RU2326878C1 - Substituted 2-(1,2,4-triazole-1-ylmethyl)-6-benzylidene-1,4-dioxaspiro[4,5]decanes, their production and application in fungicide composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention concerns new substituted 2-(1,2,4-triazole-1-ylmethyl)-6-benzylidene-1,4-dioxaspiro[4.5]decanes represented by the formula I:

where R¹, R=H, Hal etc., m, n=0-5, and with the process of their production involving condensation of substituted 2-benzylidene cyclohexanone II with 3-halogen-1,3-propanediol by acid catalysis with azeotropic distillation of water in organic dissolvent. Substituted 2-halogenmethyl-6-benzylidene-1,4-dioxaspiro[4.5]decanes represented by the formula III are obtained and further alkylated by 1,2,4-triazolates of alkali metals in polar aprotic dissolvent agent at the temperature of 60 to 180°C.

. The invention also concerns fungicide composition containing substituted 2- (1,2,4-triazole-1-ylmethyl)-6-benzylidene-1,4-dioxaspiro[4.5]decanes represented by the formula I, e.g., 2-(1,2,4-triazole-1-ylmethyl)-6-(4-chlorobenzylidene)-10-methyl-1,4-dioxaspiro[4.5]decane oxalate, which possesses higher fungitoxicity than standard triadimephon.

EFFECT: simplifies production and increases output.

3 cl, 1 tbl, 8 ex

Description

The invention relates to the chemistry of heterocyclic compounds, namely to substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans of general formula I:

where R ¹ - the same or different, mean a hydrogen atom, an alkyl group with the number of carbon atoms from 1 to 6; where R ² are the same or different, mean a hydrogen or halogen atom; m and n are integers from 0 to 5; to their salts with acids, or complexes with metal salts having fungicidal activity. The compounds of general formula I can find application as agricultural, industrial, medical or veterinary fungicides.

The invention also relates to methods for producing compounds of general formula I, to the use of these compounds in compositions with other active and auxiliary compounds for controlling fungal diseases of plant organisms, animals or humans.

Many products with azole and dioxolane rings are known, in particular substituted 4-aminomethyl-1,3-dioxolanes of the general formula II, where R1, R2, R3, R4 are alkyl, cycloalkyl, alkenyl, aryl, heterocyclic substituents [US Patent No. 4,550,359 MKI C07D 317/16, claimed 05/20/1983, publ. 03/05/85], exhibiting fungicidal properties.

4-azolylmethyl-substituted 1,3-dioxolanes with fungicidal activity of the general formula III are known, where R1 is a hydrogen atom, an alkyl, cycloalkyl or aromatic substituent, R2 and R3 are a hydrogen atom, an alkyl, aryl, and also R2 and R3 can together represent a polymethylene group , Z means a carbon atom or a nitrogen atom [Great Britain patent No. 2095236, MKI A01N 43/50, decl. 02/22/1982, publ. 09/29/1982].

The closest to the claimed substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans in structure and production method are the compounds of general formula IV, where R is a hydrogen atom, a branched or unbranched alkyl substituent with the number of carbon atoms from 1 to 6, as well as cyclohexyl and phenyl moieties substituted by hydrogen atoms or having from 1 to 3 different or identical alkyl substituents with the number of carbon atoms or halogens from 1 to four; R1 and R2 can represent a hydrogen atom, alkyl, with the number of carbon atoms from 1 to 12, alkenyl or alkynyl, with the number of carbon atoms from 3 to 8, hydroxyalkyl, with the number of carbon atoms from 3 to 6, alkoxycarbonyl, with the number of carbon atoms from 1 to 6, cycloalkyl, cycloalkylalkyl, with the number of carbon atoms from 3 to 7, dioxolanylalkyl, dioxanylalkyl, oxolanylalkyl, with the number of carbon atoms from 1 to 4, arylalkyl, arylalkenyl, arylalkynyl, with the number of carbon atoms from 6 to 10; R1 together with R2 and together with the nitrogen atom can represent heterocyclic radicals: pyrrolidinyl, morpholinyl, piperidinyl, thiomorpholinyl, azepanyl, substituted with alkyl or hydroxyalkyl substituents with the number of carbon atoms from 1 to 4 [FRG patent No. 3735555, MKI C07D 317/72 claimed 10/21/1987, publ. 09/15/1988] with fungicidal activity. Compounds of general formula IV are prepared by reacting 2-chloromethyl-1,4-dioxaspiro [4.5] decanes with amines in an amine or dimethylformamide medium under heating. The most effective of the compounds mentioned in the patent is spiroxamine (8-tert-butyl-1,4-dioxa [4.5] decan-2-ylmethyl (ethyl) (propyl) amine), which is used to combat plant fungal diseases during the growing season. The consumption rates of this preparation for the protection of, for example, grain crops are relatively high and amount to 500-750 g / ha, while such a widely used fungicide as triadimephone on cereals is used with consumption rates of 125-500 g / ha [The world compendium. The e-Pesticides Manual 2000-2001. 12 ^th Version 2.0. Ed. CDS Tomlin-British Crop Protection Council].

