RU2195447C1 - 1-(4-nitrophenyl)-4-n-x-aminopyrrolidones-2 showing growth-regulating and antistressing activity and method of their synthesis - Google Patents

Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to novel chemical biologically active compounds of order 1-(4-nitro-phenyl)-4-N-X-aminopyrrolidones of the general formula:

where X means

(II); -NH-C₄H₉ (III); -NH₂ (IV); -NH-C₂H₅ (V) showing the growth-regulating and antistressing activity and to method of their synthesis. Compounds of the formulas (II), (III) and (V) are synthesized by heating a mixture of 0.5 g (0.025 mole) of 1-(4-nitrophenyl)-pyrroline-2-one dissolved in 20 ml of dimethylformamide and 0.075 mole of a corresponding amine (cyclohexylamine, n-butylamine, ethylamine) and its stirring under thermostatic control at 90 ± 2 C for 2 h followed by reaction mixture cooling. Compound (IV) is synthesized by heating solution of 0.5 g (0.025 mole) of 1-(4-nitro-phenyl)-pyrroline-2-one in 20 ml of dimethylformamide up to 90 ± 2 C for 2 h at stirring by passing gaseous ammonia formed at heating of 60 ml of 20% ammonia solution followed by cooling. Preparations (V) and (III) show the highest efficiency for improvement of sowing quality of winter wheat seeds of the sort Pobeda-50. Preparations (III) and (II) show the most antistressing activity. EFFECT: improved method of synthesis, valuable properties of compounds. 2 cl, 2 tbl, 5 ex

Description

-NH-C₄H₉ (III); -NH₂ (IV); -NH-C₂H₅ (V),
обладающих рострегулирующей и антистрессовой активностью, и способу их получения.The invention relates to new chemical biologically active compounds from the range of 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones, of the General formula

-NH-C ₄ H ₉ (III); -NH ₂ (IV); -NH-C ₂ H ₅ (V),
with growth-regulating and anti-stress activity, and the method for their preparation.

 These compounds, their chemical and the described spectrum of biological action in the literature are not known.

 An analogue in properties is gibberellin, used to activate seed germination. However, gibberelin is inaccessible, as it is a product of microbiological synthesis. In a plant, it causes irrational waste of plastic substances. [1. Muromtsev G.S. et al. Fundamentals of chemical regulation of plant growth and productivity. Ch. 2. Gibberellin. - M .: IN "Agropromizdat", 1987, p. 33-80].

влияющее на рост растений [2. SU 584739, А 01 N 9/22, А 01 N 5/00, 15.12.1977, бюлл. 46, 8с. Средство, проявляющее гербицидные свойства и влияющее на рост растений. Даниель Беллус (ЧССР), Вернер Фери (Швейцария)].Compounds of the general formula can be referred to analogues of the claimed compounds in structure, as well as in biological action.

affecting plant growth [2. SU 584739, A 01 N 9/22, A 01 N 5/00, 12/15/1977, bull. 46, 8s. A tool that shows herbicidal properties and affects the growth of plants. Daniel Bellus (Czechoslovakia), Werner Feri (Switzerland)].

 The prototype of the claimed compounds is 1-phenyl-4-anilinopyrrolidone-2 formula I, similar in structure and having biological activity [Kozhina ND, Badovskaya LA, Sorotskaya LN, Muzychenko GF, Tyukhteneva Z .I., Latashko V.M., Korpakova I.G. Synthesis of new heterocyclic compounds promising for veterinary medicine and fish farming // Chemistry for Medicine and Veterinary Medicine: Sat. scientific Proceedings / Saratov: Publishing House of the Saratov University, 1988, - p. 86.].

Задачей настоящего изобретения является расширение ассортимента новых биологически активных соединений, перспективных для сельского хозяйства в качестве активаторов прорастания семян пшеницы.

The objective of the present invention is to expand the range of new biologically active compounds promising for agriculture as activators of germination of wheat seeds.

