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Rumeks crispus otsu bitki kökünden elde edilen antrakinonlar

Antraquinonos from roots of rumex crispus

  1. Tez No: 46131
  2. Yazar: MENAR YILMAZ
  3. Danışmanlar: DOÇ.DR. KERİMAN GÜNAYDIN
  4. Tez Türü: Yüksek Lisans
  5. Konular: Kimya, Chemistry
  6. Anahtar Kelimeler: Belirtilmemiş.
  7. Yıl: 1995
  8. Dil: Türkçe
  9. Üniversite: İstanbul Teknik Üniversitesi
  10. Enstitü: Fen Bilimleri Enstitüsü
  11. Ana Bilim Dalı: Belirtilmemiş.
  12. Bilim Dalı: Belirtilmemiş.
  13. Sayfa Sayısı: 73

Özet

ÖZET Polygonaceae familyasına ait bitkiler zengin antrakinon kaynağı olarak bilinmektedirler. Çalışmamızda bu familyaya ait Rumex Crispus bitki kökünün kimyasal yapısı incelenmiştir. İ.T.Ü. kampus bahçesinden toplanan bitki kökleri temizlenip, kurutulduktan sonra toz haline getirilerek eter ile ekstraksiyonu yapılmıştır. Glikozid şeklinde bulunan antrakinonlar serbest hale getirilmek için 2M HC1 çözeltisinde 2 gün bekletilmiş, daha sonra CHCb ile ekstraksiyona tabi tutulmuştur. Toplanan ekstraktlar bir döner buharlaştırıcıda uçurularak koyu kahve renkte bir karışım elde edilmiştir. Bu karışım birkaç kez TLC Kromotografi yöntemi ile ayrılarak saflaştırılmıştır. Yapılan preparatif TLC çalışması sonucu dört farklı bileşik saf olarak izole edilmiştir. İR, UV, MASS, ^-NMR, COSY, HETCOR, 13C-NMR-APT, HREIM spektrumlanmn yardımıyla l,5-dihidroksi-3-metoksi-7-metil-antrakinon (V), 1,5- dihidroksi-3-metil-antrakinon (2), 4,8,9-trihidroksi-2,3,4-trimetil-antron-l (3) ve l,3,5-trihidroksi-6-(hidroksimetil)-antrakinon (4) bileşiklerinin yapıları aydınlatılmıştır. 1, 2, 4 bileşiklerinin verdikleri renk reaksiyonları, UV ve İR spektrumları incelenerek, 1,5-dihidroksiantikinon türevleri oldukları anlaşılmıştır. 2 bileşiğinin UV spektrumu incelendiğinde antrakinon yapısında olmadığı, *H- NMR, ~3C-NMR-APT, COSY, HETCOR spektrumları incelendiğinde ise 8,9- dihidroksiantron-1 yapısında olduğu görülmüştür. 1 bileşiği 1992 yılında Cassia Italica ve 1994 yılında Salvia Prezewalskii bitkilerinde izole edilmiş, antitumor ve antibakterial etkili olduğu ispat edilmiştir. Literatürde 2 bileşiğinin yukarıda bahsedilen bitkilerden ve Digitalis Davisiana bitkisinden izole edildiği belirtilmektedir. 3 ve 4 bileşikleri ise ilk defa bizim tarafımızdan izole edilmiş, literatürde bu bileşiklere rastlanılmamıştır. Ayrıca bu dört bileşik Rumex Crispus bitkisinden ilk defa izole edilmiştir. 1 bileşiğini bol miktarda içermesi nedeniyle Rumex Crispus, antitumor ve antibakterial etkili bitkiler sınıfına dahil edilebilir. ıx

Özet (Çeviri)

