RU2288230C1 - 2-(5-r-aminomethylfuryl-2)-1,3-dioxalanes displaying growth-regulating and anti-stress activity - Google Patents

Abstract

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to chemistry of biologically active substances, in particular, to novel biologically active compounds, namely, 2-(5-R-aminomethylfuryl-2)-1,3-dioxalanes of the formula (I):

wherein at (Ia) R means --Ts and at (Ib) R means -CO-Ph. These compounds show properties as activating agent with respect to germination of winter wheat grains of sort "Pobeda-50" possessing growth-regulating and anti-stress activity.

EFFECT: valuable biological properties of compounds.

1 cl, 2 tbl, 2 ex

Description

The invention relates to the field of agriculture and the chemistry of biologically active substances, to new biologically active compounds of a number of furans of the formula I

Ia R = -Ts; IB R = -CO-Ph,

showing the properties of the activator of germination of seeds of winter wheat cultivar Pobeda-50, with growth-regulating and anti-stress activity.

The closest analogs in terms of the structure of the claimed compounds can be classified as 2- (furyl-2) -1,3-dioxolane, a plant growth regulator with anti-stress activity [Kulnevich VG, Kalashnikova VG, Kosulina TP , Nenko N.I., Smolyakov V.P. 2-Furyl (aryl) -1,3-dioxacyclanes, synthesis, stereochemistry, reaction rates of formation, properties and applications // New directions in the chemistry of cyclic acetals. - M .: Chemistry. - 2002].

Gibberellin, widely used to activate seed germination, is known as an analogue in properties.

However, gibberellin is an expensive preparation of microbiological synthesis and inaccessible. In addition, its use causes an irrational waste of plastic substances [G. Muromtsev et al. Fundamentals of chemical regulation of plant growth and productivity. - M .: Agropromizdat, 1987. - P.33-80].

The objective of the present invention is to identify new promising biologically active compounds - 2- (5-R-aminomethylfuryl-2) -1,3-dioxolanes of the formula I - with the aim of expanding the arsenal of biologically active substances obtained synthetically for use in agriculture as growth regulators and anti-stress drugs.

This is achieved by the synthesis of 2- (5-R-aminomethylfuryl-2) -1,3-dioxolanes I, new compounds not previously described, containing a 1,3-dioxolane fragment in their structure and capable, by analogy with the known plant growth regulator, 2- (furyl-2) -1,3-dioxolane - show the properties of activators of germination of seeds of winter wheat.

Compounds I were prepared by condensation of ethylene glycol with 5-R-aminomethylfurfural in the presence of an Amberlist 15 ion exchange resin.

The study of the effect of compounds I on the sowing qualities of winter wheat seeds, on the growth and accumulation of dry mass in seedlings and the determination of the optimal growth-regulating concentration showed that compounds I in optimal growth-activating concentrations improve the sowing qualities of Pobeda 50 winter wheat seeds and have good anti-stress activity.

Thus, the set of essential features set forth in the claims, allows to achieve the desired result.

The invention is illustrated by the following examples.

Example 1

Preparation of 2- (5-R-aminomethylfuryl-2) -1,3-dioxolanes I.

Amberlist 15 ion exchange resin in the amount of 10-15% by weight of furfural is added to a mixture of 0.01 mol of 5-R-aminomethylfurfural and 0.01 mol of ethylene glycol in 100-120 cm ^{3 of} benzene and boiled with a Dean-Stark trap, controlling the conversion of the initial furfural TLC method. The reaction mixture is cooled. The cation exchange resin is separated by filtration. 10-15 cm ^{3 of} petroleum ether are added to the filtrate. The hot solution is passed through a layer of silica gel and then evaporated to 1/3 of the original volume under reduced pressure. After crystallization, the corresponding dioxolane is obtained.

5- (1,3-dioxolan-2-yl) -2- (4-methylphenylsulfonamidomethyl) furan (Ia) is a white cotton-like substance, _mp 124-126 ° C. Yield 68%.

1 H NMR (CDCl ₃ ): 2.27 (CH ₃ , s, 3H), 3.95 (CH ₂ (dioxolane), s, 4H), 4.30 (CH ₂ , s, 2H), 5.82 ( CH, s, 1H), 6.44 (H-4 _Fur , d, 1H, J = 3.4 Hz), 6.60 (H-3 _Fur , d, J = 3.4 Hz), 7.64 (о-Н _Ar , dd, J = 2.2 Hz, J = 8.0 Hz, 2Н), 7.26 (m-Н _Ar , dd, J = 2.2 Hz, J = 8.0 Hz, 2H), 6.13 (NH, s, 1H).