Alkylation of azoles, in particular 1,2,4-triazole, is the subject of many articles. An alkali metal 1,2,4-triazolate is initially prepared, for example, by reaction with sodium hydride in DMF or sodium ethoxide in alcohol, to which an alkyl halide is then added and 1-alkyl-1,2,4-triazoles are obtained [Bergtrap M., Larsen P. Alkylation, acylation and silylation of azoles.// Acta Chem. Scand. - 1990. - Vol. 44, No. 10. - P.1050-1057].

Known methods for producing substituted 4-halogenmethyl-1,3-dioxalanes or 2-halogenomethyl-1,4-dioxaspiro [4.5] decanes by cyclization of substituted ketones or alkylcyclohexanones with 3-halo-1,2-propanediols by acid catalysis, which is carried out with azeotropic distilled water [Wolinski J., Czerwinska A. Poszukiwanie zwiazkow antycholinergicznych. // Acta Pol. Pharm. - 1976. - Vol. 33, No. 6. - P.695-699].

Substituted 2-benzylidenecyclohexanones are prepared by reacting cyclohexanones with aromatic aldehydes in the presence of bases, for example, an aqueous solution of potassium hydroxide by heating [Jonson W. Introduction of the Angular Methyl Group. The Preparation of cis- and trans-9-Methyldecalone-1. // J. Am. Chem. Soc. - 1943. - Vol. 65, No. 7. - R.1317-1324].

The technical task of this invention is to increase the effectiveness of fungicidal preparations and expand their range.

The task is to obtain compounds of general formula I with fungicidal activity, as well as to increase the effectiveness of fungicidal preparations due to the use of substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] Deans I and expanding the range of fungicidal drugs.

According to the present invention, substituted 2-halogenmethyl-6-benzylidene-1,4-dioxaspiro [4.5] decanes VII are prepared by reacting 2-benzylidenecyclohexanones V, where R ¹ are identical or different, represent a hydrogen atom, an alkyl group with carbon atoms from 1 until 6; where R ² are the same or different, mean a hydrogen or halogen atom; type means integers from 0 to 5, with 3-halogen-1,2-propanediols VI, where X means chlorine, bromine and iodine, for example, with 3-chloro-1,2-propanediol, when catalyzed by acids, for example n- toluenesulfonic acid, sulfuric acid, etc., when boiled in an organic solvent, for example benzene or toluene with azeotropic distillation of water.

According to the present invention, substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decanes of formula I are prepared by reacting substituted 2-halogenomethyl-6-benzylidene-1,4 -dioxaspiro [4.5] decans VII, where R ¹ are identical or different, represent a hydrogen atom, an alkyl group with the number of carbon atoms from 1 to 6; where R ² are the same or different, mean a hydrogen or halogen atom; m and n are integers from 0 to 5, X is chlorine, bromine and iodine, with alkali metal 1,2,4-triazolate, where M ⁺ is an alkali metal, for example sodium, potassium, etc., in a polar medium an aprotic solvent, for example, dimethylformamide, at a temperature of from 60 to 180 ° C.

