Substituted 3-(1h)-1-pyrrolyl)thieno[2,3-b]pyridine showing astragulus and anti-stress activity

 

The present invention relates to new biologically active chemical substances, substituted 3-(1H-1-pyrrolyl)thieno[2,3-b] pyridinium formula I

where I R=COOH, X=H,

II R=COOK, X=H,

III R=COOC2H5X=Cl.

Connections extend a number of biologically active substances obtained synthetically, for their application in agriculture as postregulation and anti-stress drugs. table 2.

The invention relates to new biologically active chemical substances of some heterocyclic compounds of formulas I-III

I R=COOH, X=H; II, R=COOK, X=H; III R=COOC2H5X=Cl,

showing property to activate the germination of wheat seeds.

Substituted 3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine I-III are representatives of a new conjugated heterocyclic systems.

To the closest analogs in the structure of the claimed compounds can be considered as 3-amino-6-methyl-4-ethoxymethylene[2,3-b]pyridine-2-carboxylic acid IV and its ethyl ester V [E. A. Kaygorodova, L. D. Konyushkin, M. E. Niyazymbetov, S. N. Quack, B. N. Zaplishny, V. P. Litvinov. Electrochemical synthesis and /img_data/79/790692.gif">

IV R=COOH; V R=COOC2H5.

As similar properties known gibberellins, are widely used to activate germination. However, gibberellins costly products of microbiological synthesis and inaccessible. Its use causes irrational waste of plastic substances [Muromtsev, S. and other foundations of chemical regulation of growth and productivity of plants. - Moscow: Agropromizdat, 1987. - S. 33-80].

The present invention is to expand the Arsenal of biologically active substances obtained synthetically, for their application in agriculture as postregulation and anti-stress drugs.

This is achieved by the use of substituted 3-(1H-1-pyrrolyl)thieno-[2,3-b]pyridines I-III by pre-sowing treatment of seeds.

The invention is illustrated by the following examples.

Example 1. The way to obtain 4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylic acid (I).

4,6-Dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylic acid is obtained by the alkaline hydrolysis of ethyl 4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylate by reaction

To a suspension of 3.0 g (0.01 mol) of ethyl-4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carbamoylethyl. Next, the solution is cooled and acidified with him on the litmus paper. The precipitation is filtered off, washed with water and dried in air. Product peregri-stilizovala of dioxane. Output 2,62 g (96%), so pl. 239-240C.

An NMR spectrum1H (DMSO-d6, 200 MHz), d, M. D.: 1.87 (3H, s, 4-CH3); 2.58 (3H, s, 6-CH3); 6.23 (2H, s, N); 6.73 (2H, s, N); 6.98 (1H, s, Hru), 12,97 (1H, ush. with IT).

Found, %: C 61.72; H 4.41; N, 10.28. C14H12N2O2S. Calculated, %: C 61.75; N, 4.44; N 10,29.

Example 2. The way to obtain 4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylate potassium salt(II).

4,6-Dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylate potassium was obtained by interaction of 4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylic acid (I) with potassium hydroxide by the reaction of

To a suspension of 2.72 g (0.01 mol) of 4,6-dimethyl-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylic acid in 25 ml of ethanol was added to 1.8 ml of 30% solution of potassium hydroxide. The reaction mixture is heated before homogenization. After cooling, to the solution was added 10 ml of acetone. The formed precipitate is filtered off, washed with acetone and dried in air. Output 2,48 g (80%), so pl. 193-1949,02.

The IR spectrumcm-1: 1620 (C=N), 1590 (C=C, C=N), 1560 (COO-).

Example 3. The method of obtaining ethyl-4,6-dimethyl-5-chloro-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylate (III).

Ethyl-4,6-dimethyl-5-chloro-3-(1H-1-pyrrolyl)thieno[2,3-b]pyridine-2-carboxylate (III) was obtained by interaction of ethyl-3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-carboxylate with 2.5-dimethoxytetrahydrofuran.

A solution of 2.85 g (0.01 mol) of ethyl-3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]PI-ridin-2 - carboxylate in 10 ml of glacial acetic acid is heated to boiling and contribute with stirring of 1.53 ml (0.012 mmol) of 2,5-dimethoxytetrahydrofuran. The reaction mass is boiled for 3 h, cooled and diluted with 35 ml of ice water. The formed precipitate was separated, washed until neutral wash water, air-dried. Product paracrystal-lizovyvatj of alcohol. The output g (92%), so pl. 140-141C.

An NMR spectrum1H (DMSO-d6, 200 MHz), d, M. D.: 1.17 (3H, t, CH2); 1.86 (3H, s, 4-CH3); 2.73 (3H, s, 6-CH3); 4.17 (2H, q,CH3); 6.27 (2H, s, N); 6.73 (2H, s, N).

