IR spectra of stigmastane series brassinosteroids differing in configuration and number of diol groups

Abstract

28-homosecasterol have been analyzed. The 28-homocastasterone molecule contains diol groups in ring A and in the side chain whereas that of 28-homosecasterol has one diol group in the side chain. The lack of two OH groups in ring A of homosecasterol compared to homocastasterone results in the appearance of stretching vibrational bands of H-C= (ν max = 3025 cm -1 ) and -C=C (ν max = 1656 cm -1 ) groups of ring A. Substantial changes are observed in the area of OH stretching vibrations. Homocastasterones pressed in KBr possess twice as many OH groups as homosecasterols such that absorption band total intensities in IR spectra of both isomers caused by H-bonds of the diol groups in the side chain amount to 65% whereas the share of the 2α,3α group is only 35% of the total intensity. Hence the contribution from the side-chain OH groups of the studied brassinosteroids to the integral optical density of the bands exceeds that from the ring-A OH groups. In dilute CHCl 3 solutions of the brassinosteroids, the conformations of the brassinosteroid side chains are not the same. As a result, intramolecular H-bonds of different energy are created. The optical density D max in band maxima of free OH groups for homocastasterones is three times higher than that for the corresponding band maxima of homosecasterol. This implies that D max for bands of free OH groups of the homocastasterone ring-A diol group is greater, in contrast with the relatively greater D max for bands of homosecasterol side-chain OH groups bound by an intermolecular H-bond. The homocastasterone diol groups also form intramolecular Hbonds more actively. The lack of the diol group in ring A of the homosecasterols does not affect the frequencies of the C=O stretching vibrations. This leads to the conclusion that the C=O group forms intermolecular H-bonds only with the side-chain OH groups of brassinosteroids pressed in KBr.Keywords: IR spectra, 28-homocastasterone, 28-homosecasterol, R-and S-isomers, H-bond. Introduction. Natural and synthetic brassinosteroid (BS) phytohormones [1] possess several properties that enable them to be used in biology, medicine, and veterinary medicine as new pharmacological agents. According to the literature [2][3][4], the biological activity of BS in plants is due to the presence in their ring B of a 6-keto-or 7-oxa-6-keto structural fragment; in ring A, of a 2α,3α-diol group; and trans-fusion of rings A/B. The structure of the side chain also plays an important role, especially the presence and configuration of OH groups on C22 and C23 and the nature of the substituents on C24. (22R,23R)-BS are biologically most active in the majority of tests. The corresponding (22S,23S)-isomers are not observed in nature and are prepared synthetically [1]. Slight changes in the BS structure lead to significantly different activities. However, a reliable correlation between the BS structural features and their biological properties has not been established. Therefore, investigations including the use of IR spectroscopy are interesting both pr...

Infrared spectra of brassinolide and castasterone steroid phytohormones and their 24-epi derivatives

“…High-frequency bands belonged to free C=O groups; low-frequency ones, to those bound through a H-bond to OH groups of the side chain [5]. The frequencies of band maxima for free and bound C=O groups were greater in …”