RU2440339C1 - Substituted 2-phenylindoles, synthesis method thereof and fungicide compositions based on said compounds - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the novel substituted 2-phenylindole derivatives of general formula I:

, where for R, R² and R⁴=H and R¹=OH, R³=CN,CF₃, COOEt or SO₂NH₂; for R=Me and R¹ and R³=H, R²=NO₂ R⁴=OH; for R=Me and R¹ and R³=H, R²=OH and R⁴=NO₂; for R=Me and R² and R³=H, R¹=NO₂ and R⁴=OH; for R=Me and R² and R³=H, R¹=OH and R⁴=NO₂, which exhibit fungicidal activity, which allows for their use in preparing fungicide compositions. Described is a method of producing compounds where R=Me, R¹ and R³=H, R²=NO₂ R⁴=OH, for R=Me, R¹ and R³=H, R²=OH, R⁴=NO₂, for R=Me, R² and R³=H, R¹= NO₂, R⁴= OH, for R=Me, R² and R³=H, R¹=OH, R⁴=NO₂.

EFFECT: improved method.

4 cl, 3 dwg, 2 tbl, 9 ex

Description

The invention relates to the chemistry of heterocyclic compounds, namely to previously unknown previously substituted 2-phenylindoles of the general formula I:

where R is a hydrogen atom or methyl, R ¹ , R ² and R ⁴ is a hydrogen atom, hydroxyl or nitro group, R ³ is a hydrogen atom, CF ₃ , SO ₂ NH ₂ , CN, COOEt,

possessing fungicidal activity, as well as to the method for their preparation, the use of these compounds as fungicidal agents and fungicidal compositions based on them.

The compounds of general formula I can be used 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.

The literature describes compounds containing the indole cycle and having fungicidal activity.

Closest to the claimed substituted 2-phenylindole in structure and properties are substituted 4-hydroxy-6-nitro-2-arylindoles of the general formula Ia:

where R ¹ means a hydrogen atom or alkyl, R ² means a hydrogen atom and / or alkoxyl, and / or halogen, n is 0-5, and their salts (patent RU No. 2333907, with priority dated 03/27/2007, publ. September 20, 2008, bull. No. 26), which were obtained by the method consisting in the fact that substituted O- (3,5-dinitrophenyl) ketoximes of the general formula IIIa, where R ¹ , R ² and n have the above meanings, treated with hydrazine hydrate in aliphatic alcohol while boiling in the presence of an iron salt and activated carbon, the corresponding O- (3-amino-5-nitrophenyl) ketoximes of general formula IVa being formed, where R ¹ , R ² and n have the above meanings, are subjected to treatment with a mixture of acid with aliphatic alcohol at the boiling point of the mixture according to the following scheme:

The known method is not suitable for obtaining a number of proposed compounds of General formula I.

The objective of the present invention is to expand the range of compounds with fungicidal activity, their raw materials, as well as the development of a method for their preparation.

The problem is achieved by the new substituted 2-phenylindoles of the general formula I, where at R, R ² and R ⁴ = Н and R ¹ = ОН, R ³ = CN, СF ₃ , COOEt or SO ₂ NH ₂ , at R = Me and R ¹ and R ³ = H, R ² = NO ₂ and R ⁴ = OH, with R = Me and R ¹ and R ³ = H, R ² = OH and R ⁴ = NO ₂ , with R = Me and R ² and R ³ = H, R ¹ = NO ₂ and R ⁴ = OH, with R = Me and R ² and R ³ = H, R ¹ = OH and R ⁴ = NO ₂ having fungicidal activity, methods for their preparation and fungicidal compositions based on them.

