -1H-1,2,4-triazole, m.p. 135.9 ° C;

1- (2- (3-methylphenyl) -1,3-dioxolain-2-ylmethyl) -1H-1,2,4-triazole, 1- (2- (3-bromophenyl) -1,3-dioxolane) -2-ylmethyl) -1H-1,2,4-triazole, m.p. 115.4 ° C;

1- (2- (3-nitrophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-trlazole, m.p. 154.1 ° C.

He did

The procedure was carried out by adding 4.9 parts of 1H-1,2,4-triazole to a stirred solution of sodium methoxide prepared from 1.6 parts of sodium and 48 parts of methanol. The resulting solution was stirred for 1 h. 1 hour at room temperature and then 13: 5 parts of dílů, Ν-dimethylformamide were added. Further, methanol was removed by distillation at normal pressure while maintaining the temperature inside to 130 ° C. 17.4 parts of 2- (bromoimethyl) -2-i (2,3,4-trichlorophenyl) -1,3-dioxolane and 3 parts of potassium iodide were added. The total volume obtained was stirred and heated to boiling overnight. The solution was allowed to cool to room temperature and poured into water. The product was precipitated, filtered and washed with water. The product thus obtained was dissolved in trichloromethane, purified by column chromatography using silica gel and eluting with a mixture of trichloromethane and 5% methanol. After this chromatography, pure fractions were collected and the eluent was evaporated. The obtained residue was crystallized from a mixture of 2,2'-oxybispropane and methanol (9: 1 by volume), yielding 9.3 parts (yield 55 _s 5 ° / o) 1- (2- / 2,3,4- trichlorophenyl [1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, m.p. 181.4 ° C.

Example 11

In this example, the procedure of Example 10 was repeated except that an equivalent amount of a suitable starting material other than that shown in Example 10 was used, resulting in the following 1,2,4-triazoles:

1- (2- (9H-fluoren-2-yl) -1,3-dioxolan-2-ylmiethyl) -1H-1,2,4-triazole, m.p. 186.8 ° C; 1- (2 (5-chloro-2-thiophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole having a melting point of 105.4 ° C having a melting point of 117 -1 ° C,

1- (2- (3-bromo-4-methylphenyl) -1,3-dioxolan-2-ylmiethyl) -1H-1,2,4-triazole,

which had a melting point of 120.7 [deg.] C., [eta] &lt; 1 &gt; (1,2 &apos;-( 4-broim-2-methylphenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole, mp 148.1 ° C, and

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

Example 12

To the stirred solution of sodium methoxide obtained from the initial 2.8 parts of sodium and 5.6 parts of methanol was added a mixture of 8.3 parts of 1H-1,2,4-triazode and 135 parts of sodium methoxide. parts of Ν, Ν-dimethylformamide. Thereafter, methanol was removed from the mixture at normal pressure, the temperature inside the vessel reaching 130 ° C. Then a mixture of 27.8 parts of 2-i (bromomethyl) -2- (2-chlorophenyl) -1,3-dioxolanine and 3 parts of potassium iodide * was added to this solution. The solution was stirred and heated to boiling for 6 hours. The reaction mixture was allowed to cool to room temperature, then poured into water and the product was extracted three times with 1,1'-oxybisethane. The extracts were combined, washed twice with water, dried, filtered and evaporated. This gave a compound as a residue, which was converted to the ethanedioate salt using 4-methyl-2-pentonane, yielding 16 parts of 1- (2- (2-chlorophenyl) -1,3-dioxolan-2-ylmethyl). -1H-1,2,4-triazolethanedioate, the melting point of the product thus obtained was determined to be 156.5 ° C.

Example 13

In this example, a number of reactions were carried out, following the same procedure as in Example 12, using equivalent amounts of suitable starting materials each, resulting in the following 1,2,4-triazolethanedioate salts:

Ar Acid salt Melting point

2-Br-CeH 4 (COOHJ2 172.1 ° С З-ОСНз-СбШ (СООН) 2 15'5.6 ° С 2-СНз-СбН1 (СООН) г. 177.1 ° С 4-F-C & H4 (СООН) 2 185.5 ° С 4-СНз-СбШ (COOHJ2 151.2 + 4-С1-СбШ (СООН) 2. НаО 169,1 С 4-ОСНз-СбН4 ('СООН) г. 187.1 ° С 2-Naphthalenyl (COOHJ2 175 + 2,5- (Cl) 2-Cet (C00HJ2 173.7 ’С 4-CN-C 6 H 4 (СООН) 2 186.3 ° d 3.4 <(С1) 2-С ₆ Нз 2 182.2 + 2-thie, nyl [COOHJ2 144.5 ° С 2,4- (Вг) 2-СвНз (СООН) 2 190.3 ° С

