RU2329646C2 - Application of substitutes of 1-(2-phenoxyethyl)- 1,2,4-triazoles in capacity of antifungal agents and antifungal composition on their basis - Google Patents

Abstract

FIELD: chemistry, inorganic.

SUBSTANCE: described is the application of the substitutes of 1-(2-phenoxyethyl)- 1,2,4-triazoles with the general formula of

I, where R=H, Hal, Alk, AlkO and others, n=0-5, in the capacity of fungicides and the antifungal composition on their basis. The bonds have high-performance activity and the structure of their antifungal composition can be used in the capacity of agricultural, medical or veterinary nematocides.

EFFECT: obtaining of high-performance activity antifungal agents.

2 cl, 3 tbl, 6 ex

Description

The invention relates to the chemistry of heterocyclic compounds, namely to substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of general formula I:

where R, identical or different, means a hydrogen atom, a halogen, a (C ₁ -C ₄ ) -alkyl group, a (C ₅ -C ₇ ) -cycloalkyl- (C ₁ -C ₄ ) -alkyl group, (C ₁ -C ₄ ) -alkyl- (C ₅ -C ₇ ) -cycloalkyl group, (C ₁ -C ₄ ) alkoxy group, (C ₁ -C ₄ ) perfluoroalkyl group, nitro group, cyano group,

n is an integer from 0 to 5;

the use of these compounds as fungicidal agents and fungicidal compositions based on them.

The compounds of general formula I can find application as agricultural, industrial, medical or veterinary fungicides in compositions with other active and auxiliary compounds for controlling fungal diseases of plant organisms, animals or humans.

Some compounds of general formula I are included, for example, in catalogs of new compounds: "ChemDiv., Inc. Product Library "published 04/25/2003," Pharma library Collection ", publ. 05/15/2005 and ChemBridge Corporation publ. 06/18/2004., However, neither the preparation method nor the properties of these compounds are described.

Many azole ring products are known, in particular N-alkyl-N- (phenoxyethal) carbamoylazoles with fungicidal activity of the general formula II, where Z is CH or N [UK patent No. 1469772, MKI ² C07D 233/56, publ. 04/06/1977].

Azolylalkoxymethylanilides with herbicidal activity of the general formula III are known, where R ¹ and R ^{2 are} an alkyl group with carbon atoms from 1 to 4, Z is a methylene or ethylene group unsubstituted or substituted with one or two methyl groups, A is pyrazolyl, triazole or imidazole fragments unsubstituted or containing such substituents in the ring as a halogen, methyl group or methoxy group [US patent No. 4336061, MKI ³ AN 43/50, publ. 06/22/1982], which have herbicidal activity.

Also known is 3-hydroxy-2-naphthoate (2-phenoxy) ethyldimethylbenzylammonium (IV) (naphthamone preparation), used as an anthelmintic agent with anti-nematode action [US patent No. 2918401, A41D 27/02, publ. 12/22/1959; M.V. Rubtsov, A. G. Baychikov, Synthetic Chemical-Pharmaceutical Preparations, Moscow, Medicine: 1971, P.86].

Phenoxyalkylimidazoles of general formula V are known, where R is hydrogen or an alkyl group, n is from 1 to 9 and m is from 0 to 8, Z is O, S or NH group atoms [US Patent No. 4,632,934, MKI ⁴ C07D 233 / 54, publ. 12/13/1986], which inhibit thromboxane synthase and, due to this, find use as antihypertensive, anti-inflammatory, antithrombotic agents. [Cross R.E., Dickinson RP, Parry MJ, Randall MJ Selective tromboxane synthetase Inhetitors. I. 1 - [(Aryloxy) alkyl] -lH-imidazoles. // J. Med. Chem. - 1985. - Vol. 28. - P. 1427-32]

