RU2327686C1 - 4-methyl-2-chloro-6-{[1-alkyl-2-(nitrobenzyledene)-] hydrazine}-nicotinenitriles as regulators of sugar beet - Google Patents

Abstract

FIELD: chemically and biologically active substances.

SUBSTANCE: chemically and biologically active substances have a structure represented by formula 1-2:

where 1 R=CH₃; R¹⁼2-NO₂; 2 R=C₂H₅; X=4-NO₂, as substances which stimulate growth of sugar beet.

EFFECT: obtaining of new compounds, with useful biological properties, which can be used in agriculture as regulators of the growth of plants.

1 cl, 1 tbl, 4 ex

Description

The invention relates to chemical biologically active substances from a number of heterocyclic compounds of the formula 1-2:

1 R = CH ₃ ; R ¹ = 2-NO ₂ ;

2 R = C ₂ H ₅ ; X = 4-NO ₂ ;

showing growth-regulating properties on sugar beet plants.

The closest analogs in the structure of the claimed compounds can be attributed N2-ethyl-N2- (3-cyano-4-methyl-6-chloropyridyl-2) -4-ethoxyphenylhydrazone structure:

known as the antidote of 2,4-dichlorophenoxyacetic acid on sunflower [RF Patent No. 2276664 05/20/2006, Dmitrieva IG, Dyadyuchenko LV, Strelkov VD, Isakova LI, Krapivin G.D. ., Zaplichny V.N. “N-ethyl- (3-cyano-4-methyl-6-chloropyridyl-2) ethoxyhydrazone as an antidote”].

As an analogue in properties, a preparation is known - potassium salts of humic acids - Bigus, BP (20-25 g / l in acid), (registrant of NTO Agroecologiya CJSC), which is used to increase yield on sugar beets [List of pesticides and agrochemicals, approved for use on the territory of the Russian Federation. 2004. No. 5, p. 311-313].

The objective of the present invention is to expand the arsenal of biologically active substances obtained synthetically for use in agriculture as plant growth regulators.

This is achieved by using 4-methyl-2-chloro-6 - {[1-alkyl-2- (nitrobenzylidene)] hydrazino} -nicotinonitriles 1-2 by spraying sugar beet crops. Previously, the growth-regulating properties of the claimed compounds were not identified.

In this case, the claimed compounds are obtained by a known method - the interaction of N [1- (3-cyano-4-methyl-2-chloropyridyl-6)] - N1-methyl (ethyl) hydrazine with an equimolar amount of the corresponding aldehyde when boiled in an alcohol solution [Weigand Hilgetag. Experimental methods in organic chemistry. - M .: Chemistry, 1969, p.475].

The starting N1- (3-cyano-4-methyl-6-chloropyridyl-6) -N1-methyl (ethyl) hydrazines are also obtained by a known method [Z.A. Bomika, M. B. Andaburskaya, Yu.E. Pelcher, G.Ya.Dubur. Some nucleophilic substitution reactions in the series of 2-chloro-3-cyanopyridines. - HGS, 1976, No. 8, p.1085-1088].

Used ethanol immediately before use is cleaned and dried according to the known method [A. Gordon, R. Ford. Companion chemist. M .: World. 1976. - 541 p.].

Growth-regulating activity was determined according to the standard method [Brief guidelines for conducting state tests of plant growth regulators. QINAO. Moscow - 1984, p.20].

The invention is illustrated by the following examples:

Example 1. 4-Methyl-2-chloro-6 - {[1-methyl-2- (2-nitrobenzylidene)] hydrazino} -nicotinonitrile (compound 1).

A mixture of 1.0 g (4.82 mmol) of 4-methyl-2-chloro-6-methylhydrazinonicotinonitrile and 0.79 g (4.82 mmol) of 2-nitrobenzaldehyde in 30 ml of ethanol is boiled for 2.5 hours. The reaction mixture is cooled, the precipitate formed is filtered off, washed with ethanol, and dried. After recrystallization from ethanol, 1.30 g (81%) of target compound 1 are obtained in the form of colorless crystals with a melting point of 274-276 ° C.

Found,%: C 54.79; H 3.49; N, 21.09; C ₁₅ H ₁₂ ClN ₅ O ₂ ;

Calculated,%: C 54.63; H 3.67; N, 21.24.

NMR ¹ H, δ, ppm (group): 2.55 (3H, s, 4-CH ₃ Ru); 3.62 (3H, t, N-CH ₃ ); 7.50 (1H, s, 5-N Ru), 7.65 ... 8.20 (4H, m, Ar), 8.30 (1H, s, N = CH).

Example 2. 4-Methyl-2-chloro-6 - {[1-ethyl-2- (4-nitrobenzylidene)] hydrazino} -nicotinonitrile (compound 2).

A mixture of 1.0 g (4.75 mmol) of 4-methyl-2-chloro-6-ethylhydrazinonicotinonitrile and 0.75 g (4.75 mmol) of 4-nitrobenzaldehyde in 30 ml of ethanol is boiled for 2.5 hours. The reaction mixture is cooled, the precipitate formed is filtered off, washed with ethanol, and dried. After recrystallization from ethanol, 1.37 g (84%) of target compound 2 are obtained in the form of colorless crystals with a melting point of 269-271 ° C.