The technical result of the invention is new substances - substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans of general formula I and the method for their preparation. The said patent [German patent No. 3735555, 1988] proposes to obtain substituted 2-aminomethyl-1,4-dioxaspiro [4.5] decans of technical purity in the form of a mixture of the main product with side reaction products. The authors propose to obtain new compounds 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans purified from impurities, isolating them individually, using flash chromatography. In addition, the authors propose to obtain these compounds in a storage stable crystalline form, for example, in the form of their salts with oxalic acid.

The successful use of pesticides to combat various pests largely depends on the formulation of the drug and the conditions under which the active substance is in contact with pests and pathogens of plants. Depending on the physicochemical properties of the preparation, its purpose and method of application, the most effective and economical formulation (composition) is selected, for example, dusts, granules, microencapsulated preparations, wettable powders, emulsion concentrates, ointments, water-dispersible granules, suspension concentrates. Formulations in addition to the active substance may include excipients, solvents, surfactants, water softeners, synergistic additives, etc. The known drug is heterophos, which is used in the form of 7.5% granules to protect potatoes from nematodes and sugar beets from the root aphids. [Pesticides and plant growth regulators: Ref. ed. / N.N. Melnikov, K.V. Novozhilov, S.R. Belan. - M .: Chemistry, 1995, p.24, p.347].

The technical result of the invention is also the development of fungicidal compositions consisting of substituted 2-azol-1-ylmethyl-6-benzylidene-1,4-dioxaspiro [4.5] decans of general formula I at a concentration of 0.1-99% and auxiliary substances that are successful can be used to combat harmful fungal diseases of crops, animals or humans. According to the results of fungicidal in vitro tests, substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decanes, for example 2- (1,2,4-triazole- oxalate 1-ylmethyl) -6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decane (5), superior to the known fungicide triadimephone (3,3-dimethyl-1- (1) used as a reference , 2,4-triazol-1-yl) -1- (4-chlorophenoxy) -2-butanone) with respect to most of the tested pathogen fungi species. The most effective fungicide spiroxamine mentioned in the prototype patent is proposed to be used, for example, to control cereal fungal diseases with higher consumption rates than the triazole widely used triadimefon fungicide, which is inferior to compound 5 in fungicidal activity.

The invention can be illustrated by the following examples.

Example 1. 2- (4-Chlorobenzylidene) -6-methylcyclohexanone (1). To a solution of 22.4 g (0.2 mol) of 2-methylcyclohexanone and 25.4 (0.24 mol) of 4-chlorobenzaldehyde in 50 ml of methanol was added dropwise 33 ml of a 15% aqueous potassium hydroxide solution, stirred at room temperature for 1 hour , then boiled in a water bath with stirring for 2 hours. After cooling, the reaction mixture was extracted with chloroform (2 × 70 ml), the organic layer was washed with diluted hydrochloric acid, water, dried over magnesium sulfate, chloroform was removed in vacuo, the residue was recrystallized from isopropanol and 29.2 g (62%) of 2- (4 -chlorobenzylidene) -6-methylcyclohexanone (1) with so pl. 67-68 ° C.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 1.13 (d, 3 N, CH ₃ ), 1.56-1.78 (m, 2H, 2CH cycle.), 1.87-1.95 (m, 1H, CH cycle.), 2.08-2.14 (m, 1H, CH cycle.), 2.40-2.50 (m, 1H, CH cycle.), 2.64-2.75 (m, 1H, CH cycle.), 2.96-3.04 ( m, 1H, CH cycle.) 7.26 (t, 1H, CH = C, J = 6.2), 7.48 (with 4H arom.); IR spectrum, ν / cm ^-1 : 1670 (С = O), 1580 (СН = С), 730 (С-Cl).

Example 2. 2- (4-chlorobenzylidene) -4-methylcyclohexanone (2).

