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Iristectorone K, a novel monocyclic triterpene ester from Iris germanica rhizomes growing in Turkey
Fitoterapia 73 Ž2002. 316᎐319
Iristectorone K, a novel monocyclic triterpene ester from Iris germanica rhizomes growing in Turkey Ilkay Orhan a,U , Bilge ¸ Sener a , Toshihiro Hashimoto b, ¨ ¨ c , Filiz Ayanoglu Yoshinori Asakawab, Mensure Ozguven ˘ d a
Department of Pharmacognosy, Faculty of Pharmacy, Gazi Uni¨ ersity, 06330 Ankara, Turkey b Faculty of Pharmaceutical Sciences, Tokushima Bunri Uni¨ ersity, Tokushima 770, Japan c Department of Field Crops, Faculty of Agriculture, Cukuro¨ a Uni¨ ersity, 01330 Adana, Turkey d Department of Field Crops, Faculty of Agriculture, Mustafa Kemal Uni¨ ersity, 31034 Hatay, Turkey
Received 6 July 2001; accepted in revised form 15 April 2002
Abstract A new monocyclic triterpene ester (1) was isolated from the rhizomes of Iris germanica from Turkey. Structure elucidation of compound (1) was carried out by the combined application of HMQC, HMBC, DEPT, COSY and NOESY experiments and named as iristectorone K. 䊚 2002 Elsevier Science B.V. All rights reserved. Keywords: Iridaceae; Iris germanica; Iristectorone
1. Introduction Genus Iris ŽIridaceae. is represented by 37 species in Turkey, 13 of which are endemic w1x. Most of the Iris species are cultivated for ornamental purposes worldwide. Recently, Iris species have gained great attention from the cosmetic U
Corresponding author. Tel.: q90-312-2126645; fax: q90-312-2233921. E-mail address: [email protected] ŽI. Orhan..
0367-326Xr02r$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 6 7 - 3 2 6 X Ž 0 2 . 0 0 0 9 0 - 4
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
317
and perfume industries due to the their violet-like smell caused by irone-type compounds. Besides, some of Iris species such as Iris germanica, Iris tectorum, and Iris missuriensis, were reported to have various biological activities including potent antiulcer, anticancer and piscicidal activities w2,3x. There have been no previous phytochemical and bioactivity studies on Iris species growing in Turkey. In the course of our investigations on the rhizomes of I. germanica, a new monocyclic triterpene Ž1. was isolated from the petroleum ether extract of the plant.
2. Experimental 2.1. Plant material The rhizomes of I. germanica were collected from Reyhanli, Hatay in July, 1999. A voucher specimen was deposited in the Herbarium of Faculty of Pharmacy, Gazi University ŽGUE 2229.. Identification of the plant was made by one of us ŽM.O... 2.2. Extraction and isolation Powdered air dried plant material Ž184.88 g. was percolated with petroleum ether at room temperature The combined extracts were filtered and the solvent was removed in vacuo to give a crude extract Ž7.61 g., which was subjected to Si-gel CC eluting with hexaneracetone mixture Compound (1) was eluted and purified by PTLC using chloroformrtoluene 15:1. Žyield: 598.6 mg..
3. Results and discussion FAB-MS analysis of compound (1) indicated a molecular formula of C 40 H 70 O4 , with ion peaks wM q 1x at mrz 615, wM q 1 q Nax at mrz 638, wM q Kx at mrz 653, and wM q 1-H 2 Ox at m r z 597. Furthermore, CI-MS displayed molecular ion peaks at mrz 614 ŽMq; 22.7%. and at mrz 630 wMq qCH 4 ; 24.0%.. As indicated by 13 C NMR and DEPT spectra, (1) was comprised of eight quaternary, five methine, 20 methylene, and seven methyl carbons. The new compound showed the presence of an ␣ ,-unsaturated aldehyde in the 1 H and 13 C NMR spectra w ␦ H 10.3 Ž1 H, s ., ␦ C 189.9, 133.3 and 161.3x. The ␣ ,-unsaturated aldehyde proton at ␦ 10.3 showed a coupling to an allylic methyl group at ␦ 1.85. Compound (1) displayed NMR spectra close to those of iristectorones A-H, high fatty esters of triterpene-type compounds isolated from different Iris species w2᎐8x. This helped to establish the stereochemistry of (1) w5᎐8x. The NMR data and two-dimensional correlation Žsee Table 1. allowed, therefore, to assign structure 1 to the new compound named iristectorone K ŽFig. 1..