The closest to the claimed substituted 1- (2-phenoxyethyl) -1,2,4-triazoles in structure, preparation and use are imidazole-containing fungicides of the general formula VI, where R ¹ and R ^{2 are a} phenyl, phenylalkyl, phenylalkenyl group with such substituents in the phenyl ring, as an alkyl group with carbon atoms from 1 to 4, halogen, trifluoromethyl group, or R ¹ and R ² mean an alkyl, cyclohexyl, cyclohexylalkyl group, X means oxygen or sulfur atoms, n means an integer from 1 to 8 provided that n is not equal en 1 when R ¹ means a phenyl group [US patent No. 4045568, MKI ² AK 31/415, publ. 08/30/1977], which have antimycotic, antibacterial and antiprotozoal activity. Compounds of general formula V are prepared by reacting chloralkylimidazoles with phenols or thiophenols in acetone by heating, followed by isolation by column chromatography.

Mentioned imidazoles VI exhibit antifungal, more precisely antimycotic properties and are proposed for controlling only pathogenic fungi. Substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of the general formula I simultaneously have fungicidal properties in relation to opportunistic fungi, which pose a significant danger to immunocompromised patients, and can effectively combat harmful harmful fungi crops.

The technical problem solved by this invention is to increase the effectiveness of means of combating harmful fungi and expand the range of fungicidal preparations. The problem is solved by the use of compounds of the general formula I as fungicidal agents and fungicidal compositions based on them.

According to the present invention, substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of formula I are prepared by reacting substituted 2-haloethoxybenzenes (VII) with alkali metal 1,2,4-triazolate or with 1,2,4-triazole in a polar aprotic solvent, for example acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone or in aliphatic or cycloaliphatic alcohols at a temperature of from 60 to 180 ° C.

In the above scheme, R and n have the same meanings as in the formula I, X means chlorine, bromine, mesyl or tosyl group, and M means an alkali metal, for example sodium, potassium, etc.

Substituted 2-haloethoxybenzenes (VII) and 2-phenoxyethylsulfonates are prepared by reacting phenols (VIII) with 1,2-dihaloethanes or respectively ethylene glycol ditosyl ether in the presence of bases, for example, an aqueous solution of sodium hydroxide or potash, by heating [Hey P., Willey GL Choline 2,6-xylyl ether bromide; an active quaternary local anaestetic. // Brit. J. Pharmacol. Chemather. - 1954. - Vol.9, N 4. - P.471-5.]. The reaction is also carried out in alcohol with preformed sodium phenolate [Genzer J.D., Huttrer C.P., van Wesem G.C. Phenoxy - and Benzyloxyalkyi Thiocyanates. // J. Am. Chem. Soc. - 1951. - Vol.73, N 7. - P.3159-62.].

In the above scheme, R and n have the same meanings as in formula I, X is chloro, bromo, mesyl or tosyl; B is base.

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 chosen, 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].

In this regard, the technical result of the invention is also the development of fungicidal compositions consisting of substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of the general formula I at a concentration of 0.1-99% and auxiliary substances that can be successfully used to combat harmful fungal diseases of crops, animals or humans.

The method of producing substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of general formula I, their use as fungicides, and also as part of fungicidal compositions, can be illustrated by the following examples:

Example 1. (2-Bromoethoxy) benzene.

To a mixture of 18.8 g (0.2 mol) of phenol 1a, 75.2 g (0.4 mol) of 1,2-dibromoethane and 48 ml of water heated to boiling in an oil bath, 31 ml of 23% aqueous solution was added dropwise over 0.5 h. NaOH solution and boiled with stirring for 3 hours. After cooling, the organic layer is separated, the aqueous layer is extracted with chloroform (2 × 30 ml), the organic layers are combined, washed with 5% NaOH solution, water, dried over MgSO ₄ , the solvent is removed in vacuo. The residue is distilled in vacuo, collecting the fraction with so Kip. 128-31 ° C (18 Torr), 15.7 g (39%) of (2-bromoethoxy) benzene are obtained with a melting point of 33-34 ° C. ¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 3.66 (t, 2 N, CH ₂ Br, J = 6.3), 4.32 (t, 2 N, CH ₂ O, J = 6.3 ), 6.96 (t, 3H, 3CH arom, J = 7.7), 7.31 (d, 2 H, 2CH arom, J = 8.6). IR spectrum, ν / cm ^-1 : 1265 (С _ar -O), 1095, 1040, 1020 (С _alk -O).