Example 1 4

In this example, to a stirred solution of sodium methoxide prepared from a starting 'sodium' of 2.3 parts and 48 parts of methanol was added 6.9 parts of +И + ЗЛ-Шгагol. Stirring was continued for a further 3 (9 minutes at room temperature) and 135 parts of N, N-dimethylformamide were added thereto, and methanol was distilled off at normal pressure from the solution thus obtained, keeping the temperature inside the vessel at 130 ° C. After removal of the methanol, 3 parts of potassium iodide and 16.4 parts of 2- (bromoimethyl) -2- (O-imethoxyphenyl) -1,3-dioxolane were added.

This total volume was stirred and heated to boiling for 18 hours. The resulting solution was allowed to cool to room temperature and the reaction mixture was poured into water and the solution thus obtained was extracted three times with trichloromethane. The extracts were combined and washed four times with water, then dried, filtered and evaporated. The obtained residue was purified by column chromatography using silica gel as the eluent and 5% methanol / trichloromethane in the mixture. Pure fractions were collected and the eluent was evaporated. The residue was converted to the ethanedioate salt using 4-methyl-2-pentanone. The resulting salt was filtered off and crystallized from a mixture of 2-propanone and 2,2'-oxybispropane (volume ratio 2: 1), resulting in 5.5 parts (26% yield) of 1- (272-methoxyphenyl) -1, 3-dioxolan-2-ylmethyl) -1H-1,2,4-triazolethanedial, m.p. 166.4 ° C.

Example 1 5

In this example, a series of reactions were carried out in the same manner as in Example 14. These procedures were performed with equivalent amounts of suitable starting materials, resulting in the following 1,2,4-triazolethanedioate salts:

1- (2- / 4-iodophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-lriazolethanedioate having a melting point of 169.8 ° C; 1- (2- / 3, 5-dichloro-phenyl / -l, 3-dioxolan-2-ylmethyl) -lH-l _l 2,4-triazole ethanedioate ·, which had a melting point of 204.4 ° C,

1- (2- (2,3-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazolethanedioate, m.p. 188.4 ° C;

1- (2- / 4-chloro-2-methoxylenyl) -1,3-dioxolanlan-2-ylmethyl-1H-1,2,4-triazolethanedioate having a melting point of 173.2 ° C,

1- (2- / 2,4'-1'-bis (1,1'-phenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazolethanedioate having a melting point of 178.4 ° C, and

1- (2- / 2-chloro-4-methoxylenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazolethanedioate, m.p. 188.2 ° C.

Example 16

A mixture of 9.5 parts of 1H-1,2,4-triazole and 225 parts of N, N-dimethylformamide was first stirred, and 4.2 parts of sodium hydride in portions were added in portions. 78% dispersion. Stirring was continued until foaming ceased and 16 parts of 2-bromomethyl-2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolane were added and stirring continued. for 5 hours at boiling point. The reaction mixture was cooled and poured into water. The product obtained was extracted three times with 2,2'-oxobispropane. The extracts were combined and washed with water, then dried, filtered and evaporated. The residue was purified by column chromatography using silica gel and eluting with a mixture of dichloromethane and 2% - - methanol. In this chromatography, the first fraction was collected and the eluent was evaporated. This resulted in a residual mass which was converted to the nitrate salt using 2,2'-oxybispropane as the environment in which this conversion was performed. The obtained salt was filtered and crystallized from a mixture of 2-propanone and petroleum ether to give 8.2 parts (45% yield). 1- (2 - [(2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2H-ylmethyl) -1H-1,2,4-triazolenitral, m.p. 132.6 ^° C.

