Iridoids from Centranthus longi¯orus subsp. longi¯orus L.O È . Demirezer a, *, Z. GuÈvenalp b , H.-J. Schiewe c , I. Strietzel c , M. Harmandar b , A. Zeeck c a Hacettepe University, Department of Pharmacognosy, Faculty of Pharmacy, 06100 Ankara, Turkey b Atatu Èrk University, Department of Organic Chemistry, Faculty of Education, Erzurum, Turkey c Georg-August University, Institute of Organic Chemistry, Tammannstraûe 2, D-37077 Go Èttingen, Germany Received 4 January 1999; accepted 19 February 1999 Abstract An investigation of the extracts from Centranthus longi¯orus subsp. longi¯orus has led to the isolation of seven substances. A new iridolactone has been isolated from the aerial parts of this plant and was elucidated by analysis of the spectroscopic data and named longi¯orone. The constitution of the previously described valtrate hydrine B8 was elucidated via 2D NMR analysis for the ®rst time. Additional compounds isolated were patrinoside, kanokoside A, oleanolic acid, sitosterol and quercetin 3-O- rutinoside. # 1999 Elsevier Science Ltd. All rights reserved. Keywords: Centranthus longi¯orus subsp. longi¯orus; Valerianaceae; iridoids; valepotriate; ¯avonoid; triterpenes; longi¯orone 1. Introduction The genus Centranthus belongs to the Valerianaceae and is represented by three species in the Flora of Turkey (Davis, 1972). Plants of the this family are well known for their sedative properties (HoÈlzl, 1997) and Centranthus longi¯orus subsp. longi¯orus is com- monly used in Turkey as remedy which shows similar eects. Cyclopentane monoterpenes, valepotriates, anthocyanin pigments and glyceridic acids were pre- viously isolated constituents from Centranthus species (Stoll & Seebeck, 1957; Handjieva, Popov & Marekov, 1978; Adzet & Raynaud, 1971; Khandzieva & Zaikin, 1978; Marekov, Popov & Khandzieva, 1984; HoÈlzl, 1997). In this study a new iridolactone was isolated together with a valepotriate and two known iridoid glycosides. In addition two steroids and a ¯avonol glycoside were identi®ed. All the com- pounds isolated were assigned by means of spectral evidence (UV, IR, NMR, MS). 2. Results and discussion The aerial parts of Centranthus longi¯orus subsp. longi¯orus were extracted with methanol. The concen- trated methanol extract was suspended in water. This suspension was partitioned with petroleum, Et 2 O, EtOAc and n-BuOH, respectively. The concentrated petroleum extract, after repeated column chromatog- raphy, yielded oleanolic acid (Bischo, Jeger & Ruzieka, 1949) and sitosterol (Rubinstein, Goad, Clague & Mullheirn , 1976). The n-BuOH extract, after repeated Si Gel and Sephadex LH-20 column chromatography and RP-18 MPLC, led to the querce- tin 3-O-rutinoside (Wenckert & Gottlieb, 1977), 7- hydroxy-11-glucosyl-1-isovaleryl-iridoid (patrinoside), 8,10-dihydroxy-6,7-epoxy-11-glucosyl-1-isovaleryl-iri- doid (kanokoside A) (Nishiya, Kimura, Takeya & Itokawa, 1992) and valtrate hydrine B8 (2) (Koch & HoÈlzl, 1985). Patrinoside and kanokoside A have been isolated before only from Valeriana ocinalis and val- trate hydrine B8 has been isolated before only from Valeriana alliarifolia. More remarkable is a new irido- lactone, named longi¯orone (1). Phytochemistry 51 (1999) 909±912 0031-9422/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved. PII: S0031-9422(99)00152-1 * Corresponding author.