The following compounds mentioned below in examples 2 and 3 were obtained analogously to the method described in example 1.

Example 2. 1- (2-Bromoethoxy) -3,4-dichlorobenzene, yield 59.1%, b.p. 160-161 ° C (8 Torr), n _D ¹⁸ = 1.5823. Found (%): Br 29.78. C ₈ H ₇ BrCl ₂ O. Calculated (%): Br 29.60. ¹ H NMR (CDCl ₃ , δ, ppm, J, Hz): 3.76 (t, 2 N, CH ₂ Br, J = 6.6), 4.38 (t, 2 N, CH ₂ O, J = 6.6) , 6.94 (d d, 1 H, 1CH arom., J = 9.8, 3.2), 7.14 (d, 1 H, 1CH arom., J = 3.2) 7.41 (d, 1 H, 1CH arom., J = 9.8) . IR spectrum, ν / cm ^-1 : 1290, 1260, 1225 (C _ar -O), 1075, 1015 (C _alk -O)

Example 3. 1- (2-Bromoethoxy) -3-trifluoromethylbenzene, yield 46.7%, b.p. 116-122 ° C (14 Torr), n _D ²³ = 1.4864. Found (%): Br 29.91. C ₉ H ₈ BrF ₃ O. Calculated (%): Br 29.70. ¹ H NMR spectrum (CDCl ₃ , δ, ppm, J, Hz): 3.67 (t, 2 N, CH ₂ Br, J = 6.1), 4.35 (t, 2 N, CH ₂ O, J = 6.1 ), 7.03-7.19 (m, 2 H, 2CH arom.), 7.26 (d, 1 H, 1CH arom., J = 7.5), 7.43 (t, 1 H, 1CH arom., J = 7.7). IR spectrum, ν / cm ^-1 : 1334, 1166, 1126 (CF), 1280, 1226 (C _ar -O), 1096, 1066, 1020 (C _alk- O).

Example 4. 1- (2-Phenoxyethyl) -1,2,4-triazole (1).

To a solution of sodium ethylate obtained from 0.47 g (20.4 mmol) of sodium and 20 ml of ethanol, 1.52 g (22 mmol) of 1,2,4-triazole are added and evaporated to dryness on a rotary-film evaporator in a vacuum of a water-jet pump. 20 ml of acetonitrile was added to the obtained sodium triazolate, and with stirring, a solution of 4.02 g (20 mmol) of 2-bromoethoxybenzene in 15 ml of acetonitrile was added dropwise and boiled for 6 hours with stirring, cooled, the NaBr precipitate was filtered off, and the filtrate was evaporated. The residue was dissolved in methylene chloride (30 ml), washed with water, brine and dried over MgSO ₄ . The solvent was removed and the remaining oil was crystallized from isooctane-ethyl acetate (4: 1) to give 2.46 g (65%) of (2-phenoxyethyl) -1,2,4-triazole 1 s.p. 77-8 ° C. Found (%): C 63.52; H 5.90; N, 22.35. C ₁₀ H ₁₁ N ₃ O. Calculated (%): C 63.48; H 5.86; N, 22.21.

Example 5. 1- [2- (4-Nitrophenoxy) ethyl] -1,2,4-triazole (19).

To a solution of sodium ethylate obtained from 0.46 g (20 mmol) of sodium and 20 ml of ethanol, 1.52 g (22 mmol) of 1,2,4-triazole are added and evaporated to dryness on a rotary-film evaporator in a vacuum of a water-jet pump. To the sodium triazolate obtained, 20 ml of tetrahydrofuran are added and 4.92 g (20 mmol) of 2-bromoethoxy-4-nitrobenzene are added in portions with stirring and boiled for 3 hours with stirring, cooled, the NaBr precipitate is filtered off and the filtrate is evaporated. The residue was dissolved in absolute ethanol, filtered off from the precipitate, evaporated and recrystallized from a mixture of hexane-ethyl acetate (4: 1) to obtain 4.17 g (89%) of 1- [2- (4-nitrophenoxy) ethyl] -1,2,4 triazole (19). with mp 112-113 ° C.