Example 17

In this example, 11.5 parts of 1H-1,2,4-triazole and 225 parts of N were added to a stirred solution of sodium methoxide prepared from 3.8 parts sodium and 40 parts methanol. Of N-dimethylformamide. Methanol was first distilled off from the resulting mixture, maintaining the temperature below 150 ° C. Then it was added. 19 parts 2- (bungomethyl) -2t (2,4203098)

dichlorophenyl) -4-ethyl-1,3-dioxolane, the total volume was then stirred and heated to boiling for 4 hours. The resulting reaction mixture was cooled and poured into water. The product thus obtained was extracted three times with 2,2'-oxybispropane. After this extraction, extracts were formed which were combined and washed with water, dried, filtered and finally evaporated. The residue was purified by column chromatography using silica gel and a mixture of trichloromethane and 2% methanol as eluent. The first fraction was collected and the eluent was evaporated. The residue was converted to the nitrate salt in 2,2'-oxybispropane. The resulting salt was filtered off - and crystallized from a mixture of 4-methyl-2-pentanone and 2,2'-oxybispropane, yielding 10.5 parts (49% yield) of 1- (2- (2,4-dichlorophenyl) - 4-ethyl-1,3-dioxolan-2-ylmethyl-1H-triazole nitrate, m.p. 119.8 ° C.

Example 18

In this example, a series of reactions were carried out and each procedure was carried out as in Example 17, using an equivalent amount of a suitable starting material. In these processes, the following 1,2,4-triazole acid addition salts were obtained:

1- (4-Butyl-2- (2,4-dichlorophenyl) -1,3-dioxol-an-2-ylmethyl) -1H-1,2,4-triazole esquiethanedioate having a melting point of 111.6 ° C,

1- (2- (2,4-dichlorophenyl) -4-penlyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazoinitrate having a melting point of 130.3 ° C,

1- (2- / 2,4-Difluorophenyl) -4-hexyl-1,3-dioxolan-2'-ylmethyl-1H-1,2,4-triazolonitrate having a melting point of 106.2 ° C,

1- (2- / 2,4-Chlorophenyl) -4-heptyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole nitrate having a melting point of 96.8 ° C, and

1- (2- (2,4-Dichloro-phenyl) -4-oxyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole nitrate having a melting point of 110.6 ° C.

Treasure 19

In this example, the procedure of Example 6-A was repeated except that the 2- (bromomethyl) -2- (2,4-dichlorophenyl) -1,3-dioxolane used in this above was used instead. In the above example, an equivalent amount of 2- (bromomethyl) -2-aryl-1,3-dioxolane was used to give the following compounds of Structural Formula I:

1 H -2- [2,4,6- b] T (4 H -fluorophenyl) -1 H -furan-2-ylmethyl) -1 H -1,2,4-triazole,

1- (2- (2,1-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole,

1- (2- / 2-chloro-4-methylphenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole.

Example 2 0

The procedure of Example 7 can be used to prepare compounds of structural formula I wherein Z is -CH 2 - (CH 2 CH 3) - or -CH (CH 3) - CH (CH 3) -. In an analogous manner, when an equivalent amount of a suitable 2-aryl-2- (bromomethyl) -4-methyl-1,3-dioxolane or 2-aryl-2- (bromomethyl) -4,5-methyl-4-methyl-1,3-dioxolane is used herein, 3 -dioxolane, the following compounds or their nitrate salts can be obtained, respectively:

1- (4-methyl-2-phenyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole,

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

1- (2- (2-chlorophenyl) -4-methyl-1,3-diolinyl-2-yl) ethyl-ethyl-11,1-1,2,4-triazole,

1- (4-Biphenyl-2- (4-biphenyl) -1,3-dioxola-2-ylmethyl) -1H-1,2,4-triazole, 1- (2-44-methoxyphenyl) -4-methyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole,

1- (4,5-dimethylamino-42,4-dichlorophenyl) -1,341-0x01 ^ 1-2 + 1116 ^ +) -1H-1,2,4-triazole,

1- (4,54-6-6- (2-enyl-1,3-dioxolan-2 + methyl) -1H-1,2,4-trazole), and

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

Example 21

The procedure shown in Example 6-A can be used to prepare compounds of structural formula I wherein Z is -CH 2 -CH 2 -CH 2 -. Similarly, when an equivalent amount of a suitable 2-aryl-2- (bromomethyl) -1,3-dioxane is used as the starting material, the following compounds can be obtained:

1- (2-Phenyl-1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole,

1- (2- / 2,4-Dichlorophenyl) -1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole,

1- (2- (4-Chloro-phenyl) -1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole, 1- (2-methyl-4-methyl-phenyl) -1H-1,3 -d10- (4R, 4R-2-ylmethyl-1H-1,2,4-triazole),

1- (2- (4-Methoxyphenyl) -1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole,

1- (2H-2-hiphenyl-1,3-dioxan-2-ylmethyl) -1H-1,2,4-triazole, and

1- (2- / 2-Naphthyl) -1,3-dioxan-2-ylmethyl-1H-1,2,4-trlazole.