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
318
Table 1 NMR spectral data for compound Ž1. in d-C 6 H 6 C噛
13
C NMR
1 2 3 4 5 6 7 8
189.9 133.3 64.5 28.9 27.0 43.3 161.3 23.9
9
37.1
10 11 12 13
74.4 44.9 37.6 42.7
14
124.7
15 16
136.0 22.6
17 18 19 20 21 22 23 24 25 26 27 28 29 30 1⬘ 2⬘ 3⬘ 4⬘ 5⬘ 6⬘ 7⬘ 8⬘ 9⬘ 10⬘
27.4 122.1 136.4 22.9 30.1 29.8 38.9 17.9 14.7 23.1 14.4 11.1 26.5 17.9 173.3 34.4 25.4 29.3UU 29.4UU 29.5UU 29.6UU 29.8UU 29.7UU 14.3 U
UU
1
H NMR
10.3 s ᎐ 4.02 t Ž J s 6.40.U 1.39 m 2.14 m 3.24 d Ž J s10.7. ᎐ 2.45 m Ž8a. 2.20 m Ž8b. 1.30 m Ž9a. 1.52 m Ž9b. ᎐ ᎐ 1.07 m 1.97 m Ž13a. 2.23 m Ž13b. 5.16 t Ž J s 5.76, 5.21. ᎐ 1.83 m Ž16a. 1.84 m Ž16b. 1.38 m 5.36 m ᎐ 1-30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.42 m 0.97 br s o.68 br s 1.73 s 1.54 s 1.85 s 1.17 s 1.08 s ᎐ 2.19 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 0.89 m
HMBC
1
C2, C28 ᎐ C1⬘, C4, C5 C3, C5, C6 C4, C7 C2, C7, C10, C11 ᎐ C2, C6, C7, C10
H6 ᎐ H4, H5 H3, H5 H3, H4, H6 H5 ᎐ H8b, H9 H8a, H9 H8, H9b H8, H9a ᎐ ᎐ H13a, H30 H12, H13b, H14 H13a H13a, H16a, H16b, H13b ᎐ H14, H17, H27 H14, H17 H16, H18 H17, H16 ᎐ ᎐ ᎐ ᎐ H24, H25 H25 H24 H18 H14, H16 ᎐ H30 H12 ᎐ H3⬘ H2⬘, H4⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
C7, C8, C10 ᎐ ᎐ C11 C11, C12 C13 ᎐ C14, C15, C17 C16, C18, C17, C19 ᎐ ᎐ ᎐ ᎐ C24, C25 C23, C24 C23, C25 C19, C20 C14, C15, C16 C1, C2 C10, C11 C11, C12 ᎐ C1⬘, C3⬘ C2⬘, C4⬘, C5⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
Coupling constants are given in Hertz. Signals may be interchangeable within the same column.
H᎐ 1 H COSY
NOESY H5, H6, H28 ᎐ H4, H5 H3, H6 H3, H6 H4, H5 ᎐ H5, H8b, H9a H8a, H9b H9b H9a ᎐ ᎐ H13a ᎐ ᎐ H13a, H13b, H13 ᎐ H14, H27 H14, H27 H27 H17 ᎐ ᎐ ᎐ ᎐ H25 H22, H25 H24 H18 H16 ᎐ H30 H12 ᎐ H3⬘, H4⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
319
Fig. 1. Iristectorone K Ž1.
References w1x Davis PH. Flora of Turkey and the East Aegean Islands, VIII. Edinburgh: University Press, 1984:382. w2x Muto Y, Ichikawa H, Kitagawa O et al. Yakugaku Zasshi 1994;114:980. w3x Miyake Y, Ito H, Yoshida T. Can J Chem 1997;75:734. w4x Seki K, Tomihari T, Haga K, Kaneko R. Phytochemistry 1994;37:807. w5x Marner FJ, Littek A, Arold R, Seferiadis K, Jaenicke L. Liebigs Ann Chem 1990;6:563. w6x Seki K, Tomihar T, Haga K, Kaneko R. Phytochemistry 1994;36:433. w7x Bonfils JP, Marner FJ, Sauvaire Y. Phytochemistry 1998;48:751. w8x Takahashi K, Hoshino Y, Suzuki S, Hano Y, Nomura T. Phytochemistry 2000;53:925.