A method of obtaining compounds of General formula I, where R, R ² and R ⁴ = H and R ¹ = OH, R ³ = CN, CF ₃ , COOEt or SO ₂ NH ₂ , is that substituted 3,5-dinitro compounds of the General of formula II, where R ³ has the above meanings, is reacted with the corresponding oximes of carbonyl compounds (Nu ^- ) when heated, followed by treatment of the resulting nitroximes of general formula III, where R and R ³ have the above meanings, hydrazine hydrate and the resulting amino oximes of general formula IV where R and R ³ are as hereinbefore defined, is cyclised under the action tviem alifatichskogo mixture of alcohol and acid at the boil according to the following scheme:

The interaction of the oximes of carbonyl compounds with commercially available 3,5-dinitro compounds of the general formula II is new and is not described in the literature.

Compounds of general formula I, where at R = Me and R ¹ and R ³ = H, R ² = NO ₂ and R ⁴ = OH, at R = Me and R ¹ and R ³ = H, R ² = OH and R ⁴ = NO ₂ , with R = Me and R ² and R ³ = H, R ¹ = NO ₂ and R ⁴ = OH, with R = Me and R ² and R ³ = H, R ¹ = OH and R ⁴ = NO ₂ cannot be obtained as described above.

To obtain them, a new method is proposed, which consists in the fact that substituted phenylhydrazines of the general formula VI, where R ¹ and R ² = H, MeO or NO ₂ , R ⁴ = NO ₂ or MeO, are reacted with propiophenone in a mixture of boiling formic and trifluoroacetic acid, followed by treatment of the resulting 2-phenyl substituted indoles of general formula VII, where R = Me, R ¹ and R ² = H, MeO or NO ₂ , R ⁴ = NO ₂ or MeO, tetrabutylammonium bromide when heated according to the following scheme:

The starting materials for this method are commercially available substituted anilines V. It is well known that Fischer rearrangement for hydrazone containing a nitro group in the phenylhydrazine ring is very difficult, highly dependent on the structure of the starting carbonyl compound, and often does not lead to the desired results. In particular, for phenons and methoxynitrohydrazines, this process has not been studied. We were able to carry out the conversion of methoxynitrohydrazines VI to 2-phenyl substituted indoles VII without first obtaining intermediate hydrazones in one step. This is achieved by boiling the starting hydrazine and carbonyl compound (propiophenone) in a mixture of boiling formic and trifluoroacetic acids. Known methods for converting a methoxy group to a hydroxy group in the case of indoles VII do not give positive results. We found that this is possible when carrying out the reaction by heating tetrabutylammonium bromide in a melt.

The found methods of converting VI into VII and VII into I are new and are one of the objects of this invention.

The technical result of the invention is new substances - substituted 2-phenylindoles of the general formula I, exhibiting high fungicidal activity. According to the results of in vitro fungicidal tests, the most active is 7-hydroxy-3-methyl-4-nitro-2-phenylindole (8b), superior to the reference triadimephone (3,3-dimethyl-1- (1,2,4-triazole-1 -yl) -1- (4-chlorophenoxy) -2-butanone) with respect to almost all of the tested pathogen fungi species.

This substance was additionally studied on a wider range of fungi, including potato pests.

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. Preparations in addition to the active substance may include excipients, solvents, surfactants, water softeners, synergistic additives, etc. For example, the well-known drug triadimefon is used in the form of a 10% emulsion concentrate to protect cereals, vegetables and fruit crops from fungal diseases of plants [Pesticides and plant growth regulators: Ref. ed. / N.N. Melnikov, K.V. Novozhilov, S.R. Belan. - M .: Chemistry, 1995, p.24, p.287].

In this regard, the technical result of the invention is also the development of fungicidal compositions consisting of substituted 2-phenylindoles of the general formula I at a concentration of 0.1-99% and excipients - the rest. These compositions can be successfully used to combat harmful fungal diseases of crops, animals or humans.

The invention can be illustrated by the following examples.

Example 1. 4-Hydroxy-6-cyano-2-phenylindole (1B).

a) O- (3-Nitro-5-cyanophenyl) -1-phenylethanone oxime (1a).