Found, %: 57.38; N, 4.50; N, 8.38. C16H15ClN

Astragulus and anti-stress activity of compounds I-III were determined model by laboratory screening seeds of winter wheat varieties Polovinka.

In the course of study is determined by the optimal postactivity concentration of compounds I-III, and their influence on seed quality of seed, growth of seedlings, the accumulation of dry mass and resistance of seedlings to water stress.

As similar properties used gibberellins, as control seeds treated with water.

As analogues for structure for compounds I - II used the compound IV and compound III - connection V.

Compounds I-III and analogues according to the structure used in the form of aqueous solutions with concentrations of 0.01; 0,005; 0,001; 0,0005; of 0.0001 wt.%, the gibberellins of 0.001 wt.%.

Seeds were soaked in aqueous solutions of drugs for 18 hours. Then the seeds were germinated in Petri dishes for three days at a temperature of 20-22C. Next half of germinated seeds in each sample were subjected to water stress by drying them for hours and then germination continued in rolls of filter paper. Experiment was repeated three times. In each replication were used for 50 seeds.

rgiya germination, the length and dry weight of seedlings and their potential productivity. The research results are summarized in tables 1 and 2.

Tests conducted on seeds of winter wheat varieties Polovinka, revealed that all the tested compounds in the concentration range of 0.01 and 0.0001 wt.% exhibit the properties of growth stimulants.

The connection I in the optimal growth stimulating concentration of 0.005 wt.% increases the length of the cane system of seedlings 66,1%, the length of roots 49.1% and mass by 100.0 and 23.7% respectively compared to control.

Compound II in optimal growth stimulating concentration of 0.005 wt.% increases the length of the cane system of seedlings by 44.6%, length of roots by 36.4% and their weight on 87,1 and 44.7%, respectively, and the potential productivity by 20.9% compared to control.

Similar in structure to compounds I, II - compound IV - optimal growth stimulating concentration of 0.0001 wt.% increases the length of the cane system is 41.1%, length of roots 47.3% and their weight 54.8 and 28.9 percent, respectively, and the potential productivity of 6.0% compared to control.

Compound III in optimal growth stimulating concentration of 0.0001 wt.% increases the length of the cane system by 50%, the length of roots 52.7% and mass by 90.3 and 23.7% COO III - connection V - optimal growth stimulating concentration of 0.0001 wt.% increases the length of the cane system by 57.1%, length of roots 60.0% and the weight by 51.6 and 39.4% respectively compared to control.

At the same time similar properties - gibberellin - optimal dose of 0.001 wt.% increases the height of the seedlings by 4.9%, the length of roots by 9.95, lot 7.1 and 21.0%, respectively, the potential productivity of 9.5% in comparison with control (control water).

Thus, compounds I-III in the concentration range of 0.01 and 0.0001 wt.% improve crop seed quality and optimal doses of 0.005 wt. % (compounds I and II) and 0.0001 wt.% (compound III) is not inferior in efficacy counterparts in structure (compounds IV and V) and superior to similar properties - gibberellins.

In conditions of water stress tested compounds remain active growth and synthetic processes, activating the growth of cane system of seedlings and contributing to the regeneration of roots.

The connection I in the optimal postactivity concentration of 0.005 wt.% increases the height of the seedlings by 89.9%, the length of the roots of 82.5% and a weight of 44.8 and 42,9% respectively compared to control.

Compound II in an optimal postactivity concentration of 0.0001 wt.% increase the control.

Similar in structure to compounds I, II - compound IV - optimal postactivity concentration of 0.0001 wt.% increases the length of the cane system of seedlings for 51.1%, length of roots by 65.0%, of their weight of 31.0 and 42,9% respectively compared to control.

Compound III in optimal postactivity concentration of 0.0001 wt.% increases the length of the cane system of seedlings by 53.3%, length of roots by 50%, of their weight of 44.8% and 57.1% respectively compared to control.

Similar in structure to the compound III - connection V - optimal postactivity concentration of 0.001 wt. % increases the length of the cane system of seedlings for 51.1%, length of roots on 72,5%, of their weight of 34.5 and 67.9% respectively compared to control.

Therefore, in conditions of water stress connection V in comparison with compound III has predominant effect on the growth of the root system of the seedlings.

Similar properties - gibberellin - optimal dose reduces the length of the cane system of seedlings on 5,65 and roots 14.7% and increases their mass by 9.8 and 25.6% respectively compared with control (control water).

Thus, the tested compounds exhibit properties of high performance growth stimulants and increase the sustainability of the gains is m - gibberellin - and not inferior to similar structure.

Therefore, compounds I-III can be used in arid areas to improve seed winter wheat.

Claims

Substituted 3-(1H-1-pyrrolyl)thieno[2,3-b] pyridine formulas I-III

where I R is COOH; X is H; II R - COOK, X - H; III R - COOC2H5X - Cl,

showing astragulus and anti-stress activity.

 

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6 tbl, 4 ex

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