SUMMARY ANTRAQUINONES FROM ROOTS OF RUMEX CRISPUS Many plants of the Polygonaceae family have important medicinal properties and have been shown to be rich sources of anthraquinones and flavonoids. Rumex species are rich sources of anthraquinones, too. There are 19 genus Rumex in the world and all are also present in Turkey. These plants contain anthraquinones: e.g. Rumex Orientalis contains four anthraquinones including glycosides. Sharma and coworkers were succesful to isolate chrysophanol, emodin, aloe emodin and physcion from this plant. Many of these compounds are known to be 1,8- dihydroxyanthraquinon derivatives. In this work, we report the structural elucidation of three anthraquinones and an anthrone from the Rumex Crispus roots. Recently, two of these compounds have been isolated from Cassia Italica and Salvia Prezewalskii. The other two compounds are described for the first time in this work. The roots of the Rumex Crispus was collected from the Campus of Istanbul Technical University in September, 1994. Simultaneously, the pattern was identified at Herbariums of the Foresty and Science Faculty of Istanbul University. Dried and powdered roots were extracted with ether for two weeks in dark at room temperature. The extraction was repeated several times and the solvent of the combined extracts was evaporated. The resulting crude substance was allowed to stand in an excess of 2M HC1 (100 ml) for acidic hydrolysis of the glycosidic portion of the anthraquinones. The deep red solution was extracted with CHClg and the organic phase was dried (Na2S04) and solvent was evaporated under reduced pressure. The resulting yellow solid was separated and purified by preparative TLC, using petroleum ethenbenzene (1:1) and petroleum ether: ethyl-acetate: acetic acid (90:4: 1) as eluents. The four compounds isolated from these chromatographic works are characterized by spectroscopic methods. Compound 1 gave the characteristic colour reaction of the 1,5-dihydroxy anthraquione derivatives. The high resolution mass spectrum showed the [M]+ peak at m/z:284.0680 corresponding to the molecular formula C16H1205 (calc. for C16H1205 284.0684). The UV spectrum showed absorption maxima at 254, 288, 432, 491 and 529 nm. The later was typical of the 1,5-dihydroxyanthraquinone system which was further supported by IR data (1628 cm“1 for chelated carbonyl group).The 'H-NMR spectrum of 1 showed the characteristic low field signals belonging to the chelated hydroxyl groups at 12.33 and 12.13ppm. The spectrum further exhibited signals for two meta coupled aromatic protons (5:7.09 and 5:7.63) which are assigned to H-6 and H-8. The two other meta coupled aromatic signals (5:6.70 and 5:7.38) are assigned to H-2 and H-4. Signals due to the methoxyl protons (5:3.94) attached to C-3 and methyl protons (5:2.44) attached to C-7 appeared in the required ranges. Additional support was obtained for the pruposed structure from the 13C- NMR-APT spectrum which showed the presence of methyl and methoxy carbons and the H-containing aromatic carbons at 22.2, 56, 108, 124, 106.9, 124.6 ppm, respectively. Thus, the structure of 1 is concluded to be l,5-dihydroxy-3-methoxy-7- methyl-anthraquinone. These spectral data of 1 were similar to the spectral data of phscion except for the IR data of the letter which showed two bands at 1675, 1639 for non-chelated and chelated carbonyl groups respectively and for UV data which showed a shift in Ethanol+ A1C13 at 523 nm. The spectral data of 1 are also similar to Prezewalsquinone B which was isolated from Salvia Prezewalskii. XUE ZHAOCU and coworkers identified this compound as l,5-dihydroxy-3-methyl-7- methoxy-9, 10-anthraquinone. H3CO HO 0 Prezewalsquinone B The spectral data of 1 was also similar to the anthraquinone isolated from Cassia Italica. Medhi H. Kazmi and coworkers presented this compound as a new anthraquinone and identified it as 1,5-dihydroxy-3-methoxy-7-methyl-anthraquinone. They also determined the antitumor and antibacterial effects of this anthraquinone derivative. If we consider the facts summerized above, it will be easily understood that compound 1 isolated from Rumex Crispus in the present work is the same as Prezewalsquinone B obtained from Salvia Prezewalskii and the anthraquinone