Data on the melting points of the obtained products and the yield are shown in Table 1, spectral characteristics are shown in Table 2. ¹ H NMR spectra were recorded on a Bruker AC-200 instrument (operating frequency 200 MHz), CDCl _{3 was} used as a solvent. The IR spectra of solid compounds were recorded in liquid paraffin, liquid and low melting point - in a film on a Specord M80 instrument.

Table 1. Melting points and yield of compounds of formula I Compound R Exit, % T. pl., ° C; recrystallization solvent one 2 3 four one N 65 77-78 (isooctane - EtOAc) 2 2-CH ₃ 55 24-25 ° C (hexane - EtOAc) 3 3-CH ₃ 63 22-23 (hexane - EtOAc) four 4-CH ₃ 59 47-48 (hexane - EtOAc) 5 2.6- (CH ₃ ) ₂ 43 62-63 (iPrOH - EtOAc) 6 2-CH ₃ O 21 58-59 (hexane - EtOAc) 7 3-CH ₃ O 31 71-72 (iPrOH-EtOAc) 8 4-CH ₃ O 75 64-66 (hexane - EtOAc) 9 2-f 37 58-59 (iPrOH - EtOAc) 10 2-cl 54 63-65 (hexane - EtOAc) eleven 3-cl 28 85-86 (EtOH) 12 4-cl 44 66-67 (EtOH) 13 2,4-Cl ₂ 35 111-112 (EtOH) fourteen 3,4-Cl ₂ 62 109-110 (EtOH) fifteen 2-CH ₃ -4-Cl 72 106-107 (hexane-EtOAc) 16 5-CH ₃ -2-Cl 25 128-129 (hexane - EtOAc) 17 4-br 58 86-87 (EtOH) eighteen 3-CF ₃ 60 44-45 (hexane - EtOAc) 19 4-NO ₂ 89 112-113 (hexane-EtOAc)