To a solution of 14.05 (0.1 mol) of 4-chlorobenzaldehyde in 112 g (1 mol) of 4-methylcyclohexanone was added 1.17 L of water. With effective stirring, 10.14 ml (0.875 M) of sodium hydroxide solution are added in portions, for 10 minutes, stirred for 10 hours, the organic layer is separated, the aqueous layer is extracted with chloroform (3 × 60 ml), the organic phases are combined, washed with 100 ml of water, 100 ml of ammonium chloride, then 50 ml of water, dried over magnesium sulfate, transferred to a liter round bottom flask. Chloroform and an excess of 4-methylcyclohexanone are distilled off under vacuum. To a residue of 26.2 g, which is mainly 2 - [(4-chlorophenyl) (hydroxy) methyl] -4-methylcyclohexanone as a light yellow oil, 450 ml of benzene are added, 0.534 g (0.003 mol) of it is added. n-toluenesulfonic acid and boiled for 9 hours. After cooling, the reaction mixture is washed with 5% soda solution (2 × 10 ml), water (2 × 30 ml), brine, dried on magnesium sulfate, the solvent is distilled off under reduced pressure, the residue is vacuum evacuated at room temperature for 2 hours at 0.5 mm Hg, then add 35 ml of isopropanol to it. Precipitated yellow crystals are filtered off. 10.1 g (43%) of 2- (4-chlorobenzylidene) -4-methylcyclohexanone (2) are obtained in the form of yellowish crystals, mp = 71-72 ° C.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 1.08 (d, 3 N, CH ₃ , J ³ = 6.3), 1.49-1.75 (m, 1H, CH cycle.), 1.80 -2.10 (m, 2H, 2CH cycle.), 2.21-2.60 (m, 2H, 2CH cycle.), 2.60-2.66 (m, 0.7H, CH cycle.), 2.66-2.75 (m, 0.3H, CH cycle .), 2.94-2.98 (m, 0.7H, CH cycle.), 3.02-3.08 (m, 0.3H, CH cycle.) 7.26 (t, 1H, CH = C, J ³ = 6.2), 7.36 (with 4H arom.), 7.42 (ws 1H CH = C);

IR spectrum, ν / cm ^-1 : 1670 (С = О), 1590 (СН = С), 725 (С-Cl).

Example 3. 2-Chloromethyl-6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decane (3).

A mixture of 20 g (0.085 mol) of 2- (4-chlorobenzylidene) -6-methylcyclohexanone (1), 18.83 g (0.170 mol) of 3-chloro-1,2-propanediol, 0.731 g (0.00425 mol) n- toluenesulfonic acid in 120 ml of benzene is boiled for 8 hours with a Dean-Stark nozzle until 1.7 ml of water is separated. After cooling, the reaction mass is washed with 5% sodium hydroxide solution (2 × 50 ml), water, dried over magnesium sulfate, benzene is distilled off in vacuo. 25.4 g (91%) of 2-chloromethyl-6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decane (3) are obtained as a yellow oil, n _D ²⁰ = 1.5604.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 1.00 (d, 3 N, CH ₃ ), 1.25-1.48 (m, 2H, CH ₂ cycle.), 1.52-1.60 (m , 1H, CH cycle.), 1.60-1.75 (m, 2H, CH ₂ cycle.), 1.75-1.87 (m, 1H, CH cycle.), 1.87-2.00 (m, 1H, CH cycle.), 3.45- 3.60 (dd, 1 H, CH ₂ Cl, J ³ = 10.2), 3.61-3.73 (dd, 1H, CH ₂ Cl, J ³ = 10.2), 3.75-4.12 (dd, 2 N, CH ₂ O, J ³ = 7.4), 4.35-4.50 (m, 1H, CHO), 6.62 (s, 1H, C = CH), 7.15 (d, 2H, ^3.5 N arom. J ³ = 7.4), 7.32 (d, 2H C, ^2.6 H arom. J ³ = 7.4).

IR spectrum, ν / cm ^-1 : 1590 (СН = С), 1090, 1175 (ССОС), 720 (С-Cl).

The subsequent compound mentioned in Example 4 was obtained analogously to the method described in Example 3.

Example 4. 2-Chloromethyl-6- (4-chlorobenzylidene) -8-methyl-1,4-dioxaspiro [4.5] decane (4), yield 92%, n _D ²⁰ = 1.5561.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 1.07 (d, 3 N, CH ₃ ), 1.39-1.69 (m, 2H, CH ₂ cycle), 1.69-2.06 (m , 3Н, С Н- СН ₃ , СН ₂ cycle.), 2.21-2.77 (m, 2Н, СН ₂ cycle.), 3.42-3.81 (m, 2 Н, СН ₂ Cl), 3.84-4.00 (dd, 2 H, CH ₂ O, J ³ = 7.3), 4.21-4.45 (m, 1H, CHO), 6.58 (s, 1H, C = CH), 7.13 (d, 2H C ^3.5 N arom. J ³ = 7.4), 7.31 (d, 2H C, ^2.6 N arom. J ³ = 7.4).