 The proposed pyrrolidones-2 are obtained from available 1- (4-nitrophenyl) pyrrolin-2-one [3. Muzychenko G.F., Burlaka S.D., Kulnevich V.G., Zavodnik V.E., Pushkareva K.S., Zimina M.A. Synthesis and reactivity of N-aryl-substituted pyrrolin-2-ones // Ivanovo. University proceedings: Chemistry and chemical technology. 1999, v. 42, issue 4, p. 37-46] and commercial aliphatic and alicyclic amines.

-NH-C₄H₉ (III); -NH₂ (IV); -NH-C₂H₅ (V)
обладающих рострегулирующей и антистрессовой активностью.The essence of the task is achieved by the synthesis of 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones-2, of the General formula

-NH-C ₄ H ₉ (III); -NH ₂ (IV); -NH-C ₂ H ₅ (V)
with growth-regulating and anti-stress activity.

In the method for producing 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones-2, (X = -NH-C ₆ H ₁₁ , -NH-C ₄ H ₉ , -NH ₂ , -NH-C ₂ H ₅ ) to obtain compounds II, III, V, a mixture of 0.025 mol of 1- (4-nitrophenyl) pyrrolin-2-one dissolved in 20 ml of dimethylformamide (DMF) and 0.075 mol of the corresponding amine (cyclohexylamine, n-butylamine, ethylamine) is heated with stirring and thermostating at 90 ± 2 ^o C for 2 hours, followed by cooling of the reaction mixture, and to obtain compound IV in a solution of 0.025 mol of 1- (4-nitrophenyl) pyrrolin-2-one in 20 ml of DMF, heated to 90 ± 2 ^o C for 2 hours under stirring, about OSCAL ammonia gas formed by heating 60 ml of 20% ammonia solution, followed by cooling the reaction mixture.

The invention is illustrated by the following examples:
Example 1

Synthesis of 1-phenyl-4-anilinopyrrolidone-2 (I)
To 8.4 g (0.1 mol) of 5H-furanone-2, 46.5 g (0.5 mol) of aniline (b / c oil. Liquid, d = 1.02 ²⁰ , T _{boiling point} = 184, are added with stirring) 4 ^o C) and heated at a temperature of 170-180 ^o C for 6 hours. The excess of aniline is distilled off, and the crystalline residue is subjected to vacuum filtration and washed with sulfuric ether. Recrystallized from ethanol.

Yield 16.88 g (65% of theory), T _mp = 127 ^o C.

 Found,%: C 76.0; H 6.60; N, 11.10. Calculated,%: C 76.19; H 6.34; N, 11.11.

1 H-NMR spectrum (CDL ₃ ): 1.70-2.70 (ref. M, 3H, 3-CH ₂ and 4-CH), 4.30 (d, J _ab 80 Hz, 1H, 5-CH _A ), 5.40 (m, 1H, 5-CH _B ), 6.20-7.40 (m, 11H, Ph and NH).

Example 2
Synthesis of 1- (4-nitrophenyl) -4-N-cyclohexylaminopyrrolidone-2 (II)
0.5 g (0.025 mol) of 1- (4-nitrophenyl) -5H-pyrrolin-2-one (yellow crystalline solid, _mp = 177 ^° C) was dissolved in 20 ml of DMF and 0.91 ml (0.075 mol) was added cyclohexylamine (b / c liquid, d = 0.81 ²⁰ , T _bale = 134 ^o C). The reaction mixture was heated with vigorous stirring and a temperature of 90 ± 2 ^o C for 2 hours. Then the mixture was cooled with stirring, the resulting crystals were filtered and washed with acetone, then diethyl ether.

Yield: 2.94 g (39% of theory), T _mp = 246 ^° C.

 Found,%: C 66.29; H 6.84; N, 13.91. Calculated,%: C 66.36; H 6.93; N, 13.86.

IR spectrum (ν, cm ^-1 , liquid paraffin): 1695 (C = O), 3510-3330 (NH), 1607; 1503 (benzene ring), 1595 (δ _HN ). The purity was verified by thin-layer chromatography in the system - toluene: ethanol = 10: 3, R _f -0.36.