Iristectorone K, a novel monocyclic triterpene ester from Iris germanica rhizomes growing in Turkey Ilkay Orhan a,U , Bilge ¸ Sener a , Toshihiro Hashimoto b, ¨ ¨ c , Filiz Ayanoglu Yoshinori Asakawab, Mensure Ozguven ˘ d a
Department of Pharmacognosy, Faculty of Pharmacy, Gazi Uni¨ ersity, 06330 Ankara, Turkey b Faculty of Pharmaceutical Sciences, Tokushima Bunri Uni¨ ersity, Tokushima 770, Japan c Department of Field Crops, Faculty of Agriculture, Cukuro¨ a Uni¨ ersity, 01330 Adana, Turkey d Department of Field Crops, Faculty of Agriculture, Mustafa Kemal Uni¨ ersity, 31034 Hatay, Turkey
Received 6 July 2001; accepted in revised form 15 April 2002
Abstract A new monocyclic triterpene ester (1) was isolated from the rhizomes of Iris germanica from Turkey. Structure elucidation of compound (1) was carried out by the combined application of HMQC, HMBC, DEPT, COSY and NOESY experiments and named as iristectorone K. 䊚 2002 Elsevier Science B.V. All rights reserved. Keywords: Iridaceae; Iris germanica; Iristectorone
1. Introduction Genus Iris ŽIridaceae. is represented by 37 species in Turkey, 13 of which are endemic w1x. Most of the Iris species are cultivated for ornamental purposes worldwide. Recently, Iris species have gained great attention from the cosmetic U
Corresponding author. Tel.: q90-312-2126645; fax: q90-312-2233921. E-mail address: [email protected] ŽI. Orhan..
0367-326Xr02r$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 6 7 - 3 2 6 X Ž 0 2 . 0 0 0 9 0 - 4
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
317
and perfume industries due to the their violet-like smell caused by irone-type compounds. Besides, some of Iris species such as Iris germanica, Iris tectorum, and Iris missuriensis, were reported to have various biological activities including potent antiulcer, anticancer and piscicidal activities w2,3x. There have been no previous phytochemical and bioactivity studies on Iris species growing in Turkey. In the course of our investigations on the rhizomes of I. germanica, a new monocyclic triterpene Ž1. was isolated from the petroleum ether extract of the plant.
2. Experimental 2.1. Plant material The rhizomes of I. germanica were collected from Reyhanli, Hatay in July, 1999. A voucher specimen was deposited in the Herbarium of Faculty of Pharmacy, Gazi University ŽGUE 2229.. Identification of the plant was made by one of us ŽM.O... 2.2. Extraction and isolation Powdered air dried plant material Ž184.88 g. was percolated with petroleum ether at room temperature The combined extracts were filtered and the solvent was removed in vacuo to give a crude extract Ž7.61 g., which was subjected to Si-gel CC eluting with hexaneracetone mixture Compound (1) was eluted and purified by PTLC using chloroformrtoluene 15:1. Žyield: 598.6 mg..
3. Results and discussion FAB-MS analysis of compound (1) indicated a molecular formula of C 40 H 70 O4 , with ion peaks wM q 1x at mrz 615, wM q 1 q Nax at mrz 638, wM q Kx at mrz 653, and wM q 1-H 2 Ox at m r z 597. Furthermore, CI-MS displayed molecular ion peaks at mrz 614 ŽMq; 22.7%. and at mrz 630 wMq qCH 4 ; 24.0%.. As indicated by 13 C NMR and DEPT spectra, (1) was comprised of eight quaternary, five methine, 20 methylene, and seven methyl carbons. The new compound showed the presence of an ␣ ,-unsaturated aldehyde in the 1 H and 13 C NMR spectra w ␦ H 10.3 Ž1 H, s ., ␦ C 189.9, 133.3 and 161.3x. The ␣ ,-unsaturated aldehyde proton at ␦ 10.3 showed a coupling to an allylic methyl group at ␦ 1.85. Compound (1) displayed NMR spectra close to those of iristectorones A-H, high fatty esters of triterpene-type compounds isolated from different Iris species w2᎐8x. This helped to establish the stereochemistry of (1) w5᎐8x. The NMR data and two-dimensional correlation Žsee Table 1. allowed, therefore, to assign structure 1 to the new compound named iristectorone K ŽFig. 1..
