Digitalis antrakinonları üzerinde teşhis ve yapı aydınlatılması çalışmaları

Abstract

ÖZET Bu çalışmada digitalis antrakinonlarmın kromatografik ve spektroskopik tutumları incelendi ve yeni incelemeye alınan bir türdeki antrakinonlardan bilinenlerin teşhisi ve bilinmeyenlerin saptanması için nispeten kolay ve çabuk bir kromatografik yöntem geliştirildi. Bu yöntem D. grandiflora ve D.cariensis kök antrakinonlanna uygulandı: 1. Digitalis grandiflora kökünde ondört bilinen antrakinon bileşiği yanında altı yeni antrakinon bileşiği saptandı. Bilinen antrakinon bileşikleri test maddelerle kromatografik ve spektroskopik yönden (UV.IR) karşılaştırılarak ; Digitopurpone (DG-1), Ziganein (DG-2), Pachybasin (DG-3), İsochıysophanol-8-methylether (DG-7), Ziganein- 1 -methylether (DG-8), Digitopurpone- 1 -methylether (DG-9), Digitolutein (DG-10), 5-Hydroxydigitolutein (DG-11), 6-Methoxydigitolutein (DG-12), Digiferrol (DG-13), a>-Hydroxypachybasin (DG-14), co-Hydroxyziganein (DG-15), oo-Hydroxyisochrysophanol-8-methylether (DG-1 7), 1 -Hidroksiantraki- non-3-karboksilik asit (DG-1 9) olarak bulundu.89 Bitkideki yeni antrakinon bileşiklerinden DG-4, DG-6, DG-16, DG-18 ve DG-20 maddelerinin miktarları son derece az (<lmg) olduğundan yapılan aydınlatılamadı. 2.5 mg olarak elde edilen DG-5 maddesinin yapısı ise spektroskopik yöntemler yardımıyla (UV, İR, MS, ^-NMR) 4-Hidroksi-l,2-dimetoksi-3-metilantrakinon (4-Hydroxy- digitolutein-2-methylether) olarak aydınlatıldı. 2. Digitalis cariensis kökünden daha önce elde edilen sekiz antrakinon bileşiğine ilave olarak beş bilinen ve bir yeni antrakinon bileşiği daha elde edildi. Bilinen antrakinon bileşikleri test maddelerle kromatografik ve spektroskopik yönden (UV.IR) karşılaştırılarak; Ziganein (DC-1), Pachybasin (DC-2), Phomarin-6-methylether (DC-3), Digitopurpone (DC-4), Madeirin (DC-5), Digitopurpone- 1 -methylether (DC-6), 5-Hydroxydigitolutein (DC-7), co-Hydroxyphomarin (DC-8), m-Hyd- roxyziganein (DC- 10), a>-Hydroxydigitolutein (DC-11), Digiferruginol (DC-12), cD-Hydroxypachybasin (DC-13) ve Phomarin (DC-14) olarak bulundu. Bitkide bulunan yeni antrakinon bileşiğinin yapısı (DC-9 maddesi) spektroskopik yöntemler yardımıyla (UV, İR, MS, XH-NMR, DNOE) 5-Hidroksi- 1 -metoksi-3-hidroksimetilantrakinon (co-Hydroxyziganein- 1 - methylether) olarak aydınlatıldı.

SUMMARY In this study, chromatographic and spectroscopic feature of digitalis anthraquinones was investigated and a simple and rapid chromatographic method was developed for the identification of known anthraquinones and detection of unknown ones present in a digitalis species under investigation. This method was applied to anthraquinones of the roots of D. cariensis and D. grandtflora. The roots of Digitalis grandtflora afforded fourteen known and six new anthraquinones. The known compounds were identified by comparison of their chromatographic and spectral data (UV.IR) with those of authentic material. These anthraquinones are: Digitopurpone (DG-1), Ziganein (DG-2), Pachybasin (DG-3), Isochrysophanol- 8 -methyl- ether (DG-7), Ziganein- 1 -methylether (DG-8), Digitopurpone- 1 -methyl- ether (DG-9), Digitolutein (DG-10), 5-Hydroxydigitolutein (DG-11), 6-Methoxydigitolutein (DG-12), Digiferrol (DG-1 3), to-Hydroxypachybasin (DG-14), «j-Hydroxyziganein (DG-15), <o-Hydroxyisochiysophanol-8- methylether (DG-17),l-Hydroxyanthraquinone-3-carboxylic acid (DG-19).91 Since the amount of the new anthraquinones (DG-4, DG-6, DG-16, DG-18 and DG-20) were very small, their structure could not be established. The structure of the compound DG-5, 2.5mg in amount was determined elucidated by spectroscopic methods (UV, IR, MS, ^-NMR) as 4-Hydroxy-l,2-dimethoxy-3-methylanthraquinone (4-Hydroxydigitolu- tein-2 -methylether). The roots of Digitalis cariensis yielded five known and one new anthraquinones in addition to eight anthraquinone previously isolated. The followings are the known compounds of this plant which were identified by comparison of their spectral and chromatographic properties with those of authentic samples. These anthraquinones are: Ziganein (DC-1), Pachybasin (DC-2), Phomarin-6 -methylether (DC-3), Digitopurpone (DC-4), Madeirin (DC-5), Digitopurpone- 1 -methylether (DC-6), 5-Hydroxydigitolutein (DC-7), co-Hydroxyphomarin (DC-8), oi-Hyd- roxyziganein (DC- 10), oo-Hydroxydigitolutein (DC-11), Digiferruginol (DC- 12), oj-Hydroxypachybasin (DC- 13) and Phomarin (DC- 14). The structure of the new anthraquinone, the compound DC-9, was determined by spectral methods (UV, IR, MS, ^-NMR, DNOE) as 5-Hydroxy- 1 -methoxy-3-hydroxymethylanthraquinone (oo-Hydroxyziga- nein- 1 -methylether).