To a mixture of 13.5 g (0.1 mol) of acetophenone oxime and 13.8 g (0.1 mol) of ₂ CO ₃ in 120 ml of 1-methyl-2-pyrrolidone was added 19.3 g (0.1 mol) 3,5-dinitrobenzonitrile. The reaction mass is heated to 50 ° C and stirred at this temperature until complete conversion of the dinitro compound (3-8 h). The reaction mass is poured into 600 ml of water. The precipitate formed is filtered off, washed with water and dried. The precipitate was recrystallized from EtOH to give 20.22 g (72%) of O- (3-nitro-5-cyanophenyl) -1-phenylethanone oxime (1a), mp. 138-139 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 7.48-7.54 (m, 3H); 7.87-7.90 (m, 2H); 8.26 (s, 1H); 8.32-8.33 (m, 1H); 8.41 (s, 1H).

Found,%: C 64.42, H 3.56; N, 14.52. Calculated for C ₁₅ H ₁₁ N ₃ O ₃ ,%: C 64.05; H 3.94; N, 14.94.

b) O- (3-amino-5-cyanophenyl) -1-phenylethanone oxime (1b).

A mixture of 28.1 g (0.1 mol) of O- (3-nitro-5-cyanophenyl) acetophenone oxime, 0.216 g (0.0008 mol) of iron (III) chloride hexahydrate, 12 g of activated carbon, 40 ml (0.8 mol) of hydrazine hydrate and 700 ml of methanol are refluxed for 3 hours. The reaction mass is filtered hot, the filtrate is cooled. The precipitate formed is filtered off and 18.83 g (75%) of O- (3-amino-5-cyanophenyl) -1-phenylethanone oxime (1b) are obtained, mp. 106-107 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 2.42 (s, 3H); 5.75 (s, 2H); 6.58 (s, 1H); 6.76 (s, 1H); 6.83 (s, 1H); 7.46-7.50 (m, 3H); 7.80-7.83 (m, 2H).

Found,%: C 71.42, H 5.57; N, 16.43. Calculated for C ₁₅ H ₁₃ N ₃ O,%: C 71.70, H 5.21, N16.72.

c) 4-Hydroxy-6-cyano-2-phenylindole (1c).

2.51 g (0.01 mol) of O- (3-amino-5-cyanophenyl) -1-phenylethanone oxime (1b) is placed in a mixture of 10 ml of ethyl alcohol and 10 ml of concentrated hydrochloric acid. The reaction mass is refluxed for 2 hours. It is cooled to room temperature, the precipitate formed is filtered off. Using column chromatography, 4-hydroxy-6-cyano-2-phenylindole (1c) was isolated. Yield 1.497 g, 64%, mp. 222-223 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 6.62 (s, 1H); 7.06 (s, 1H), 7.33-7.39 (m, 2H), 7.46-7.51 (m, 2H), 7.87-7.89 (m, 2H), 10.22 (s, 1H), 11.98 (s, 1H).

Found,%: C 76.73, H 4.16; N, 12.16. Calculated for C ₁₅ H ₁₀ N ₂ O,%: C 76.91, H 4.30, N 11.96.

Example 2. 4-Hydroxy-6-trifluoromethyl-2-phenylindole (2B).

a) O- (3-Nitro-5-trifluoromethylphenyl) -1-phenylethanone oxime (2a).

From 1,3-dinitro-5- (trifluoromethyl) benzene analogously to example 1a), 25.92 g (80%) of O- (3-nitro-5-trifluoromethylphenyl) -1-phenylethanone oxime (2a) are obtained, mp 107 -108 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 7.51-7.53 (m, 3H); 7.84-7.86 (m, 2H); 8.04 (s, 1H); 8.15 (m, 1H); 8.32 (s, 1H).

Found,%: C 55.26, H 3.23; N, 8.41. Calculated for C ₁₅ H ₁₁ F ₃ N ₂ O ₃ ,%: C 55.56; H 3.42; N, 8.64.

b) O- (3-amino-5-trifluoromethylphenyl) -1-phenylethanone oxime (2b).