Found,%: C 55.73; H 4.23; N, 20.15; C ₁₆ H ₁₄ ClN ₅ O ₂ ;

Calculated,%: C 55.90; H 4.10; N, 20.37.

NMR ¹ H, δ, ppm (group): 1.14 (3H, t, N-CH ₂ CH ₃ ); 2.55 (3H, s, 4-CH ₃ Ru); 4.32 (3H, t, N-CH ₂ CH ₃ ); 7.65 (1H, s, 5-N Ru), 7.75 ... 8.42 (4H, m, Ar), 8.60 (1H, s, N = CH).

Example 3. N2-ethyl-N2- (3-cyano-4-methyl-6-chloropyridyl-2) -4-ethoxyphenylhydrazone (compound 3).

A mixture of 1.0 g (4.8 mmol) of 4-methyl-6-chloro-2-ethylhydrazinonicotinonitrile and 0.72 g (4.8 mmol) of 4-ethoxybenzaldehyde in 30 ml of ethanol is boiled for 2.5 hours. The reaction mixture is cooled, the precipitate formed is filtered off, washed with ethanol, and dried. After recrystallization from ethanol, 1.18 g (76%) of target compound 3 are obtained in the form of colorless crystals with a melting point of 172-173 ° C.

Found,%: C 63.30; H 5.71; N, 16.21; C ₁₈ H ₁₉ N ₄ ClO.

Calculated,%: C 63.06; H 5.60; N, 16.36; Cl 10.32.

NMR ¹ H, δ, ppm (group): 1.12 (3H, t, N-CH ₂ CH ₃ ); 1.35 (3H, t, OCH ₂ CH ₃ ); 2.55 (3H, s, 4-CH ₃ Ru); 4.08 (3H, t, N-CH ₂ CH ₃ ); 4.30 (2H, q, O CH ₂ CH ₃ ); 7.55 (1H, s, 5-H Py), 7.00 and 7.60 (2H each, two d, Ar), 8.12 (1H, s, N = CH).

Example 4. Evaluation of the growth-regulating activity of the claimed compounds on sugar beet plants.

Spraying crops of sugar beet cultivar Druzhba MS 34 was carried out twice: in the phase of 6-8 leaves and when closed in rows [Brief guidelines for conducting state tests of plant growth regulators. QINAO. Moscow - 1984, p.20].

The flow rate of the working fluid is 250 l / ha. Working solutions were prepared in tap water (pH = 6.8) with the addition of OP-7 (0.1%).

Spraying was carried out using a backpack sprayer. The area of the experimental plot of 5.6 m ² 4-fold repetition, the allocation of plots randomized.

At the end of the growing season, root crops were recorded and the sugar content was determined. The mass of root crops from the plot was weighed on a commodity scale, the sugar content was determined refractometrically (IRF-22) [A.V. Peterburgsky. Workshop on agronomic chemistry. State Publishing House of Agricultural Literature. 1959, p. 192-197]. The accounting data was subjected to statistical processing using HCP ₀₅ [B.A. Dospekhov. Methodology of field experience. - M .: Kolos, 1979, S. 294-303].

The data obtained are presented in the table.

Tests conducted on sugar beets, it was found that the claimed compounds 1-2 in a dose of 28-40 g / ha exhibit the properties of growth stimulants.

Compound 1 at a dose of 28 g / ha increased the yield of root crops by 5.25 t / ha and increased the sugar content by 2.2% relative to the control, at a dose of 40 g / ha the yield of root crops increased by 7.37 t / ha, and the sugar content - by 2.9%.

Compound 2 at a dose of 28 g / ha increased the yield of root crops by 3.8 t / ha and increased sugar content by 3.2% in relation to the control, at a dose of 40 g / ha the yield of root crops increased by 6.41 t / ha, and sugar content - by 3.6%.

The structural analogue of compound 3 at doses of 28 g / ha and 40 g / ha did not exhibit growth-regulating properties.

Thus, compounds 1-2 stimulate the growth of sugar beet plants, increase its yield and sugar content, and surpass the analog in the properties of Bigus, BP and the analog in structure of compound 3.

Table. Growth-regulating activity of compounds 1-3 and the preparation "Bigus, BP" on sugar beet cultivar Druzhba MS-34. Preparations Dose g / ha Root crop productivity, t / ha The increase to the control, t / ha Sugar content,% Sugar collection, t / ha The control - 34,20 - 21.8 7.45 Compound 1 28 39.45 5.25 24.2 9.46 40 41.57 7.37 24.7 10.21 Compound 2 28 38.00 3.80 25.3 9.50 40 40.61 6.41 25,4 10.30 Compound 3 28 35,20 1.00 20,0 7.04 40 36.00 1.80 21,2 7.63 Bigus, BP 300 l / ha 37.50 3.30 22.0 8.43 NDS ₀₅ = 2.11

Claims (1)

4-Methyl-2-chloro-6 - {[1-alkyl-2- (nitrobenzylidene)] hydrazino} -nicotinonitriles of the formula 1-2

1: R = CH ₃ ; R ¹ = 2-NO ₂ ; 2: R = C ₂ H ₅ ; X = 4-NO ₂ , as sugar beet growth regulators.