Table 2. Spectal properties of compounds of formula I Compound Spectrum ¹ H NMR, δ, ppm, (J / Hz), in CDCl ₃ IR spectrum, ν / cm ^-1 one 2 3 one 4.34 (t, 2 H, CH ₂ N, J = 5.0), 4.58 (t, 2 H, CH ₂ O, J = 5.0), 6.86 (d, 2 H, 2CH arom., J = 7.9), 6.99 ( t, 1 H, 1CH arom., J = 7.3), 7.29 (kb, 2 H, 2CH arom., J = 6.9), 7.97 (s, 1 H, 1CH triaz.), 8.23 (s, 1 H, 1CH triaz.). 1270, 1245 (C _ar -O), 1080, 1050, 1020 (C _alk -O) 2 2.16 (s, 3 N, CH ₃ ), 4.35 (t, 2 N, CH ₂ N, J = 5.0), 4.66 (t, 2 N, CH ₂ O, J = 5.0), 6.77 (d, 1 N, 1CH arom., J = 8.4),), 6.90 (t, 1 H, 1CH arom., J = 7.4), 7.13 (d, 1 H, 1CH arom., J = 6.5), 7.97 (s, 1 N, 1CH triaz.), 8.23 (s, 1 H, 1CH triaz.). 1270, 1240 (C _ar -O), 1050, (C _alk -O) 3 2.32 (s, 3 N, CH ₃ ), 4.33 (t, 2 N, CH ₂ N, J = 5.0), 4.58 (t, 2 N, CH ₂ O, J = 4.9), 6.67 (d, 1 N, 1CH aromatic, J = 7.2),), 6.69 (s, 1 H, 1CH aromatic), 6.80 (d, 1 H, 1CH aromatic, J = 7.6), 7.17 (t, 1 H, 1CH aromatic, J = 7.5), 7.98 (s, 1 H, 1CH triaz.), 8.28 (s, 1 H, 1CH triaz.). 1285, 1260 (C _ar -O), 1060 (C _alk -O) four 2.29 (s, 3 N, CH ₃ ), 4.31 (t, 2 N, CH ₂ N, J = 5.0), 4.56 (t, 2 N, CH ₂ O, J = 5.0), 6.76 (d, 2 N, 2CH arom., J = 8.5), 7.08 (d, 1 H, 1CH arom., J = 8.4), 7.97 (s, 1 H, 1CH triaz.), 8.24 (s, 1 H, 1CH triaz.). 1235 (C _ar -O), 1040, 1015 (C _alk -O) 5 2.01 (s, 3 N, (CH ₃ ) ₂ ), 4.05 (t, 2 N, CH ₂ N, J = 5.0), 4.54 (t, 2 N, CH ₂ O, J = 5.0), 6.77-6.83 ( m, 1 H, 1CH arom.), 6.88 (d, 1 H, 1CH arom., J = 8.0), 7.77 (s, 1 H, 1CH triaz.), 8.38 (s, 1 H, 1CH triaz.). 1270 (C _ar -O), 1085, 1055 (C _alk -O) 6 3.87 (s, 3 N, CH ₃ O), 4.37 (t, 2 N, CH ₂ N, J = 4.9), 4.59 (t, 2 N, CH ₂ O, J = 5.0), 6.81-7.03 (m, 4 H, 4CH aromat.), 7.96 (s, 1 H, 1CH triaz.), 8.40 (s, 1 H, 1CH triaz.). 1250, 1225 (C _ar -O), 1050, 1015 (C _alk -O) 7 3.78 (s, 3 N, CH ₃ O), 4.33 (t, 2 N, CH ₂ N, J = 4.5), 4.59 (t, 2 N, CH ₃ O, J = 4.4), 6.42 (d, 2 N , 2CH aromatic, J = 2.5), 6.52 (t, 1 H, 1CH aromatic, J = 8.1), 7.18 (t, 1 H, 1CH aromatic, J = 8.1), 8.01 (s, 1 H, 1CH triaz.), 8.33 (s, 1 H, 1CH triaz.). 1265 (C _ar -O), 1050 (C _alk -O) 8 3.76 (s, 3 N, CH ₃ O), 4.28 (t, 2 N, CH ₂ N, J = 4.9), 4.55 (t, 2 N, CH ₃ O, J = 4.9), 6.80 (s, 4 N , 4CH arom), 7.97 (s, 1H, 1CH triaz.), 8.26 (s, 1H, 1CH triaz.). 1270, 1240, 1220 (C _ar -O), 1060, 1030, 1015 (C _alk -O) 9 4.39 (t, 2 H, CH ₂ N, J = 5.0), 4.62 (t, 2 H, CH ₂ O, J = 4.9), 6.91 (d, 1 H, 1CH arom., J = 8.3), 6.94- 7.12 (m, 3 H, 3CH arom.), 7.98 (s, 1 H, 1CH triaz.), 8.31 (s, 1 H, 1CH triaz.). 1265 (C _ar -O), 1045 (C _alk -O) 10 4.36 (t, 2 H, CH ₂ N, J = 4.9), 4.66 (t, 2 H, CH ₂ O, J = 4.9), 6.86 (d, 1 H, 1CH arom., J = 8.2), 6.94 ( t, 1 H, 1CH arom., J = 7.5), 7.21 (t, 1 H, 1CH arom., J-7.5), 7.37 (d, 1 H, 1CH arom., J = 7.7), 7.97 (s, 1 H, 1CH triaz.), 8.39 (s, 1 H, 1CH triaz.). 