Analogously to example 1b with the difference that they boil under reflux for 2 hours. Yield 26.46 g (90%) O- (3-amino-5-trifluoromethylphenyl) -1-phenylethanone oxime (2b), mp. 52-53 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 2.42 (s, 3H); 5.72 (s, 2H); 6.55 (s, 1H); 6.61 (s, 1H); 6.77 (s, 1H); 7.48-7.50 (m, 3H); 7.78-7.83 (m, 2H).

Found,%: C 61.63, H 4.27; N, 9.68. Calculated for C ₁₅ H ₁₃ F ₃ N ₂ O,%: C 61.22, H 4.45, N9.52.

c) 4-Hydroxy-6-trifluoromethyl-2-phenylindole (2c).

Analogously to example 1c. Yield 2v 2.16 g (78%), mp. 153-154 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 6.62 (s, 1H); 7.03 (s, 1H); 7.19 (s, 1H); 7.32-7.37 (m, 1H), 7.46-7.51 (m, 2H), 7.85-7.87 (m, 2H), 10.10 (s, 1H), 11.84 (s, 1H).

Found,%: C 64.63, H 3.84; N, 5.16. Calculated for C ₁₅ H ₁₀ F ₃ NO,%: C 64.98, H 3.64, N 5.05.

Example 3. Ethyl 4-hydroxy-2-phenylindole-6-carboxylate (3c).

a) 3-Nitro-5 - ({[[1-phenylethylidene] amino} oxy) benzamide (3a).

From 3,5-dinitrobenzamide analogously to example 1a with the difference that the reaction mass is kept at 60 ° C, 20.61 g (69%) of 3-nitro-5 - ({[1-phenylethylidene] amino} oxy) benzamide (3a) are obtained ), mp 176-177 ° С.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 7.50-7.53 (m, 3H); 7.76 (s, 1H); 7.86-7.87 (m, 2H); 8.17-8.20 (m, 2H); 8.40-8.41 (m, 2H).

Found,%: C 60.56, H 4.13; N, 14.38. Calculated for C ₁₅ H ₁₃ N ₃ O ₄ ,%: C 60.20; H 4.38; N 14.04.

b) 3-amino-5 - ({[[1-phenylethylidene] amino} oxy) benzamide (3b).

Similarly to example 1b. Yield 3b 18.56 g (69%), mp. 148-149 ° C. ¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 2.42 (s, 3H); 5.35 (s, 2H); 6.71 (s, 1H); 6.79 (s, 1H); 6.86 (s, 1H); 7.12 (s, 1H); 7.47-7.51 (m, 3H); 7.72-7.84 (m, 3H).

Found,%: C 66.53; H 5.80; N, 15.44. Calculated for C ₁₅ H ₁₅ N ₃ O ₂ ,%: C 66.90; H 5.61; N15.60.

c) Ethyl 4-hydroxy-2-phenylindole-6-carboxylate (3c).

Analogously to example 1 c. Yield 3v 2.41 g (86%), mp. 189-190 ° C.

Spectrum ¹ H NMR, δ (ppm (DMSO-d ₆ ) :): 1.31-1.36 (m, 3H); 4.26-4.33 (m, 2H); 6.99-7.02 (d, 2H); 7.32-7.37 (m, 1H); 7.46-7.51 (m, 2H); 7.60 (s, 1H); 7.85-7.87 (d, 2H); 9.80 (s, 1H); 11.74 (s, 1H).

Found%: C 72.71; H 5.49; N, 4.87. Calculated for C ₁₇ H ₁₅ NO ₃ ,%: C 72.58; H 5.37; N, 4.98.

Example 4. 4-Hydroxy-2-phenylindole-6-sulfonamide (4B).

a) 3-Nitro-5 - ({[[1-phenylethylidene] amino} oxy) sulfonamide (4a).