 Example 3

Synthesis of 1- (4-nitrophenyl) -4-N-n-butylaminopyrrolidone-2 (III)
0.5 g (0.025 mol) of 1- (4-nitrophenyl) -5H-pyrrolin-2-one (yellow crystalline solid, _mp = 177 ^° C) was dissolved in 20 ml of DMF and 0.74 ml (0.075 mol) was added n-butylamine (b / c liquid, d = 0.74 ²⁰ , T _bale = 77.8 ^o C). The reaction mixture was heated with vigorous stirring and a temperature of 90 ± 2 ^o C for 2 hours. Then the mixture was cooled with stirring, and then the resulting crystals were filtered off, washed with acetone and diethyl ether.

Yield: 2.76 g (40% of theory), T _mp = 323 ^o C.

 Found,%: C 56.02; H, 6.14; N, 15.01. Calculated,%: C 55.91; H 6.09; N, 15.05.

IR spectrum (ν, cm ^-1 , liquid paraffin): 1690 (C = O), 3510-3350 (NH), 1605; 1500 (benzene ring), 1590 (δ _HN ). The purity was verified by thin-layer chromatography in the system - toluene: ethanol = 10: 3, R _f -0.33.

 Example 4

Synthesis of 1- (4-nitrophenyl) -4-aminopyrrolidone-2 (IV)
0.5 g (0.0025 mol) of 1- (4-nitrophenyl) -5H-pyrrolin-2-one (yellow crystalline solid, _mp = 177 ^{° C.} ) and 20 ml of dimethylformamide (DMF) were charged into the flask. Ammonia gas, which was formed by heating 60 ml of a 20% ammonia solution, was passed into the reaction mixture heated to 90 ^° C for 2 hours with stirring.

 Then the reaction mixture was cooled with stirring. The precipitated crystals were filtered off and washed with acetone and diethyl ether.

The product yield of 2.09 g (38% of theory), T _PL = 329 ^o C.

 Found,%: C 63.41; H, 6.21; N, 13.97. Calculated,%: C 63.37; H 6.27; N, 13.86.

IR spectrum (ν, cm ^-1 , liquid paraffin): 1700 (С = O), 3500-3200 (NH), 1605; 1510 (benzene ring); 1620 (δ _HN ). The purity was verified by thin-layer chromatography in the system - toluene: ethanol = 10: 3, R _f -0.51.

 Example 5

Synthesis of 1- (4-nitrophenyl) -4-N-ethylaminopyrrolidone-2 (V)
0.5 g (0.025 mol) of 1- (4-nitrophenyl) -5H-pyrrolin-2-one (yellow crystalline solid, _mp = 177 ^° C) was dissolved in 20 ml of DMF and 0.48 ml (0.075 mol) was added ethylamine (b / c liquid, d = 0.71 ²⁰ , T _bales = 16.6 ^o C). The reaction mixture was heated with stirring for 2 h, maintaining a temperature of 90 ± 2 ^o C. Then the mixture was cooled with stirring, the resulting crystals were filtered off, washed with acetone and diethyl ether.

Yield: 2.79 g (45% of theory), T _mp = 319 ^o C.

 Found,%: C 65.31; H 5.49; N, 13.37. Calculated,%: C 65.38; H 5.45; N, 13.46.

IR spectrum (ν, cm ^-1 , liquid paraffin): 1695 (C = O), 3500-3350 (NH), 1605; 1503 (benzene ring), 1598 (δ _HN ). The purity was verified by thin-layer chromatography in the system-toluene: ethanol = 10: 3, R _f - 0,31.

 Study of growth-regulating and anti-stress activity of 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones-2 on seeds of winter wheat cultivar Pobeda-50.

 The growth-regulating activity of compounds II-V, a chosen analogue in structure I and an analogue in the properties of gibberellin, was studied on seeds of Pobeda-50 wheat by laboratory screening methods.

 The preparations were tested in the form of aqueous solutions, having previously dissolved them in dimethyl sulfoxide (DMSO).