P-example 2 2

Compositions of the compounds of the present invention are used in those forms in which they are generally prepared for use in combating fungi or bacteria, for example, suspensions, dusts, solutions, pastes and the like. Some of the following forms are given below to further illustrate the present invention, all parts being by weight unless otherwise indicated:

(1) Suspension:

kg

1

350 ml water

1- (2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -N-4-triazole technical xylene surfactant to dilute to the desired concentration of active ingredient.

The compound 1- (2 - / - ^{2,4-de-t-yo-,} 3- ^ 5 ^^^^^ - dioxolan-2-yУmethy1) ^ lH-l, 2,4-triazole, according to the invention, · Forms a stable aqueous suspension when dissolved in xylene and emulsified with surfactants.

(2) Dust:

parts of 1- (2,4-dichloro-phenyl) -13-di-oxolan-2-ylmethyl-1H-1,2,4-triazole are ground with 3 parts of talc in a ball mill, then 8 parts of olein are added and milling is continued. Finally, the mixture is mixed with 4 parts of slaked lime. The powder thus formed can be successfully sprayed and has good adhesive ability. Can be used for spraying or plant protection.

(3) Solution:

parts of 1-2-72,4-dichlorotenyl / -1,3-dioxolan-12-yl · methyl) 11H-1,2,41-triazole are dissolved in 95 parts of alkylated naphthalene and used in the form of a spray to treat fungal infested objects or used on walls, floors or other objects to prevent fungal infestation.

(4) Paste:

parts of 1- (2 / 2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl) -1H-1,2,41-triazole were dissolved in a warm liquid mixture consisting of 400 parts of polyethylene glycol 400 and 590 parts of polyethylene glycol 1500 The resulting solution was stirred while cooling and then used as a paste to treat objects against fungi or bacteria.

Claims (13)