From 3,5-dinitrobenzenesulfonamide, analogously to Example 1a, 24.72 g (74%) of 3-nitro-5 - ({[1-phenylethylidene] amino} oxy) sulfonamide (4a) are obtained, mp 185-186 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 7.52-7.54 (m, 3H); 7.78 (m, 2H); 7.84-7.87 (m, 2H); 8.13 (s, 1H); 8.23-8.26 (m, 2H).

Found,%: C 50.56, H 4.13; N, 12.68. Calculated for C ₁₄ H ₁₃ N ₃ O ₅ S,%: C 50.14; H 3.91; N, 12.53;

b) 3-amino-5 - ({[[1-phenylethylidene] amino} oxy) sulfonamide (4b).

Analogously to example 1 b with the difference that they boil under reflux for 3 hours. Yield 25.93 g (85%) of 3-amino-5 - ({[[1-phenylethylidene] amino} oxy) sulfonamide (4b), mp. 143-144 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 2.43 (s, 3H); 5.66 (s, 2H); 6.65 (s, 1H); 6.73 (s, 1H); 6.86 (s, 1H); 7.19 (s, 2H); 7.48-7.50 (m, 3H); 7.80-7.83 (m, 2H).

Found,%: C 55.29; H 4.79; N 13.92 ;. Calculated for C ₁₄ H ₁₅ N ₃ O ₃ S,%: C 55.07; H 4.95; N 13.76.

c) 4-Hydroxy-2-phenylindole-6-sulfonamide (4c).

Analogously to example 1 c. Yield 4v 2.33 g (81%), mp. 123-124 ° C.

¹ H NMR spectrum, δ ppm (DMSO-d ₆ ): 6.86 (s, 1H); 6.99 (s, 1H); 7.13 (s, 2H); 7.34-7.37 (m, 1H); 7.40 (s, 1H); 7.46-7.51 (m, 2H); 7.85-7.87 (d, 2H); 10.01 (s, 1H); 11.81 (s, 1H).

Found,%: C 58.18; H 4.39; N, 9.57. Calculated for C ₁₄ H ₁₂ N ₂ O ₃ S,%: C 58.32; H 4.20; N, 9.72.

Example 5. 7-Hydroxy-3-methyl-5-nitro-2-phenylindole (5b).

a) 3-Methyl-7-methoxy-5-nitro-2-phenylindole (5a).

To a solution of 1.83 g (0.01 mol) (2-methoxy-4-nitrophenyl) hydrazine in formic acid (15 ml) was added 1.34 g (0.01 mol) of propiophenone and 0.5 g (0.004 mol) trifluoroacetic acid and boiled for 2 hours. The reaction mass is cooled, the precipitate formed is filtered off, dried and purified by column chromatography. Obtain 2.06 g (73%) of 3-methyl-7-methoxy-5-nitro-2-phenylindole, so pl. 175-176 ° C.

¹ H NMR spectrum, δ DMSO-d ₆ , δ, ppm): 2.42 (s, 3H), 4.05 (s, 3H), 7.38-7.43 (m, 1H), 7.48-7.53 (m, 3H), 7.68-7.71 (m, 2H), 8.21 (s, 1H), 11.98 (s, 1H).

Found,%: C 68.41; H 5.14; N, 9.67. Calculated for C ₁₆ H ₁₄ N ₂ O ₃ ,%: C 68.07; H 5.00; N, 9.92.

b) 7-Hydroxy-3-methyl-5-nitro-2-phenylindole (5b).

A mixture of 2.82 g (0.01 mol) of 3-methyl-7-methoxy-5-nitro-2-phenylindole and 10 g of tetrabutylammonium bromide is heated to a temperature of 150 ° C and stirred for 90 minutes. The reaction mass was poured into 5% HCl and extracted with chloroform. The extract was dried over Na ₂ SO ₄ , the solvent was distilled off. The dry residue was purified by column chromatography. 1.71 g (64%) of 7-hydroxy-3-methyl-5-nitro-2-phenylindole are obtained, m.p. 196-197 ° C.