Found for C ₁₅ H ₁₇ NSO ₅ : C 55.69 H 5.34 N 4.26 S 9.90%. Calculated: C 55.72 H 5.30 N 4.33 S 9.92%.

5- (1,3-dioxolan-2-yl) -2-phenylcarboxamidomethylfuran (Ib) is a cream-colored powder, _mp 103-104 ° C. Yield 63%.

1 H NMR (CDCl ₃ ): 3.94 (CH ₂ (dioxolane) s, 4H); 4.48 (CH ₂ s, 2H); 5.80 (CH s, 1H); 5.97 (H-4 _Fur , d, 1H, J = 3.4 Hz); 6.21 (H-3 _Fur , d, J = 3.4 Hz); 7.31 ... 7.67 (H _Ar , m, 5H); 8.64 (NH c, 1H).

Found for C ₁₅ H ₁₅ NO ₄ : C 65.98 H 5.42 N 5.17%. Calculated: C 65.93 H 5.53 N 5.13%.

Example 2

The growth-regulating and anti-stress (resistance of seedlings to drying) activity of compounds I was studied by model laboratory screening methods modified by us on seeds of winter wheat cultivar Pobeda 50.

The studies determined:

- optimal growth-regulating concentration of compounds, the effect on sowing qualities of seeds of winter wheat,

- growth and accumulation of dry mass in seedlings when grown under normal conditions and under the influence of a stress factor (drying of seedlings).

To study the growth-regulating and anti-stress activity, the tested compounds I were previously dissolved in acetone and then in water.

Gibberellin was used as an analogue in properties, and furolan in the form of 0.001% aqueous solutions was used as an analogue in structure.

The seeds of winter wheat were soaked in aqueous solutions of the preparations for 18 hours, and then germinated in Petri dishes on wet filter paper for three days.

To identify the anti-stress activity of the compounds, half of the three-day-old seedlings in each variant were dried for an hour, then the germination of all seeds was continued in rolls of filter paper for four days,

The experiment was repeated three times. In each repetition, 50 pieces were used. seed.

The optimal growth-stimulating concentration of compounds was judged by the totality of such indicators as germination energy, length and dry weight of seedlings, and their potential productivity.

The results of determining the optimal concentration of compounds and their effect on the sowing quality of seeds are shown in table 1.

The tests carried out allowed us to establish that all tested compounds in the concentration range of 0.01-0.0001 wt.% Exhibit the properties of growth regulators.

Compound Ia at an optimal growth-promoting dose of 0.001 wt.% Increases the seed germination energy by 3%, the length of the shoot system of 7-day-old seedlings by 8.6%, the length of the roots of seedlings by 67.5% and their weight by 31.0 and 78.9%, respectively, and potential productivity - by 35.6% in comparison with the control.

Compound Ib in the optimal growth-promoting concentration of 0.001 wt.% Does not affect the growth of the shoot system of seedlings, increases the root length by 51.9%, the weight of the shoot system by 22.5%, the root mass by 71.1%, respectively, and potential productivity - by 43.3% in comparison with the control.

Thus, compounds I in optimal activating growth concentrations improve the sowing qualities of seeds of winter wheat cultivar Pobeda 50.

The results of the effect of the tested compounds on the resistance of Pobeda-50 winter wheat seedlings to water stress (drying of seedlings) are shown in Table 2.

The tests carried out allowed us to establish that all tested compounds in optimal concentrations have good anti-stress activity.

Compound Ia in the optimal dose of 0.005 wt.%, Increases the length of the shoot system of 7-day-old seedlings by 24.3%, the length of the roots of seedlings by 53.6% and their mass by 36.2 and 100.0%, respectively, in comparison with control.

Compound 1b at an optimal concentration of 0.0001 wt.% Increases the length of the shoot system of seedlings by 16.2%, the length of the roots by 16.1% and their mass by 36.2 and 63.3%, respectively, compared with the control.

Thus, compound Ia among the tested preparations has the greatest growth-regulating and anti-stress activity.

The obtained results allow us to recommend compound Ia as a means of increasing plant resistance to water stress and improving the sowing qualities of seeds of winter wheat cultivar Pobeda 50.

