RU2644763C2 - N-[2'-(phenyl)ethyl]amide3-amino(4,6-dimethyl-5-chlorothieno[2,3-b]pyridine)-2-carboxylic acid as growth regulator of winter wheat and soybean - Google Patents

Abstract

FIELD: biotechnology.

SUBSTANCE: invention relates to regulator of growth of winter wheat and soybean, which is N-[2'-(phenyl)ethyl]amide 3-amino(4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-carboxylic acid of the formula 1:

.

EFFECT: regulator of winter wheat and soybean growth.

1 cl, 2 tbl, 4 ex

Description

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

showing growth-regulating properties on plants of winter wheat and soy. Compound 1 is known as a regulator of the growth of sunflower ["A way to increase the yield of sunflower", Strelkov VD, Dyadyuchenko LV et al. Pat. RF №2298324 dated 05/10/2007, application No. 2005103548 dated 02/11/2005], its growth-promoting properties on wheat and soy were revealed for the first time.

The closest analogs in structure to the claimed compound can be attributed to N-o-bromophenylamide 3-amino (4,6-dimethyl-5-chlorothieno [2,3-b] pyridine-2-carboxylic acid (compound 2) structure:

known as the antidote of 2,4-dichlorophenoxyacetic acid on sunflower ["Antidotes of the herbicide of 2,4-dichlorophenoxyacetic acid", Strelkov VD, Dyadyuchenko LV, Isakova LI, Dmitrieva IG et al. Pat. RF №2421992 dated 06/27/2011, application No. 2009149496 dated 12/29/2009].

The growth regulator Bigus, BP (State catalog of pesticides and agrochemicals approved for use in the Russian Federation. Ministry of Agriculture of Russia. Moscow - 2015), which is used to increase productivity on wheat, soy and other crops, is known as an analogue in properties.

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

This is achieved by the use of N- [2 '- (phenyl) ethyl] amide 2-amino (4,6-dimethyl-5-chlorothieno [2,3-b] pyridine-2-carboxylic acid 1 by spraying the crops of winter wheat and soybeans.

The inventive compound was first obtained by the authors according to the scheme:

The initial 4,6-dimethyl-3-cyano-2 (1H) -pyridinethione 3 was synthesized by a known method - the interaction of 4,6-dimethyl-2-chloronicotinonitrile with thiourea [Strelkov V.D., Dyadyuchenko L.V., Dmitrieva I. G. Synthesis of new herbicidal antidotes for sunflower. ICBN 978-5-93491-610-8. Krasnodar. Enlightenment-South. 2014. S. 96].

Growth-regulating activity was determined according to the standard method [Brief guidelines for conducting state tests of plant growth regulators. QINAO. Moscow - 1984. p. twenty]. The invention is illustrated by the following examples.

Example 1. N- [2 '- (phenyl) ethyl] 3-amino (4,6-dimethyl-5-chlorothieno [2,3-b] pyridine-2-carboxylic acid amide (compound 1).

To a suspension of 1.0 g (5.0 mmol) of 4,6-dimethyl-5-chloro-3-cyano-2 (1H) -pyridinethione in 25 ml of DMF, a solution of 0.28 g (5.0 mmol) of KOH is added in a minimum amount of water and mix until the precipitate is completely dissolved. Then, a solution of 1.0 g (5.0 mmol) of N- [2- (phenyl) ethyl] amide of chloroacetic acid in 10 ml of DMF was added to the reaction mixture, and after 40 minutes stirring, a solution of 0.28 g ( 5.0 mmol) KOH and stirring is continued for 1 h. After the reaction is completed, the reaction mixture is diluted with water twice and the precipitate formed is filtered off and dried. After recrystallization from ethyl acetate, 1.42 g (71%) of the desired product 1 are obtained in the form of crystals with a melting point of 170-171 ° C.

Found,%: C 60.45; H 5.22; N, 11.54; S 8.72. C ₁₈ H ₁₈ ClN ₃ OS;

Calculated,%: C 60.08; H 5.04; N, 11.68; S 8.91.

¹ H NMR spectrum, δ, ppm (group): 2.49 (s, 3H, 6-CH ₃ Ru); 2.71 (s, 3H, _5-CH3 Py); 2.61 (t, 2H, CH ₂ C ₆ H ₅ , J = 7.0); 3.58 (dt, 2H, NHCH ₂ , J = 6.0); 5.80 (s, 2H, NH ₂ ); 6.77 ... 7.06 (m, 5H, Ar-H); 8.41 (br s, 1H, NH).