1270, 1245 (C _ar -O), 1065, 1040 (C _alk -O) eleven 4.32 (t, 2 H, CH ₂ N, J = 5.0), 4.57 (t, 2 H, CH ₂ O, J = 5.0), 6.74 (d d, 1 H, 1CH arom., J = 8.3, 2.4) , 6.86 (t, 1 H, 1CH arom., J = 2.2), 6.96 (d d, 1 H, 1CH arom., J = 8.7, 0.9), 7.19 (t, 1 H, 1CH arom., J = 8.1 ), 7.96 (s, 1 H, 1CH triaz.), 8.21 (s, 1 H, 1CH triaz.). 1250 (C _ar -O), 1065, 1050 (C _alk -O) 12 4.28 (t, 2 H, CH ₂ N, J = 5.0), 4.57 (t, 2 H, CH ₂ O, J = 5.0), 6.79 (d, 2 H, 2CH arom., J = 8.9), 7.24 ( d, 2 H, 2CH arom., J = 8.9), 7.97 (s, 1 H, 1CH triaz.), 8.23 (s, 1 H, 1CH triaz.). 1270, 1240 (C _ar -O), 1085, 1050 (C _alk -O) 13 4.34 (t, 2 H, CH ₂ N, J = 4.9), 4.65 (t, 2 H, CH ₂ O, J = 4.9), 6.77 (d, 1 H, 1CH arom., J = 8.7), 7.17 ( d d, 1 H, 1CH arom., J = 8.8, 2.1), 7.36 (d, 1 H, 1CH arom., J = 2.0), 7.97 (s, 1 H, 1CH triaz.), 8.36 (s, 1 H, 1CH triaz.). 1270, 1255 (C _ar -O), 1065, 1050 1015 (C _alk -O) fourteen 4.28 (t, 2 H, CH ₂ N, J = 5.0), 4.56 (t, 2 H, CH ₂ O, J = 5.0), 6.66 (d d, 1 H, 1CH arom., J = 9.0, 2.8) , 6.93 (d, 1 H, 1CH arom., J = 2.5), 7.28 (d, 1 H, 1CH arom., J = 8.0), 7.94 (s, 1 H, 1CH triaz.), 8.19 (s, 1 H, 1CH triaz.). 1260, 1230 {C _ar -O), 1055 (C _alk -O) fifteen 2.11 (s, 3 H, CH ₃ ), 4.30 (t, 2 H, CH ₂ N, J = 5.1), 4.61 (t, 2 H, CH ₂ O, J = 5.0), 6.68 (d, 1 H, 1CH arom., J = 7.7), 7.05-7.17 (m, 2 H, 2CH arom.), 7.98 (s, 1 H, 1CH triaz.), 8.23 (s, 1 H, 1CH triaz.). 1270, 1240 (C _ar -O), 1045, 1015 (C _alk -O) 16 2.31 (s, 3 H, CH ₃ ), 4.29 (t, 2 H, CH ₂ N, J = 5.0), 4.54 (t, 2 H, CH ₂ O, J = 5.0), 6.61 (d d, 1 H , 1CH arom., J = 8.7, 2.8), 6.71 (d, 1 H, 1CH arom., J = 2.7), 7.20 (t, 1 H, 1CH arom., J = 8.7), 7.95 (s, 1 H , 1CH triaz.), 8.20 (s, 1 H, 1CH triaz.). 1240 (C _ar -O), 1070, 1040 (C _alk -O) 17 * 4.35 (t, 2 H, CH ₂ N, J = 5.1), 4.57 (t, 2 H, CH ₂ O, J = 5.1), 6.89 (d d, 2 H, 2CH arom., J = 6.8, 2.2 ), 7.43 (d d, 2 H, 2CH arom., J = 6.8, 2.1), 7.96 (s, 1 H, 1CH triaz.), 8.53 (s, 1 H, 1CH triaz.). 1270, 1240 (C _ar -O), 1070, 1055 (C _alk -O) eighteen 4.39 (t, 2 H, CH ₂ N, J = 4.9), 4.61 (t, 2 H, CH ₂ O, J = 4.9), 7.02 (d, 1 H, 1CH arom., J = 8.3), 7.09 ( s, 1 H, 1CH arom.), 7.24 (d, 1 H, 1CH arom., J = 7.7), 7.39 (t, 1 H, 1CH arom., J = 8.0), 7.98 (s, 1 H, 1CH triaz.), 8.24 (s, 1 H, 1CH triaz.). 1252 (C _ar -O), 1088, 1058 (C _alk -O) 19 4.45 (t, 2 H, CH ₂ N, J = 5.1), 4.65 (t, 2 H, CH ₂ O, J = 5.0), 6.94 (d, 2 H, 2CH arom., J = 8.9), 7.97 ( s, 1 H, 1CH triaz.), 8.21 (d, 2 H, 2CH arom., J = 8.9), 8
.23 (s, 1 H, 1CH triaz.). 1270, 1240 (C _ar -O), 1112, 1048 (C _alk -O) * in d _{6 -} DMSO