IR spectrum, ν / cm ^-1 : 1590 (СН = С), 1090, 1180 (ССОС), 715 (С-Cl).

Example 5. 2- (1,2,4-Triazol-1-ylmethyl) -6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decal oxalate [5].

A mixture of 10.8 g (0.033 mol) of 2-chloromethyl-6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decane (3), 3.03 g (0.033 mol) of sodium triazolate and 40 ml of dry DMF is boiled with stirring for 20 hours. The reaction mass is cooled, filtered, the filtrate is evaporated under reduced pressure. The residue was dissolved in chloroform and washed with water (2 × 40 ml), dried over magnesium sulfate and evaporated under reduced pressure. The product is purified using flash chromatography: silica gel "Acros Organics" 35/70), system: a mixture of hexane and acetone (from 10 to 40 vol.% Acetone). 10.33 g (87%) of 2- (1,2,4-triazol-1-ylmethyl) -6- (4-chlorobenzylidene) -10-methyl-1,4-dioxaspiro [4.5] decane are obtained in the form of a yellowish oil . While stirring, a solution of 2.58 g (0.287 mol) of oxalic acid in 30 ml of acetone is added to the oil. The precipitated white crystals are filtered off, washed with hexane and dried in air to obtain 12.71 g of 2- (1,2,4-triazol-1-ylmethyl) -6- (4-chlorobenzylidene) -10-methyl-1,4- oxalate dioxo-spiro [4.5] dean (5) with so pl. 108-109 ° C.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 0.96 (d, 3H, CH ₃ , J ³ = 5.34), 1.22-1.46 (m, 1H, CH cycle.), 1.48- 1.74 (m, 2H, CH cycle.), 1.74-2.00 (m, 2H, CH cycle.), 2.12-2.46 (m, 1H, CH cycle.), 2.51-2.73 (m, 1H, CH cycle.), 3.74-3.95 (m, 1.12Н, СН ₂ O), 4.02 (dd, 0.44Н, СН ₂ O, J ³ = 8.1), 4.17 (dd, 0.44Н, СН ₂ O, J ³ = 8.1 ), 4.29-4.54 (m, 2.56Н, CH ₂ N, СН ₂ O), 4.63 (q, 0.44Н, СНО), 6.52 (d, 1 Н, С = СН, J ⁴ = 3.8), 7.13 (d , 2H C, ^3.5 N arom., J ³ = 8.6), 7.31 (d, 2H C, ^2.6 H arom., J ³ = 8.6), 7.95 (s, 1H, C ³ H _triaz. ), 8.23 ( _. s, 1H C ⁵ H _triazenes) IR, ν / cm ^-1 1560 (C = C), 1270 (CH _triazenes), 1080, 1170 (SOSOS), 720 _(C-Cl)..

The subsequent compound mentioned in Example 6 was obtained analogously to the method described in Example 5.

Example 6. Oxalate 2- (1,2,4-triazol-1-ylmethyl) -6- (4-chlorobenzylidene) -8-methyl-1,4-dioxaspiro [4.5] decane (6), yield 47%, t .pl. 140-141 ° C.

¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 0.86 (d, 3 N, CH ₃ , J ³ = 5.34), 1.21-1.57 (m, 2H, CH ₂ cycle.), 1.58-1.94 (m, 5H, CH cycle), 3.77-3.96 (m, 2H, CH ₂ O), 4.04-4.16 (m, 0.4H, CHO), 4.27-4.46 (m, 2H, CH ₂ N) 4.04-4.16 (m, 0.4H, CHO), 4.50-4.66 (m, 0.6H, CHO), 6.51 (d, 1 N, С = СН, J ⁴ = 3.8), 7.22 (d, 2Н С ^{3, 5} N arom., J ³ = 8.6), 7.40 (d, 2H C ^2.6 N arom., J ³ = 8.6), 8.00 (s, 1H, C ³ H _triaz. ), 8.53 (s, 1H C ⁵ H _triaz. )

IR spectrum, ν / cm ^-1 : 1565 (СН = С), 1270 (СН _triaz. ), 1085, 1170 (ССОС), 720 (С-Cl).