derivative isolated from Cassia Italica. This compound could be represented in four structures shown below as la-d. OH 0 la OCH- XIHo CO. OH 0 OCH. lc Id In conclusion these three compounds isolated from three different plants are exactly the same structures and their formula correspond to 1,5~dihydroxy-3- methoxy-7-methyl-anthraquinone. The presence of compound I in Rumex Crispus is reported here for the first time. OH O OCH3 (I) Compound 2 showed absorption maxima at 253, 288, 460, 492 and 526 nm in UV spectrum and gave the characteristic colour reaction of the 1,5- dihydroxyanthraquinone derivatives. The IR spectrum supported the presence of a chelated carbonyl group giving a band at 1628 cm”1. The 'H-NMR spectrum showed the chelated hydroxyl groups at 12.01 and 12.12 ppm (meso OH) and also revealed a methyl group at 2.47 ppm. The high resolution mass spectrum showed the [M]+ peak at m/z: 254. 0584 corresponding to the molecular formula C15H10O4 (calcd. for C15Hu,04 254.0579). The.H-NMR spectrum of 2 is comparable with the known compound Ziganein isolated from Salvia Prezewalskii, Cassia Italica and Turkish Digitalis species. Ziganein and compound 2 has the same 'H-NMR spectra (Table- 1). As a consequence of these data, 2 can be described as 1,5-dihydroxy-3-methyl- anthraquinone and its presence in Rumex Crispus is reported here for the first time. 0 OH HO 0 a) xnTable 1. 'H-NMR spectral data of Ziganein and 2. Compound 3 did not appear to be an anthraquinone derivative since it does not give a colour reaction with ethanolic magnesium acetate. The UV spectrum also supported this conclusion. The 'H-NMR spectrum showed signals of two chelated hydroxyl groups, three methyl groups and four aromatic protons. The yellow coloured pigment 3 have a weakly chelated hydroxyl at 10.15 ppm (brs) and a strongly chelated hydroxyl at 17.50 ppm (brs). During the experiments, the colour of 3 darkened to black on TLC plates by the effect of air. The 4-substituted anthrone-1 structures are known to be sensitive to air. The presence of an anthrone group was also supported by the UV-VIS data (Xmax 253, 312, 325 nm). HREIM analysis of this compound showed a molecular ion peak at m/z:284 corresponding to the molecular formula Ci7H1604. The fragment ion peak at m/z: 198 corresponds to the residual cation after the losses of CH3OH and CHg-C = C-CH.3. In the 13C-NMR spectrum of 3, individual carbon atoms could be assigned as seven signals on the basis of two dimensional ('H-^C) correlation shift experiments (Table 2), COSY spectroscopy and the published data for antrochrysone. The hydroxylated quarternary carbon appeared at 71.1 ppm. Based on this evidence compound 2 could be identified as 4,8,9-trihydroxy-2,3,4-trimethyl- anthrone-1. OH OH 0 HO CH- O) xinTable 2. 2 rH and 'H-^C correlation data for 3. The high resolution mass spectrum of 4 gave [M]+ peak at 286.0442 corresponding to the molecular formula C15H10O6 (calcd. for C15H10O6 286.0477). Its UV spectrum showed the maxima very similar to the UV spectrum of physcion which is a 1,8-dihyroxyanthraquinone derivative and possesed a methoxy and a methyl group. H3CO Physcion Compound 4 appeared to be an anthraquinone derivatie as deduced from its colour reaction with ethanolic magnesium acetate (purple) and A1C13 (brown). According to the literature, the existence of jS-hydroxyl groups chelated with the 9, 10 carbonyl groups cause a bathochromic shift in the UV spectrum in the presence of AICI3. The presence of /3-hydroxyl group chelated to a quinone carbonyl group was proved by this bathochromic shift from \mJx'OH 430 nm to >wEt“OH+Alc13 460 nm and by a new absorption band at 513 nm. The IR spectrum of 4 showed a strong absorption band at 3460 cm”1 due to a free hydroxyl group and a chelated carbonyl group at 1640 cm"1. The IR data supported the compound to be a 1,5-dihydroxyanthraquinone derivative. The XH-NMR spectrum in CDCl3+DMSO revealed the presence of a hydroxymethyl group (5:4.3), a hydroxyl group (5:4.98) and four aromatic protons (5:7.5, 5:7.7, 5:7.25, 5:6.9). XIVAll the spectral data confirm the structure of compound 4 to be 1,3,5- trihydroxy-6-(hydroxymethyl)-anthraquinone. OH O (4) O OH CH2OH xv

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