CS276523B6 - 3-Butenolide delta derivatives and their preparation - Google Patents

Abstract

The solution relates to new substances of Δ^-buteno- ! lide of the general formula I, where R represents a cyano group or 2-benzothiazolyl. The substances of the general formula I are prepared by reacting Δ -butenolide of the general formula II with furaldehyde in a molar ratio of Δ-butenolide : 2-furaldehyde of 1.0 : 1, .1 to 1.15 in the presence of alkali metal hydroxides in absolute methanol at the boiling temperature of the reaction system for 0.5 to 1 hour. The above substances are effective as growth regulators and inducers of morphogenic transformation of plants.

Description

△-Butenolide derivatives and method for their preparation

Field of technology

The invention relates to β-butenolide derivatives of the general formula I

wherein R represents a cyano group or 2-benzothiazolyl and a process for their preparation.

According to the available literature, the substances according to the invention are not yet known. <

A more detailed literature search was made in the works of Perjessy, A., Avetysyan, A. A., Akuzaryan, A. A., Melikyan, G. S .: Collect. Czech. Chem. Commun., Vol. 54, 1666-1674, 1989; Avetysyan, A. A., Melikyan, G. S., Sogomonian, S. A .: Biological Journal of Armenia, 9-10, 956, 1989; Avetysyan, A. A., Galstyan, A. V., Melikyan, G. S., Sogomonyan, S. A .: Biologičeskij žurnál Armenia, 11, 1006-1009, 1989 «

These works point to the growth-stimulating activity of derivatives of unsaturated functional groups of lactates in pre-sowing treatment of onion, tomato and carrot seeds.

The essence of the invention.

The process for the preparation of the substances according to the invention is based on the fact that the β-butenolide of the general formula II

wherein R is the same as in formula I is treated with 2-furaldehyde in a molar ratio of N-butenolide: 2-furaldehyde of 1.0: 1.1 to 1.15 in the presence of alkali metal hydroxides in absolute methanol at the boiling point of the reaction system for 0.5 to 1 h.

The compounds according to the invention produce analogous growth and morphological effects as the phytohormonal substances IAA (3-indolyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) in vivo and in vitro.

Probative elongation stimulation of cell growth occurs at 10 'and 10 ^' ¹¹ mol.1 ^one derivative of 3-cyano-4- [2- (2-furylvinyl)] -5,5-dimethyl-N -butenolidu and at 10 ^ mol.1 ¹ u 3- (2-benzothiazolyl) -4- [2- (2-furylvinyl)] - 5,5-dimethyl-N-butenolide.

Dedifferentiation processes of callogenesis occurs at 10 ^ mol.Å ^"1 9 11 -1 when organogenesis at concentrations of 10-10 mol.1.

The degree of effectiveness of the substances in question depends on the concentration used and on the nature of the substituents bound to the core.

Examples of embodiments of the invention

Example 1

To a solution of 0.05 g NaOH in 10 mL absolute methanol was added 1.51 g (0.01 mol.1 ^L ) 3 O 1

-cyano-4,5,5-trimethyl-β-butenolide and 1.1 g (0.011 mol.1) of 2-furaldehyde. The reaction mixture was boiled for 1 h. The precipitate is filtered off and recrystallized from ethanol. 1.86 g (81.2%) of the product 3-cyano-4- [2- (2-furylvinyl)] - 5,5-dimethyl-N-butenolide with a melting point of 196 DEG C. are obtained.

Proven%: C 68.35 H 5.01 N 5.99 C

Calculated%: 0 68.11 H 4.84 N 6.12

CS 276 523 B6 2

Molecular Weight 229.24

IR spectra (CHCl ₃ ) 1763.5 22391617

In a similar manner, 3- (2-benzothiazolyl) -4 [2- (2-furylvinyl)] - 5,5-dimethyl-N-butenolide was prepared in a yield of 75.7%.

t. t. 201-202 ° C

Molecular Weight 337.42

Proven%: C 67.48 H 4.28 N 3.85. S 9.71 '

Calculated%. C 67.63 H 4.49 N 4.15 S 9.50

IR spectrum (CHCl ₃ ) 1580 1590 1605 1730.

Example 2 -.

In a series of experiments to test β-butenolide derivatives, a bioassay with isolated segments of summer wheat coloptils (Tritucum aestivum 1,) floating in solutions of the test substances with 2% sucrose was used. The elongation of the coleopts in a certain range was directly proportional to the concentration of the substance.