Example 6. The composition of the emulsion concentrate

Active ingredient (substituted 1- (2-phenoxyethyl) -1,2,4-triazole of general formula I) 80 g

Alkylbenzenesulfonic acid calcium salt (ABSK) 20 g

Oxyethylated Octylphenol (OP-7) 80 g

Cyclohexanone 300 g

Xylene 150 g

Oil solvent 370 g.

Example 7. Tests for the fungicidal activity of the compounds was performed in vitro experiments. [Guidelines for determining the fungicidal activity of new compounds. Cherkasy: NIITEKHIM. 1984. 34 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 the potato-sucrose agar at 50 ° C to a concentration of 30 mg / l according to the active substance. The final concentration of acetone in control solutions and in solutions with active substances was 1%. In Petri dishes 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. As a reference, the commercial fungicide triadimefon (3,3-dimethyl-1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -2-butanone) in the same concentration was used. The test results are presented in table 3.

Table 3. Test results of substituted 1- (2-phenoxyethyl) -1,2,4-triazoles for fungicidal activity at a concentration of 30 mg / L. Compound Suppression of radial growth of fungal mycelium,% of control V.i. R.s. F.o. F.m. B.s. S.s. one 19 26 6 one 0 0 12 5 46 13 40 26 6 13 60 73 27 46 40 thirty fourteen fifty 68 57 64 27 twenty fifteen 32 46 27 42 26 twenty 17 four 22 fourteen fifteen eighteen four eighteen 52 68 51 63 one hundred one hundred 19 40 40 17 28 19 12 Reference 53 54 72 90 45 65 Designations: V.i. - Venturia inaequalis, R.s. - Rhizoctonia solani, F.o. - Fusarium oxysporum, F.m. - Fusarium moniliforme, B.s. - Bipolaris sorokiniana (Helminthosporium sativum), S.s. - Sclerotinia sclerotiorum.

The test data for the biological activity of compounds 1, 12-15 and 17-19 are given, however, all the obtained compounds of formula I exhibit fungicidal activity.

The use of compounds of the general formula I in compositions with other active and auxiliary compounds makes it possible to more effectively combat fungal diseases of agricultural crops in comparison with, for example, such a widely used triazole fungicide as triadimephone.

Claims (2)

1. The use of substituted 1- (2-phenoxyethyl) -1,2,4-triazoles of the general formula I

where R, identical or different, means a hydrogen atom, a halogen, a (C ₁ -C ₄ ) -alkyl group, a (C ₅ -C ₇ ) -cycloalkyl- (C ₁ -C ₄ ) -alkyl group, (C ₁ -C ₄ ) -alkyl- (C ₅ -C ₇ ) -cycloalkyl group, (C ₁ -C ₄ ) alkoxy group, (C ₁ -C ₄ ) perfluoroalkyl, nitro group, cyano group, n means an integer from 0 to 5, in as fungicidal agents. 2. A fungicidal composition containing a fungicide in a concentration of 0.1-99% and excipients, characterized in that substituted 1- (2-phenoxyethyl) -1,2,4-triazoles I according to claim 1 are used as a fungicide.