RU2515894C2 - Preparations which possess fungicidal activity - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described are preparations, which possess fungicidal activity, containing hydrazones of nitro-1,2,3-tiazol-4-yl-carbaldehyde of formula

Ia-c,

in concentration 30 mg/l in acetone, which can be applied in agriculture for fight against fungal diseases of plants.

EFFECT: improved qualities of claimed preparations.

1 tbl, 4 ex

Description

The invention relates to the field of organic chemistry, namely to hydrazones of nitro-1,2,3-triazol-4-yl carbaldehydes of the formula Ia-b,

and the use of these compounds as fungicides in agriculture for controlling undesired fungal diseases of plants.

A known method for producing analogues in structure, based on the reaction of heme.-nitrooxadiazolemethylation of 3-aryl-5-trinitromethyl-1,2,4-oxadiazoles 1,1-diphenylhydrazine under mild conditions (0 ° C, 2 hours) [A.G. Tyrkov. Zhurn. organ, chemistry. 2002. 38 (12), 1874].

Known substituted 1- (2-phenoxyethyl) -1,2,4-triazoles and compositions based on them, exhibiting fungicidal activity [patent RU No. 2229646], as well as benzotriazole derivatives and their salts, which are effective in combating undesirable fungi when protecting plants and materials [patent RU No. 2158740].

The 1,2,3-triazole cycle associated with the nitrohydrazone function is a practically unexplored system. Nevertheless, compounds containing a 1,2,3-triazole framework are promising from the point of view of their practical application.

In particular, substituted 2-aryl-1,2,3-triazole-1-oxides are recommended as insecticides [T.I. Godovikova, E.L. Ignatiev, L.I. Khmelnitsky. Synthesis and properties of 1,2,3-triazole-1-oxides. Chemistry of heterocyclic compounds. 1989. No. 2. S.147-156]. 1-Phenyl-4 (5) - (aryloxymethyl) -1,2,3-triazoles have high fungicidal activity [G.I. Kaplan, S.S. Kupolenko. Triazoles and their pesticidal activity. M. 1983. 38 s]. However, the method of obtaining such representatives of 1,2,3-triazoles is quite laborious.

The technical result is a substance having fungicidal activity and representing hydrazones of nitro-1,2,3-triazol-4-yl carbaldehyde Ia-b. Compounds were obtained by heme-nitrotriazolemethylation by substituted derivatives of 4-trinitromethyl-1,2,3-triazoles IIa-1,1-diphenylhydrazine, which allows to expand the base of substances with fungicidal activity.

The technical result obtained allows us to expand the range of biologically active substances with fungicidal activity.

The method for producing hydrazones of nitro-1,2,3-triazol-4-yl carbaldehyde Ia-b is illustrated in the following examples.

Example 1

1-Nitro-3,3-diphenyl-1- (2-methyl-1,2,3-triazol-4-yl) -2,3-diazoprop-1-ene (compound Ia).

To a solution of 1 g of 2-methyl-4-trinitromethyl-1,2,3-triazole IIa in 20 ml of dried ethoxyethane at 0 ° C, 0.74 g of 1,1-diphenylhydrazine in 10 ml of the same solvent was added with stirring. The reaction mixture was incubated for 2 hours at a temperature of 0 ° C. The solvent is evaporated, the residue is subjected to column chromatography on a glass column (l 500 mm, d 10 mm), using Silicagel 100 / 400µ grade silica gel as a sorbent, benzene eluate is collected. Obtain 0.57 g (42%) of compound Ia, so pl. 123 ° C (from ethanol).

IR spectrum, ν, cm ^-1 , CHCl ₃ : 1555, 1290 (NO ₂ ).

¹ H NMR (80 MHz), δ, ppm, d _6: 7.25 s (1H, CH), 7.10-7.15 m (10H, 2C ₆ H _5), 3.78 s (3H, _CH3).

Electronic spectrum, nm (logε), СН ₃ ОН: 235 (4.10), 370 (3.98).