Spectrum ¹ H NMR (DMSO-d ₆ , δ, ppm): 2.41 (s, 3H), 7.37-7.42 (m, 2H), 7.48-7.53 (m, 2H), 7.68-7.71 (m, 2H), 8.05-8.06 (d, 1H), 0.57 (s, 1H), 11.80 (s, 1H).

Found,%: C 67.31; H 4.26; N 10.32. Calculated for C ₁₅ H ₁₂ N ₂ 0 ₃ ,%: C 67.16; H 4.51; N, 10.44.

Example 6.5-Hydroxy-3-methyl-7-nitro-2-phenylindole (6b).

a) 3-Methyl-5-methoxy-7-nitro-2-phenylindole (6a).

From (4-methoxy-2-nitrophenyl) hydrazine, analogously to Example 5, 2.22 g (83%) of 3-methyl-5-methoxy-7-nitro-2-phenylindole (6a) are obtained, m.p. 127-128 ° C.

¹ H NMR spectrum (DMSO- (d ₆ , δ, ppm): 2.37 (s, 3H), 3.90 (s, 3H), 7.40-7.45 (m, 1H), 7.50-7.55 (m, 2H); 7.63-7.70 (m, 4H); 11.27 (s, 1H).

Found,%: C 68.38; H 4.89; N, 9.69. Calculated for C ₁₆ H ₁₄ N ₂ O ₃ ,%: C 68.07; H 5.00; N, 9.92.

b) 5-Hydroxy-3-methyl-7-nitro-2-phenylindole (6b).

Analogously to example 5 b. Yield 2.30 g (81%), mp. 172-173 ° C. ¹ H NMR Spectrum (DMSO- (d ₆ , δ, ppm): 2.33 (s, 3H), 7.40-7.44 (m, 2H), 7.49-7.56 (m , 2H), 7.66-7.68 (m, 2H), 9.62 (s, 1H), 11.14 (s, 1H).

Found,%: C 67.42; H 4.12; N, 10.53. Calculated for C ₁₅ H ₁₂ N ₂ O ₃ ,%: C 67.16; H 4.51; N, 10.44.

Example 7. 7-Hydroxy-3-methyl-4-nitro-2-phenylindole (7b).

a) 3-Mtil-7-methoxy-4-nitro-2-phenylindole (7a).

From (2-Methoxy-5-nitrophenyl) hydrazine analogously to example 5a, 2.06 g (73%) of 3-methyl-7-methoxy-4-nitro-2-phenylindole (7a) are obtained, mp. 130-131 ° C.

Spectrum ¹ H NMR (DMSO-d ₆ , δ, ppm): 2.31 (s, 3H), 4.05 (s, 3H), 6.81-6.84 (d, 1H), 7 41-7.46 (m, 1H); 7.49-7.54 (m, 2H); 7.60-7.63 (m, 2H); 7.84-7.87 (d, 1H) 12.00 (s, 1H).

Found%: C 68.18; H 5.21; N, 9.61. Calculated for C ₁₆ H ₁₄ N ₂ O ₃ ,%: C 68.07; H 5.00; N, 9.92.

b) 7-Hydroxy-3-methyl-4-nitro-2-phenylindole (7b). Similarly to example 5b. Yield 1.9 g (61%), mp. 219-220 ° C.

Spectrum ¹ H NMR (DMSO-d ₆ , δ, ppm): 2.33 (s, 3H), 6.61-6.64 (d, 1H, ³ J = 8.5), 7.42 -7.46 (m, 1H), 7.50-7.55 (m, 2H), 7.61-7.64 (m, 2H), 7.77-7.80 (d, 1H, ³ J = 11.10 (s, 1H), 11.83 (s, 1H).