The wheat grain swelled in distilled water for 3 h at room temperature and germinated in the dark at 25 ° C. After germinating from a 20 to 25 mm long coloptile, a 3 mm long segment 2 mm below the apex was cut using a segment cutter under red illumination. Coleptyl segments of 10 pieces were placed in tubes in distilled water for 2 h, then transferred to test solutions with 2% sucrose. To avoid curvature of the segments, the incubation was performed on a shaker in the dark at 25 ° C. After 24 hours, the elongation of the coleopts was measured using a photographic camera. Differences in colonoptil length were expressed in% of control and significance was determined by t-test. The solutions were diluted - 5 7 q 11 -1 in a concentration scale of 10, 10, 10, 10 mol.1. A 2% sucrose solution was used as a control.

The results are documented by the enclosed camp no. 1 ..

Example 3.

In a series of in vitro experiments, callogenesis and organogenesis were induced on explants of Vicia sativa L., ev. Patima. Selected seeds of approximately the same size and seed color were sterilized in 70% ethanol for 15 min. To increase sterility, a method of single ionization using an ion generator using a negative corona discharge was used (Sekerka 1984) ·

Sterile seeds were planted in aseptic medium (sterile Fatran IF box) on solid agar medium (OXOID No-4 0.8%). The seeds germinated in petri dishes for 48 h, in the dark at 25 ° C + 1 ° C. To induce morphogenesis and callogenesis, explants were isolated from sterile seedlings and planted on the surface of 0.6% culture medium (Baeto-agar OXOID No-1) saturated with inorganic and organic components according to Murashige and Skoog (1982) with the addition of growth regulators - tested β-butenolide derivatives. Control media contained the phytohormonal substances IAA and 2,4-D.

In each variant of the experiment, a total of 75 copies were used after 3 repetitions. Explants were grown in sets of 5 in petri dishes at 25 ° C + 1 ° C in the dark. The degree of callogenesis and morphogenic activity was compared with that of IAA and 2,4-D and was evaluated on day 21 of culture.

The results are documented in the attached table no. 2.

CS 276 523 B6

Table no. 1

Elongation growth of summer wheat coleoptils (Triticum sestivum 1.) 1 2 mol.1 " , me % mm + s— % K 4.49 and 0.094 100 5.09 and 0.199 100 10 ” ¹¹ 5.11 ± 0.204 113.80 4.84 and 0.099 95.08 10 “ ⁹ 4.98 ± 0.145 110.91 5.29 ± 0.200 103.92 10 ⁷ 4.71 and 0.128 104.89 4.88 ± 0.098 95.87 1 or ⁵ 4.91 ± 0.141 109.35 4.97 and 0.147 97.64 10 ” ⁴ 5.72 ± 0.245 127.59 5.49 and 0.215 107.85

R 1

2,4-D - max. elongation growth 51.09% at a concentration of 1.10 " ³ mol.1" IAA - max. elongation growth of 100.33% at a concentration of 1.10 " ⁹ mol.1" ¹ 1. 3-cyano-4- (2 (2-furylvinyl)] -5,5-dimethyl-Δ 4 -butenolide

2. 3- (2-Benzothiazolyl) -4- [2- (2-furylvinyl)] - 5,5-dimethyl-N-butenolide

Table δ. 2

Calogen and morphological activity of the investigated derivatives

• Fabric Calogenesis Organogenesis Prolonged growth Toxicity Control - 18.49 43.12 - 1 48.12 19.04 32.84 - 2. 5.40 11.15 78.94 4.51

· 3-cyano-4- [2- (2-furylvinyl)] - 5,5-dimethyl-β-butenolide

2. 3- (2-Benzothiazolyl) -4- [2- (2-furylvinyl)] - 5,5-dimethyl-N-butenolide

Industrial applicability

The identified properties of the substances according to the invention highlight their importance as potential growth and morphogenic regulators of the plant organism and plant cells for the purpose of biotechnological manipulations.

Claims (2)

PATENT CLAIMS 1. N-Butenolide derivatives of the general formula I (I) wherein R represents a cyano group or 2-benzothiazolyl. . 2. A process for the preparation of compounds of formula I according to claim 1, characterized in that Δ3-butenolide of formula II (II), Where R is the same as in 1, is treated with 2-furaldehyde in a molar ratio of ^{3 3} -butenolide: 2-furaldehyde of 1.0: 1.1 to 1.15 in the presence of alkali metal hydroxides in absolute methanol at the boiling point of the reaction system for 0.5 to 1 hour.