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
318
Table 1 NMR spectral data for compound Ž1. in d-C 6 H 6 C噛
13
C NMR
1 2 3 4 5 6 7 8
189.9 133.3 64.5 28.9 27.0 43.3 161.3 23.9
9
37.1
10 11 12 13
74.4 44.9 37.6 42.7
14
124.7
15 16
136.0 22.6
17 18 19 20 21 22 23 24 25 26 27 28 29 30 1⬘ 2⬘ 3⬘ 4⬘ 5⬘ 6⬘ 7⬘ 8⬘ 9⬘ 10⬘
27.4 122.1 136.4 22.9 30.1 29.8 38.9 17.9 14.7 23.1 14.4 11.1 26.5 17.9 173.3 34.4 25.4 29.3UU 29.4UU 29.5UU 29.6UU 29.8UU 29.7UU 14.3 U
UU
1
H NMR
10.3 s ᎐ 4.02 t Ž J s 6.40.U 1.39 m 2.14 m 3.24 d Ž J s10.7. ᎐ 2.45 m Ž8a. 2.20 m Ž8b. 1.30 m Ž9a. 1.52 m Ž9b. ᎐ ᎐ 1.07 m 1.97 m Ž13a. 2.23 m Ž13b. 5.16 t Ž J s 5.76, 5.21. ᎐ 1.83 m Ž16a. 1.84 m Ž16b. 1.38 m 5.36 m ᎐ 1-30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.42 m 0.97 br s o.68 br s 1.73 s 1.54 s 1.85 s 1.17 s 1.08 s ᎐ 2.19 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 1.30᎐1.22 m 0.89 m
HMBC
1
C2, C28 ᎐ C1⬘, C4, C5 C3, C5, C6 C4, C7 C2, C7, C10, C11 ᎐ C2, C6, C7, C10
H6 ᎐ H4, H5 H3, H5 H3, H4, H6 H5 ᎐ H8b, H9 H8a, H9 H8, H9b H8, H9a ᎐ ᎐ H13a, H30 H12, H13b, H14 H13a H13a, H16a, H16b, H13b ᎐ H14, H17, H27 H14, H17 H16, H18 H17, H16 ᎐ ᎐ ᎐ ᎐ H24, H25 H25 H24 H18 H14, H16 ᎐ H30 H12 ᎐ H3⬘ H2⬘, H4⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
C7, C8, C10 ᎐ ᎐ C11 C11, C12 C13 ᎐ C14, C15, C17 C16, C18, C17, C19 ᎐ ᎐ ᎐ ᎐ C24, C25 C23, C24 C23, C25 C19, C20 C14, C15, C16 C1, C2 C10, C11 C11, C12 ᎐ C1⬘, C3⬘ C2⬘, C4⬘, C5⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
Coupling constants are given in Hertz. Signals may be interchangeable within the same column.
H᎐ 1 H COSY
NOESY H5, H6, H28 ᎐ H4, H5 H3, H6 H3, H6 H4, H5 ᎐ H5, H8b, H9a H8a, H9b H9b H9a ᎐ ᎐ H13a ᎐ ᎐ H13a, H13b, H13 ᎐ H14, H27 H14, H27 H27 H17 ᎐ ᎐ ᎐ ᎐ H25 H22, H25 H24 H18 H16 ᎐ H30 H12 ᎐ H3⬘, H4⬘ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐ ᎐
I. Orhan et al. r Fitoterapia 73 (2002) 316᎐319
319
Fig. 1. Iristectorone K Ž1.
References w1x Davis PH. Flora of Turkey and the East Aegean Islands, VIII. Edinburgh: University Press, 1984:382. w2x Muto Y, Ichikawa H, Kitagawa O et al. Yakugaku Zasshi 1994;114:980. w3x Miyake Y, Ito H, Yoshida T. Can J Chem 1997;75:734. w4x Seki K, Tomihari T, Haga K, Kaneko R. Phytochemistry 1994;37:807. w5x Marner FJ, Littek A, Arold R, Seferiadis K, Jaenicke L. Liebigs Ann Chem 1990;6:563. w6x Seki K, Tomihar T, Haga K, Kaneko R. Phytochemistry 1994;36:433. w7x Bonfils JP, Marner FJ, Sauvaire Y. Phytochemistry 1998;48:751. w8x Takahashi K, Hoshino Y, Suzuki S, Hano Y, Nomura T. Phytochemistry 2000;53:925.