the subject of the invention CLAIMS 1. A fungicidal and plant growth regulating composition comprising an inert carrier material and, as active ingredient, 1- (0-3-4) ethyl-1H-1,2,4-1 -riazocapta of the formula I CH »- C — Ar O O (I) in which is Z alkylene comprising the groups —CH2 —CH2, —CH (Cft) —CH1 (CH3) - and —CH2 —CH (alkyl) -, wherein said alkyl contains 1 to 10 carbon atoms, and Ar is a radical selected from the group consisting of phenyl, thienyl, halothienyl, naphthyl, fluorophenyl, and substituted phenyl, wherein the substituted phenyl is a phenyl radical having 1 to 3 substituents independently selected from the group consisting of halogen, straight or branched chain alkyl, A C 1 -C 6 alkoxy group, a C 1 -C 6 alkoxy group, a cyano group and a nitro group, or an acid addition salt thereof. 2. A fungicidal and plant growth regulating agent as claimed in claim 1, wherein the active ingredient is 1- [beta] -aryl] ethyl-1H-1,2,4-triazoketal of the formula Ia; CHrC-Ar O O (kterém in which means Z alkylene comprising the groups —CH — CH2 — —CH2 —CH2 —CH2—, —CH (C8) —CH (CH3) —or. —CH2 —CH (methyl) - a Ar is phenyl, thienyl, halo-thienyl, naphthyl or substituted phenyl, wherein substituted phenyl means a phenyl moiety having 1 to 3 substituents selected independently from the group consisting of halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, cyano or nitro groups, or an acid addition salt thereof. 3. A fungicidal and plant growth regulating composition according to claim 1, wherein the active ingredient comprises 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-ylmethyl-1H-1 as active ingredient; 2,4-trCazole or an acid addition salt thereof. 4. A fungicidal and plant growth regulating composition according to claim 1, wherein the active ingredient is 1- [2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxolane-2. -ylmethyl-1H-1,2,4-triazole or an acid addition salt thereof. 5. A fungicidal and plant growth regulating composition according to claim 1, wherein the active ingredient is 1- [2- (2,4-diclorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] - 1H-1,2,4-triazole or an acid addition salt thereof. 6. A fungicidal and plant growth regulating composition according to claim 1, wherein the active ingredient is 1- (2- (2,4-dihenylphenyl) -4-propyl-1,3-dioxide). N-N-methylbenzyl-1H-H-, 2,4-triazole or an acid addition salt of this compound. 9. A fungicidal and plant growth regulating composition according to claim 1, wherein the active ingredient comprises 1-) 2- (1,4-pentyl-1,3-dioxolan-2-ylmethyl) -1H- 1,2,4-triazole or an acid addition salt thereof. 8. The method of LHL-aryljethyl-lH-1,2,4-triazoketalu general formula ^I CH-Ar ₉ -C y '\ O O (I) wherein represents Z alkylene including —CH — CH2—, —CH2 — CH2 —CH2—, —CH (CH3) —CH (CH3] - or —CH2 — CH (alkyl) - and wherein said alkyl group contains 1 to 10 atoms carbon, and Ar is phenyl, thienyl, halothienyl, naphthyl, fluorophenyl or substituted phenyl, wherein said substituted phenyl is a phenyl radical having 1 to 3 substituents independently selected from halogen, straight or branched chain alkyl comprising (C 1 -C 6), (C 1 -C 6) alkoxy, cyano or nitro, or an acid addition salt of the compound of claim 1, wherein the metal salt of the compound of formula (II) is reacted with a compound of formula (III) in which means Y halogen, a Ar and Z have the same meaning as above, preferably in a polar organic solvent which is inert to the refluxing reaction, optionally further separating and isolating the stereochemical optical isomers of the compounds thus obtained and further optionally converting these compounds to acid addition salts. 9. A process for the preparation of 1- [S-aryl] ethyl-1H-1,2,4-riazoctal of the formula Ia C ^ A O 0 'Z' (kterém in which means Of alkylene, including —CH2 —CH2—, —CH2 —CH2 —CH2—, —СН (СНз) —СН [СНз) - or —CH2 — CH (methyl) - and Ar is (enyl, thienyl, halo-thienyl, na (tyl and substituted) (enyl, by which is meant substituted (enyl) (an enyl radical having 1 to 3 substituents selected independently from the group consisting of halogen, alkyl of 1 to 6 carbon atoms) , (C1-C6) alkoxy, cyano or nitro, or an acid addition salt thereof, as active ingredient according to item 1 or 2, characterized in that the metal salt of the compound of formula II is reacted with a compound of the formula lila Y ~ CH _Z ~ C o in which is. Y halogen, a Ar and Z are as hereinbefore defined, preferably in a polar organic solvent which is inert to the reaction at reflux, and optionally followed by the preparation of an acid addition salt of said product. 10. A process for the preparation of 1- [2- (2,4-Isobutyl) -13-dioxolane-2-methyl-1H-1,2,4-triazole or an acid addition salt thereof, according to item 8, characterized by reacting 1H-1,2,4-triazole and 2- [bromomethyl] -2- 2,4,4-1H-11 (10) -1,3-dioxolane, and optionally adding an addition salt with acid of this compound. 11. A process for the preparation of 1- [2- (2,4'-1'Ыnyг (гnyl) -4-111 (1111x1-13- ^ OX01 ^ 1-2-11111 ^ 1111) -1H-1,2,4-lriazole or acid addition salts of this compound according to Claim 8, characterized in that 1H-1,2,4-triazole and 2-bromomethyl] -2- 2,4,4-trisol (-) - 4-methyl-1,3-dioxolane; and optionally forming an acid addition salt thereof. A process for the preparation of 1- [2- (2,4,4-bis (гnyl) -4-ethyl-13-dioxolan-2-χ1-methyl-11-1H-1,2,4-riazole or an acid addition salt thereof, according to Item 8, characterized in that 1H-1,2,4-triazole and 2- [bromomethyl] -2- 2,4,4-bis (4-fluorophenyl) -4-fluorobenzoate are reacted, and optionally - followed by the preparation of an acid addition salt of this compound. 13. A process for the preparation of the compound of claim 8, wherein the compound is an acid addition salt thereof. A process according to claim 1, characterized in that the reaction is carried out by reacting 1H-1,2,4-triazole and 2-bromomethyl) -2-2,4,4-chlorophenyl] -4-propyl-1,3-dioxolane, and optionally followed by the preparation of an acid addition salt of this compound. 14. A process for the preparation of 1- [2- [2,4-bis (4-ynyl) -4-pennyl, 3-dioxolane-2-xlmethyl] -1H-1,2,4-triazole or an acid addition salt thereof according to Claim 8, characterized in that 1H-1,2,4-triazole and 2- [bromomethyl] -1- [2,4-dichlorophenyl] -4-pmtyl-1H-dioxolane are reacted, and optionally followed by the preparation of an acid addition salt of this compound.