Example 2. N- (o-bromophenyl) amide 3-amino-4,6-dimethyl-5-chlorothieno [2,3-b] pyridyl-2-carboxylic acid (compound 2).

To a suspension of 1.45 g (7.3 mmol) of 4,6-dimethyl-5-chloro-3-cyano-2 (1H) -pyridinethione in 30 ml of DMF was added a solution of 0.41 g (7.3 mmol) of KOH in a minimum amount of water and mix until the precipitate is completely dissolved. Then, a solution of 1.8 g (7.3 mmol) of N- (o-bromophenyl) chloroacetic acid amide in 10 ml of DMF was added to the reaction mixture and stirred at room temperature for 30-40 minutes. After repeated addition of an aqueous solution of 0.41 g (7.3 mmol) KOH, stirring was continued for another 40 minutes, at the end, the reaction mixture was diluted with water twice and the precipitate formed was filtered off and dried. After recrystallization from a mixture of ethanol: DMF = 1: 1, 2.40 g (80%) of target product 2 are obtained in the form of crystals with a melting point of 242-244 ° C.

Found,%: C 46.61; H 3.31; N, 10.42. C ₁₆ H ₁₃ BrClN ₃ OS;

Calculated,%: C 46.79; H 3.19; N, 10.23. ¹ H NMR spectrum, ppm (group): 2.56 (s, 3H, CH ₃ -4); 2.87 (s, 3H, CH ₃ -6); 6.97 (s, 2H, NH ₂ ); 7.20 ... 7.72 (m, 4H, Ar); 9.48 (br s, 1H, NH).

Example 3. Evaluation of the growth-regulating activity of the claimed compounds on plants of winter wheat

Kalym winter wheat plants were treated with an aqueous solution of the claimed compound twice in the tillering phase (dose of 30 g / ha) and in the flag leaf phase (dose of 30 g / ha) and Bigus solution, BP in the same phases (dose of 250 ml / ha) s the working fluid flow rate is 300 l / ha.

Spraying was carried out using an OEMP-16 sprayer. The experimental plot area is 8 m ² , the repetition is 4-fold, the allocation of plots is consistent. Wheat harvesting was carried out during the period of full ripening of grain.

Growth-regulating activity was determined by increasing the grain yield of plants processed by the proposed method and by the reference method, in comparison with the control (untreated plants).

The data obtained are presented in table 1.

Tests conducted on winter wheat, it was found that the claimed compound 1 when applied twice at a dose of 30 g / ha exhibits the properties of a growth stimulant. The structural analogue of compound 2 at a dose of 30 g / ha did not exhibit growth-regulating properties, the analogue of the Bigus and BP properties is inferior to the claimed compound in growth-promoting properties.

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

The treatment of experimental plots with soybean cultivars of variety 201, elite with solutions of the tested preparations was carried out twice: in the phase of 4-5 leaves and in the phase of budding - branching. The area of the experimental plot of 5.6 m ² (1.4 × 4 m), four repetition. Treatment with a solution of compound 2 (analogue in structure) and a solution of Bigus, BP (analogue for use) was carried out in the same phases.

Harvesting and recording of crops was carried out in a separate way. Soybean plants were cut into sheaves, and then threshed on a Hehe 125 combine. The mass of grain from each repetition of the variant was weighed with an accuracy of ± 5.0 g.

Growth-regulating activity was determined by increasing the grain yield of plants processed by the proposed method and by the reference method, in comparison with the control (untreated plants).

The data obtained are presented in table 2.

Tests conducted on soybean plants, it was found that the claimed compound 1 when applied twice at a dose of 30 g / ha exhibits the properties of a growth promoter. The structural analogue of compound 2 at a dose of 30 g / ha did not exhibit growth-regulating properties, the analogue of the Bigus and BP properties is inferior to the claimed compound in growth-promoting properties.

Thus, the present invention implements the indicated purpose, providing an increase in wheat yield of 2.7 c / ha (6.6%) and an increase in soybean yield of 3.1 c / ha (9.3%). At the same time, Bigus, BP (the benchmark for properties) contributes to an increase in wheat productivity by 1.4 kg / ha (3.5%), soybeans - by 1.9 kg / ha (5.2%); structural standard - compound 2 does not exhibit growth-regulating properties.

Claims (2)

The growth regulator of winter wheat and soybean, which is N- [2 '- (phenyl) ethyl] amide 3-amino (4,6-dimethyl-5-chlorothieno [2,3-b] pyridine-2-carboxylic acid of the formula 1