Table 1
The influence of growth regulators on the sowing qualities of seeds of winter wheat cultivar Pobeda 50 Experience option The concentration of the aqueous solution,% Germination energy,% Sprout length Mass of seedlings Potential productivity seedling root seedling root cm ± to control,% cm ± to control,% mg ± to control,% mg ± to control,% mg / cm ± to control,% Control - Water - 90 10.9 - 9.3 - 7.4 - 4.2 - 1.06 - Gibberellin 0.001 94 11.7 7.3 9.9 6.5 7.9 6.8 4.4 4.8 1.05 -0.1 Furolan 0.001 92 11.7 7.3 12,2 31,2 8.4 13.5 5.3 26.2 1.17 10,4 Control - Acetone 0.1 86 10.5 -3.6 7.7 -17.2 7.1 -4.1 3.8 -9.5 1,04 -1.9 Compound 1a 0.01 94 9,4 -10.5 8.8 14.3 6.7 -5.6 5.1 34.2 1.26 21,2 0.005 96 10.7 1.9 10.7 38.9 8.3 16.9 5.5 44.7 1.29 24.0 0.001 93 11,4 8.6 12.9 67.5 9.3 31,0 6.8 78.9 1.41 35.6 0,0005 89 11.2 6.7 10,4 35.1 7.4 - 5,4 42.1 1.14 9.6 0.0001 91 11.3 7.6 12,4 61.1 8.1 14.1 6.6 73.7 1.30 25.0 Compound 1b 0.01 89 11.0 4.8 10.8 40.1 9.0 26.8 6.6 73.7 1.42 36.5 0.005 89 10,2 -2.9 9.1 18.2 8.8 23.9 4.6 21.1 1.31 25.9 0.001 90 10,2 -2.9 11.7 51.9 8.7 22.5 6.5 71.1 1.49 43.3 0,0005 86 10.6 0.9 9.9 28.6 8.9 25,4 5.3 39.5 1.34 28.9 0.0001 91 11.9 13.3 10,4 36,4 9.2 29.6 6.3 65.8 1.30 25.0 NDS _0.95 1.4 0.4 0.5 0.3 0.4 0.01 P _0.95 % 1.4 3.8 4.7 5.5 5.1 3.4 Note:
НСР0.95 smallest significant difference at 5% significance level, Р0.95 - experimental error,% at 5% significance level

table 2
The influence of growth regulators on the resistance of winter wheat seedlings of the variety Pobeda 50 to water stress Experience option The concentration of the solution,% Sprout length Mass of seedlings seedling root seedling root cm ± to control,% cm ± to control,% mg ± to control,% mg ± to control,% Control - Water 0 7.5 - 5.7 - 5,6 - 3.2 - Gibberellin 0.001 7.9 5.3 6.1 7.0 5.9 5,4 3.9 21.9 Furolan 0.001 8.6 14.7 6.8 19.3 6.1 8.9 4,5 40.6 Control - Acetone 0.1 7.4 -1.3 5,6 -1.8 4.7 -16.1 3.0 -6.3 Compound 0.01 8.6 16,2 5.9 5,4 6.6 40,4 3.8 26.7 Ia 0.005 9.2 24.3 8.6 53.6 6.4 36,2 6.0 100.0 0.001 9.0 21.6 7.2 28.6 6.3 34.0 4.6 53.3 0,0005 8.2 10.8 7.0 25.0 5.9 25.5 4.7 56.7 0.0001 8.1 9.5 5.5 -1.8 5.7 21.3 3.4 13.3 Compound 0.01 8.3 12,2 5.9 5,4 6.6 38,4 4.4 46.7 Ib 0.005 8.8 18.9 5,6 - 6.7 42.6 3.0 - 0.001 8.5 14.9 6.0 7.1 6.5 38.3 4.7 56.7 0,0005 8.1 9.5 4.9 -12.5 6.3 34.0 4.1 36.7 0.0001 8.6 16,2 6.5 16.1 6.4 36,2 4.9 63.3 NDS _0.95 0.3 0.5 0.33 0.36 P _0.95 % 3.4 4.2 5,6 5,4

Claims (1)

2- (5-R-Aminomethylfuryl-2) -1,3-dioxolanes of formula 1

, where Ia R = -Ts; IB R = -CO-Ph, showing growth-regulating and anti-stress activity.