Seeds were soaked in aqueous solutions of the preparations for 18 hours, then germinated in Petri dishes for three days, then germination continued in rolls of filter paper. The repetition of experiments three times. In each repetition, 50 pieces of seeds were used. Seeds soaked in water and in an aqueous 0.01% DMSO solution served as a control. The mass fraction of DMSO in aqueous solutions of the preparations was 0.01%. The compounds were used in the form of aqueous solutions with a mass fraction,%:
I - 0.0003; 0.00015; II - 0.0002; 0.0001; 0.00002; 0.00001; 0.000002; III - 0.0002; 0.0001; 0.00002; 0.00001; 0.000002; IV - 0.0004; 0,0002; 0.00004; 0.00002; 0.000004; V is 0.001; 0,0005; 0.0001; 0.00005; 0.00001, and the analogue in properties - gibberellin - in the form of an aqueous solution with a mass fraction of 0.001%.

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

 The energy of seed germination was determined according to GOST 50555-56. The height of seven-day-old seedlings (the length of the shoot system) and the length of the roots were measured using a strip of graph paper. Determination of the dry mass of seedlings was carried out according to GOST 3040-55.

 The research results are shown in tables 1 and 2.

The studies carried out allowed us to establish that the optimal growth-promoting concentration for the tested compounds was,%:
II - 0.0001; III - 0.0001; IV - 0.0002; V - 0.00005.

 Compound II in an optimal concentration of 0.0001% increases the length of seedlings by 5.2%, their weight by 23.7% and increases potential productivity by 13.5% compared to the control.

 Compound III in optimal concentration increases the height of seedlings by 4.2%, their weight by 37.3% and increases potential productivity by 15.3% in comparison with the control.

 Compound IV in optimal concentration increases the mass of seedlings by 13.6% and their potential productivity by 8.1%, reducing the height by 5.2% in comparison with the control.

 Compound V in optimal growth-promoting concentration increases the height of seedlings by 14.6%, their weight by 42.4%, root length by 8.3%, their weight by 6.3%, potential productivity by 10.8% compared with the control .

 Compounds II, III, and V exert an effect mainly on the growth of the shoot system of seedlings, activating the accumulation of biomass in them, i.e., attraction processes. Of these, compound V most effectively improves the sowing qualities of seeds of winter wheat cultivar Pobeda-50.

By the effectiveness of the impact, the drugs can be arranged in a row:
V>III>II> IV
Compounds V, II, III are more effective than the analogue in the properties of gibberellin and the analogue in structure I.

 The effects of compounds I-V on the resistance of seedlings to water stress are shown in table 2.

Compounds II, III, V at a concentration of 0.00001-0.00005%, and compound IV at a concentration of 0.000004% maintain a high growth rate of the shoot system of seedlings under conditions of water stress and are located as increase their activity in a row:
III> II = V>IV> I
Thus, compounds III and II most effectively maintain a high growth rate of seedlings subjected to water stress, and therefore exhibit high anti-stress activity, which allows them to be recommended as a means of cultivating winter wheat in arid regions.

 Compounds V, III can be recommended as a plant growth regulator to improve the sowing quality of seeds.

Claims (2)

1. 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones-2, of the General formula

-NH-C ₄ H ₉ (III); -NH ₂ (IV); -NH-C ₂ H ₅ (V)
with growth-regulating and anti-stress activity. 2. The method of obtaining 1- (4-nitrophenyl) -4-N-X-aminopyrrolidones-2, (X = -NH-C ₆ H ₁₁ , -NH-C ₄ H ₉ , -NH ₂ , -NH-C ₂ H ₅ ), characterized in that for the preparation of compounds II, III, V, a mixture of 0.025 mol of 1- (4-nitrophenyl) pyrrolin-2-one dissolved in 20 ml of dimethylformamide (DMF) and 0.075 mol of the corresponding amine (cyclohexylamine, n -butylamine, ethylamine) is heated with stirring and thermostating at 90 ± 2 ^o C for 2 hours, followed by cooling of the reaction mixture, and to obtain compound IV in a solution of 0.025 mol of 1- (4-nitrophenyl) pyrrolin-2-one in 20 ml DMF heated to 90 ± 2 ^o C for 2 h While stirring, gaseous ammonia, which is formed by heating 60 ml of a 20% ammonia solution, is passed through, followed by cooling of the reaction mixture.

Images