Found,%: C 67.21; H 4.30; N, 10.57. Calculated for C ₁₅ H ₁₂ N ₂ O ₃ ,%: C 67.16; H 4.51; N, 10.44.

Example 8. 4-Hydroxy-3-methyl-7-nitro-2-phenylindole (8b).

a) 3-Methyl-4-methoxy-7-nitro-2-phenylindole (8a).

From (5-methoxy-2-nitrophenyl) hydrazine analogously to example 5 a), 2.20 g (78%) of 3-methyl-4-methoxy-7-nitro-2-phenylindole (8a) are obtained, m.p. 139-140 ° C.

¹ H NMR spectrum (DMSO-d ₆ , δ, ppm): 4.03 (s, 3H), 6.75-6.78 (d, 1H, ³ J = 9), 7.39-7 44 (m, 1H), 7.48-7.53 (m, 2H), 7.60-7.62 (m, 2H), 8.10-8.13 (d, 1H, ³ J = 9 ), 11.36 (s, 1H).

Found,%: C 68.23; H 5.11; N, 9.81. Calculated for C ₁₆ H ₁₄ N ₂ O ₃ ,%: C 68.07; H 5.00; N, 9.92.

b) 4-Hydroxy-3-methyl-7-nitro-2-phenylindole (8b).

Analogously to example 5 b. Yield 2.30 g (86%), mp. 201-202 ° C.

Spectrum ¹ H NMR (DMSO-d ₆ , δ, ppm): 6.56-6.59 (d, 1H, ³ J = 8.9), 7.38-7.43 (m, 1H) 7.48-7.53 (m, 2H), 7.61-7.64 (m, 2H), 7.98-8.01 (d, 1H, ³ J = 8.9), 11.19 (s, 1H); 11.32 (s, 1H).

Found,%: C 67.03; H 4.68; N, 10.37. Calculated for C ₁₅ H ₁₂ N ₂ O ₃ ,%: C 67.16; H4.51; N, 10.44.

Example 9. Obtaining a fungicidal composition (emulsion concentrate).

To a solution of the active ingredient - 90 g of 7-hydroxy-3-methyl-4-nitro-2-phenylindole (7b) in 290 g of cyclohexanone, 15 g of calcium salt of alkylbenzenesulfonic acid (ABSK), 75 g of ethoxylated octylphenol (OP-7) are added with stirring , 110 g of a mixture of xylene and 420 g of oil solvent, get 1000 g of the composition of the emulsion concentrate of the following composition (wt.%):

7-hydroxy-3-methyl-4-nitro-2-phenylindole - 9%

cyclohexanone - 29%

calcium salt of alkylbenzenesulfonic acid (ABSK) - 1.5%

ethoxylated octylphenol (OP-7) - 7.5%

xylene mixture - 11%

oil solvent - 42%

Example 10. Tests for the fungicidal activity of the compounds was carried out in experiments in vitro [Guidelines for determining the fungicidal activity of new compounds. Cherkasy: VNIIKHSZR, ONIITEKHIM, 1983, 2 pp.].

The effect of the preparations on the radial growth of mycelium was determined by dissolving the composition of the compound in acetone and introducing an aliquot in potatoes — sucrose agar at 50 ° C to a concentration of 30 mg / L for 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. A commercial fungicide triadimefon in the same concentration was used as a reference. The test results are presented in table 1.

Table 1 Test results of 4-hydroxy-6-nitroindoles 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. H.s. S.s. 1c 54 one hundred 71 63 75 57 2c 81 one hundred 84 70 one hundred 97 3c 51 one hundred 56 61 88 35 4c 5 10 12 7 13 fifteen 5 B 48 89 63 71 95 94 6b 41 91 34 54 83 51 7b 65 one hundred 91 88 87 54 8b 70 one hundred 73 84 83 51 Reference 53 54 72 90 45 59 The standard is triadimephone (3,3-dimethyl-1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -2-butanone).
Phytopathogenic fungi designations: Vi - Venturia inaequalis, Rs - Rhizoctonia solani, Fo - Fusarium oxysporum, Fm - Fusarium moniliforme, Hs - Helminthosporum sativum, Ss - Sclerotinia sclerotiorum.