Found,%: C 59.58; H 4.37; N, 26.02. C ₁₆ H ₁₄ N ₆ O ₂ . Calculated,%: C 59.70; H 4.68; N 26.22.

Example 2

1-Nitro-3,3-diphenyl-1- (1-methyl-1,2,3-triazol-4-yl) -2,3-diazoprop-1-ene (compound IB).

Obtained analogously to compound Ia from 1 g of 1-methyl-4-trinitromethyl-1,2,3-triazole IIb and 0.74 g of 1,1-diphenylhydrazine, eluate-benzene.

Obtain 0.6 g (44%) of compound IB, so pl. 144 ° C (from ethanol).

IR spectrum, ν, cm ^-1 , CHCl ₃ : 1555, 1290 (NO ₂ ).

¹ H NMR (80 MHz), δ, ppm, d _6: 7.31 s (1H, CH), 7.12-7.17 m (10H, 2C ₆ H _5), 3.67 s (3H, _CH3).

Electronic spectrum, nm (logε), СН ₃ ОН: 235 (4.11), 370 (4.0).

Found,%: C 59.62; H 4.34; N 26.08. C ₁₆ H ₁₄ N ₆ O ₂ . Calculated,%: C 59.70; H 4.68; N 26.22.

Example 3

1-Nitro-3,3-diphenyl-1- (5-methoxycarbonyl-2H-1,2,3-triazol-4-yl) -2,3-diazoprop-1-ene (compound IB).

Obtained analogously to compound Ia from 1 g of 5-methoxycarbonyl-4-trinitromethyl-2H-1,2,3-triazole IIc and 0.74 g of 1,1-diphenylhydrazine, eluate-chloroform.

Obtain 0.63 g (48%) of compound IB, so pl. 201-202 ° C (from CHCl ₃ : 1: 1 hexane).

IR spectrum, ν, cm ^-1 , CHCl ₃ : 1550, 1285 (NO ₂ ); 1730 (CO).

¹ H NMR spectrum, (80 MHz), δ, ppm, d ₆ : 7.10-7.16 m (10Н, 2С ₆ Н ₅ ), 3.73 s (3Н, СН ₃ О).

Electronic spectrum, nm (logε), СН ₃ ОН: 235 (4.07), 372 (4.06).

Found,%: C 55.73; H 3.82; N, 22.95. C ₁₇ H ₁₄ N ₆ O ₄ . Calculated,%: C 56.14; H 3.95; N 23.06.

The use of hydrazones of nitro-1,2,3-triazol-4-yl carbaldehyde Ia-b as fungicides is illustrated by the following example.

Example 4

A test for the fungicidal activity of the compounds was carried out in experiments in vitro [Methodological tests to determine the fungicidal activity of new compounds. Cherkasy: NIITEKHIM. 1984. 34 s]. The effect of drugs on the radial growth of mycelium was determined by dissolving the compounds in acetone and adding an aliquot to potato sugar agar at 50 ° C to a concentration of 30 mg / L for the active substance. The final concentration of acetone in control solutions and 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. The samples were kept in a thermostat at 25 ° С ± 1 ° С 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) was used in the same concentration. The test results are presented in the table.

Table. Test results of hydrazones of nitro-1,2,3-triazol-4-yl carbaldehydes Ia-b for fungicidal activity at a concentration of 30 mg / l in acetone Connection No Compound Suppression of radial growth of fungal mycelium,% of control Sclerotinia scleorotiorum Helminthosporum satovum Venturia inaequalis Ia

one hundred one hundred one hundred Ib

75 64 80 Ic

one hundred one hundred one hundred Reference fifty 60 44

The data in the table show that compounds Ia-B exhibit a higher fungicidal activity compared to the widely used triadimelic fungicide "Triadimefon".

Thus, the technical result is the hydrazones of nitro-1,2,3-triazol-4-yl carbaldehyde Ia-b, having fungicidal activity.

Claims (1)

Funds having fungicidal activity, containing hydrazone nitro-1,2,3-triazol-4-yl carbaldehyde fragment of the formula Ia-b,

at a concentration of 30 mg / l in acetone.