Example 7. The composition of the emulsion concentrate

Active ingredient: (substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans) - 70 g (7%).

Alkylbenzenesulfonic acid calcium salt (ABSK) - 15 g (1.5%)

Oxyethylated octylphenol (OP-7) - 70 g (7%)

Cyclohexanone - 280 g (28%)

A mixture of xylolols - 110 g (11%)

1-Methylnaphthalene - 45 g (4.5%)

Kerosene 410 g (41%).

Example 8. Tests for the fungicidal activity of the compounds was carried out in in vitro experiments. [Guidelines for the testing of chemicals for fungicidal activity. Cherkasy: NPO Plant Protection, VNIIKHSZR, 1990. - 68 p.]

The effect of the preparations on the radial growth of mycelium was determined by dissolving the composition of the compound in acetone and adding an aliquot to potato-sucrose agar at 50 ° C to a concentration of 30 mg / l of the active substance. The final concentration of acetone in control solutions and in solutions with active substances was 1%. In a Petri dish containing 15 ml of agar medium, a fungal culture needle was applied onto the agar surface. Samples were kept in an incubator at 25 ° C and radial growth was measured after 3 days. The percent inhibition was calculated by Abbot with respect to the untreated control. A commercial fungicide triadimefon in the same concentration was used as a reference. The test results are presented in table 3.

Table 1. Test results of substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans for fungicidal activity at a concentration of 30 mg / L. Compound Inhibition of radial growth of fungal mycelium in% of control V.i. R.s. F.o. F.m. B.s. 5 61 76 69 77 81 6 42 67 45 70 62 Reference 53 54 72 90 45 Designations of phytopathogenic fungi: V.i. - Venturia inaequalis, R.s. - Rhizoctonia solani, F.o. - Fusarium oxysporum, F.m. - Fusarium moniliforme, B.s. - Bipolaris sorokiniana.

The use of compounds of the general formula I both individually and in compositions with other active and auxiliary compounds makes it possible to more effectively combat fungal diseases of agricultural crops in comparison with the agricultural fungicide triadimefon used.

Claims (3)

1. Substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans of general formula I,

where R ¹ , identical or different, mean a hydrogen atom, an alkyl group with the number of carbon atoms from 1 to 6, where R ² - same or different, mean a hydrogen atom, halogen, type means an integer from 0 to 5, to their salts with acids, or complexes with metal salts. 2. A method of producing substituted 2- (1,2,4-triazol-1-ylmethyl) -6-benzylidene-1,4-dioxaspiro [4.5] decans of the general formula I,

where R ¹ , identical or different, mean a hydrogen atom, halogen, an alkyl group with the number of carbon atoms from 1 to 6, where R ² - same or different, mean a hydrogen atom, halogen, type means an integer from 0 to 5, consisting in the fact that substituted 2-benzylidenecyclohexanones II, where R ¹ , R ² , m and n have the same meanings as in formula I, are condensed with 3-halogen-1,3-propanediols when catalyzed by acids with azeotropic distillation of water in organic solvents to give substituted 2-halogenmethyl-6-benzylidene-1,4-dioxaspiro [4.5] decans of general formula III, where R, m, n have the same meanings as in formula I, X means halogen, which are reacted with alkali metal 1,2,4-triazolates in a polar aprotic solvent at a temperature of from 60 to 180 ° C

3. A fungicidal composition containing the active substance in a concentration of 0.1-99% and excipients, characterized in that substituted 2-azol-1-ylmethyl-6-benzylidene-1,4-dioxaspiro [4.5] decanes are used as fungicide formula 1, where R ¹ are the same or different, mean a hydrogen atom, an alkyl group with the number of carbon atoms from 1 to 6, where R ² are the same or different, mean a hydrogen atom, halogen, m and n means an integer from 0 to 5 , and their salts with acids, or complexes with metal salts.