Example 11. Tests for fungicidal activity on fungi - pests of potatoes were carried out in experiments in vitro in a similar manner.

The effect of the preparations was determined by the rate of radial growth of mycelium on an agarized nutrient medium based on beer wort with the test compound dissolved in relation to the growth rate on the medium without it. The test compound dissolved in acetone was introduced into a sterile agar medium heated to 50 ° C with a final concentration of the compound in the medium of 1, 10 and 100 mg / L, according to the active substance. An agar block with the mycelium of the test fungus 5 × 5 mm in size was laid down in Petri dishes on the surface of the agar medium. Samples were kept at 23-25 ° C and radial growth was measured after 3 days, subtracting the diameter of the placed agar block. The percent inhibition was calculated by Abbot with respect to the untreated control. When testing the growth of Phytophthora infestans, oat agar medium was used, the same concentrations of fungicides were incubated at 18 ° C, measurements were performed after 7 days. When testing Phizopus sp. measurements were performed after 2 days. The test results are presented in table 2.

table 2 Test results 8b for fungicidal activity at concentrations of 1.10 and 100 mg / l Compound Concentration, mg / L Suppression of radial growth of fungal mycelium,% of control A.s. A.i. F.s. P.i. * R.z. R.S. P.o. 8b one 9 0 9 twenty fourteen fifteen 6 10 fourteen 0 eleven 42 44 24 9 one hundred 51 31 36 one hundred 83 43 62 Designation of mushrooms: A.s. - Alternaria solani Sorauer, A.i. Alternaria infectoria E. G. Simmons, F.s. - Fusarium solani (Mart.) Sacc, P.i. - Phytophthora infestans (Mont.) De Bary, Rz. - Rhizopus sp., P.c. - Penicillium cyclopium Westling, P.o. - Pleurotus ostreatus (Jacq.) P. Kumm.

Claims (4)

1. Substituted 2-phenylindoles of the general formula I

where at R, R ² and R ⁴ = H and R ¹ = OH, R ³ = CN, CF ₃ , COOEt or SO ₂ NH ₂ ;
when R = Me and R ¹ and R ³ = H, R ² = NO ₂ , R ⁴ = OH;
when R = Me and R ¹ and R ³ = H, R ² = OH and R ⁴ = NO ₂ ;
when R = Me and R ² and R ³ = H, R ¹ = NO ₂ and R ⁴ = OH;
when R = Me and R ² and R ³ = H, R ¹ = OH and R ⁴ = NO ₂ . 2. The compound according to claim 1, having fungicidal activity. 3. The method of producing compounds according to claim 1 or 2 of the general formula I, where at R = Me and R ¹ and R ³ = H, R ² = NO ₂ and R ⁴ = OH, at R = Me and R ¹ and R ³ = H, R ² = OH and R ⁴ = NO ₂ , with R = Me and R ² and R ³ = H, R ¹ = NO ₂ and R ⁴ = OH, with R = Me and R ² and R ³ = H , R ¹ = OH and R ⁴ = NO ₂ , which is that the substituted phenylhydrazines of the general formula VI, where R ¹ and R ² = H, MeO or NO ₂ , R ⁴ = NO ₂ or MeO, are reacted with propiophenone in mixture boiling formic and trifluoroacetic acid followed by treatment of the obtained 2-phenyl-substituted indoles of the general formula VII, where R = Me, R ¹ and R ² = H, MeO or NO _2, R ⁴ = NO ₂ or MeO, tetrabutylammonium bromide when LOAD Vania

4. Fungicidal composition containing the compounds according to claim 1 or 2 at a concentration of 0.1-99% and excipients - the rest.