Tanacetum bitki türlerinden elde edilen seskiterper laktonlar ve yapı tayini

Abstract

201 ÖZET Bu çalışmada Compositae familyasına ait Tanacetum türlerinden, Tanacetum argenteum bitkisinin alt türleri; subsp. argenteum, subsp. flabellifolium ve subsp. canum var canum' un kimyasal kompozisyonu karşılaştırmalı olarak incelendi. Her üç bitkinin gölgede kurutulan toprak üstü kısmı değirmende toz edildikten sonra, sırasiyle petrol eteri (40-60°), kloroform ve metanol ile ekstre edildi. Ekstreler ÎTK ile kontrol edilerek seskiterpen lakton içermeyen petrol eteri ekstresi incelenmedi. Kloroform ve metanol ekstreleri benzer madde içerdikleri için birleştirilerek sütun kromatografısi yapıldı. Sütundan alman eluatlar ÎTK' de incelendi ve maddeler silikajel sütun kromatografısi ve preparatif ÎTK ile ayırılarak saflaştırıldı. Bilinen yapıda oldukları düşünülen bileşiklerin, XH NMR spektrumları, İTK' sindeki Rf değerleri ve belirteçle vermiş oldukları renkleri daha önce izole edilmiş standart bileşiklerle kıyaslanarak yapıları tayin edildi. Yeni bileşiklerin yapıları ise, İR, NMR yöntemleri ('H,,3C APT, Spin decoupling, COSY, HETCOR, NOE), MS ve X-ray analizi gibi spektroskopik yöntemler ve bazı kimyasal reaksiyonlarla aydınlatıldı (asetilasyon, oksidasyon, siklizasyon, epoksidasyon). Kimyasal olarak incelenen TAA bitkisinden, parthenolide, peroxyparthenolide, stizolin, desacetyllaurenobiolide, spiciformin, isospicifomin, desacetyltulipinolid- 1 p/ 1 0a-epoxide, 1 0, 1 Oa-epoxy- 1, 1 0H- desacetyllaurenobiolide, tatridin A, l-ep/'-tatridin B, tamirin, 8a- hydroxycostunolide, sivasinolide, lp/4a,6a-trihydroxyeudesm-l l(13)-en- 8,12-olide, desacetyl-P-cycloprethrosine, michelenolide olarak bilinen bileşiklerin yanısıra, germakranolid yapısında iki yeni bileşik; 8a-202 angeloyloxycostunolide ve ip-peroxy-8a-angeloyloxycostunolide izole edildi. TAF bitkisinden, parthenolide, desacetyllaurenobiolide, desacetyltulipinolide-ip,10a-epoxide, spiciformin, isospiciformin, tatridin A, l-epı'-tatridin B, tamirin, deacetyl-P-cycloprethrosine, sivasinolide ve dentatin A olarak bilinen bileşiklere ilaveten Flabellin olarak adlandırılan gayanolid yapısında yeni bir bileşik elde edildi. T AC bitkisinden ise, parthenolide, peroxyparthenolide, dihydroparthenolide, santamarin, douglanin, ip,4a- dihydroxy-6a-angeloyloxyeudesm-l l(13)-en-8,12-olide, magnograndiol, ip- hydroxy-6o>angeloyloxyeudesm-4( 1 5), 1 1 ( 1 3)-dien-8, 1 2-olide 1 -epi-tatridin B, michelenolide, sivasinolide, ve flabellin olarak bilinen bileşiklerin yanısıra, ip-Hydroxy-6a-angeloyloxy-4(5),ll(13)-germacradien-8,12-olide, ip,4a- Dihydroxy-6a-isobuthyloxyeudesm-ll(13)-en-8,12-oIide, Epoxyflabellin, A3(4)-4-Hydroxyraethyinabellin, A3(4)-4-Oxo-flabelIin, 1 la-Methylflabellin ve lip-Methylflabellin olarak adlandırılan yedi yeni bileşik izole edildi.

203 SUMMARY In Turkey these are three Tanacetum argenteum (Compositae) subspecies; subsp. argenteum, subsp. flabellifolium, subsp. canum var. canum. In this work, the chemical compositions of these three subsp. were investigated by spectral methods and some chemical reaction as well. The aerial parts of all the three plants were powdered and extracted by petrol (40-60°), chloroform and methanol respectively. Controlling of the extracts were made by thin layer chromatography (TLC). Petroleum extracts which did not contain sesquiterpene lactones, were not studied. The chloroform and the methanol extracts contained similar compounds, were combined and the residue was applied on a silica-gel column. Eluents taken from the column were separated and purified by preparative TLC. The structure of the known compounds were determined by comparing their spectral data and Rf values with those of the standards. The other compounds supposed to be unknown were subjected to numerous spectral methods such as IR, NMR (*H NMR, 13C APT, spin decoupling, COSY, HETCOR, NOE) MS, X-ray, and some chemical methods i.e. acetylation, cyclization, oxydation and epoxydation to identify their structures. TAA yielded the known compounds; parthenolide, peroxyparthenolide, stizolin, spiciformin, isospicifomin, tatridin A, l-e/w'-tatridin B, desacetyllaurenobiolide, desacetyltulipinolid- 1 J3, 1 Oa-epoxide, 1J},1 Oa-epoxy- l,10H-desacetyllaurenobiolide, tamirin, 8o>hydroxycostunolide, lp/4a,6ct- trihydroxyeudesm- 11(13 )-en-8, 1 2-olide, si vasinolide, michelenolide, desacetyl-P-cycloprethrosine and two new compounds called as 8a- Angeloyloxycostunolide and ip-Perox-8a-angeloyoxycostunoIide.204 T AF gave the known compounds; parthenolide, desacetyllaurenobiolide, desacetyltulipinolide-ip,10a-epoxide, spiciformin, isospiciformin, tatridin A, 1-e/w-tatridin B, tamirin, deacetyl-P-cycloprethrosine, sivasinolide, dentatin A and a new compound named as Flabellin whih was a guaianolide. T AC afforded seven new compounds, ip-Hydroxy-6a-angeloyloxy- 4(5),ll(13)-germacradien-8,12-olide, Epoxyflabellin, A3(4)-4-Oxo- flabellin, A3(4)-4-Hydroxymethylflabellin, lla-Methylflabellin llp- Methylflabellin and ip,4a-Dihydroxy-6a-isobuthyloxyeudesm-ll(13)-en- 8,12-olide, and the following known compounds parthenolide, peroxyparthenolide, dihydroparthenolide, santamarin, douglanin, ip,4a- dihydroxy-6a-angeloyloxyeudesm-l l(13)-en-8,12-olide, magnograndiol, ip~ hydroxy-6a-angeloyloxyeudesm-4(15),l l(13)-dien-8, 12-olide l-e/?/-tatridin B, michelenolide, sivasinolide, and flabellin.