A Novel 3a-p-Nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate and Two New Triterpenoids from the Seeds of Zucchini (Cucurbita pepo L)
Abstract
:1. Introduction
2. Results and Discussion
Position | 1 | 2 | 3 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
δH (J in Hz) | δC | δH (J in Hz) | δC | δH (J in Hz) | δC | |||||||
1α | 1.78 | m | 30.8 | (t) | 1.67 | m | 30.2 | (t) | 1.76 | td (14.0, 4.3) | 30.3 | (t) |
1β | 1.62 | m | 1.48 | m | 1.72 | m | ||||||
2α | 1.92 | m | 23.3 | (t) | 1.73 | m | 23.0 | (t) | 1.82 | m | 22.8 | (t) |
2β | 2.07 | m | 1.92 | m | 2.06 | m | ||||||
3 | 4.97 | t (2.7) | 80.7 | (d) | 4.67 | t (2.7) | 78.2 | (d) | 4.75 | dd(3.5, 2.4)(3.0) | 77.4 | (d) |
4 | 37.4 | (s) | 36.1 | (s) | 38.9 | (s) | ||||||
5 | 1.77 | m | 43.8 | (d) | 1.63 | d (4.9) | 42.8 | (d) | 148.9 | (s) | ||
6α | 2.21 | m | 24.0 | (t) | 2.12 | brt (4.9) | 23.7 | (t) | 5.85 | d (6.4) | 118.1 | (d) |
6β | 2.21 | m | 2.02 | m | ||||||||
7 | 5.53 | brs | 118.3 | (d) | 5.49 | brs | 118.1 | (d) | 5.61 | d (6.4) | 114.4 | (d) |
8 | 142.3 | (s) | 141.8 | (s) | 141.2 | (s) | ||||||
9 | 144.6 | (s) | 144.3 | (s) | 144.6 | (s) | ||||||
10 | 36.4 | (s) | 36.1 | (s) | 39.2 | (s) | ||||||
11 | 5.24 | brd (4.5) | 114.3 | (d) | 5.20 | d (5.3) | 113.8 | (d) | 5.34 | dt (5.0, 2.1) | 118.4 | (d) |
12α | 2.10 | m | 39.6 | (t) | 2.07 | m | 39.3 | (t) | 2.16 | dd (17.4, 6.2) | 40.1 | (t) |
12β | 1.77 | dd (11.7, 4.8) | 1.75 | m | 1.83 | m | ||||||
13 | 37.5 | (s) | 37.3 | (s) | 38.2 | (s) | ||||||
14 | 40.3 | (s) | 40.0 | (s) | 40.0 | (s) | ||||||
15α | 1.85 | m | 27.6 | (t) | 1.71 | m | 27.3 | (t) | 1.77 | m | 26.8 | (t) |
15β | 1.42 | m | 1.37 | m | 1.36 | m | ||||||
16α | 1.69 | m | 36.8 | (t) | 1.70 | m | 36.6 | (t) | 1.74 | m | 36.6 | (t) |
16β | 1.52 | m | 1.50 | t (3.8) | 1.52 | dt (10.0, 3.1) | ||||||
17 | 31.8 | (s) | 31.5 | (s) | 31.6 | (s) | ||||||
18 | 1.65 | m | 44.8 | (d) | 1.65 | m | 44.6 | (d) | 1.7 | dd (9.2, 2.6) | 44.6 | (d) |
19α | 1.81 | m | 28.6 | (t) | 1.82 | m | 28.3 | (t) | 1.84 | m | 27.9 | (t) |
19β | 1.61 | m | 1.54 | m | 1.55 | m | ||||||
20 | 31.9 | (s) | 31.6 | (s) | 31.6 | (s) | ||||||
21α | 1.48 | 2H, m | 30.2 | (t) | 1.58 | 2H, m | 30.0 | (t) | 1.46 | m | 30.1 | (t) |
21β | 1.60 | m | ||||||||||
22α | 1.79 | m | 34.4 | (t) | 1.80 | dd (10.1, 4.4) | 34.0 | (t) | 1.81 | m | 34.0 | (t) |
22β | 0.94 | m | 0.94 | m | 0.95 | dt (13.8, 3.1) | ||||||
23 | 0.92 | s | 27.7 | (q) | 0.84 | s | 22.0 | (q) | 1.08 | s | 26.8 | (q) |
24 | 1.07 | s | 22.2 | (q) | 0.98 | s | 27.2 | (q) | 1.22 | s | 31.6 | (q) |
25 | 0.99 | s | 20.7 | (q) | 0.93 | s | 20.4 | (q) | 1.17 | s | 30.7 | (q) |
26 | 0.95 | s | 22.1 | (q) | 0.93 | s | 21.7 | (q) | 1.04 | s | 21.0 | (q) |
27 | 0.91 | s | 19.7 | (q) | 0.88 | s | 19.6 | (q) | 0.83 | s | 19.8 | (q) |
28 | 1.13 | s | 31.3 | (q) | 1.12 | s | 31.0 | (q) | 1.13 | s | 31.1 | (q) |
29A | 4.11 | d (10.7) | 73.0 | (t) | 4.10 | d (10.7) | 72.8 | (t) | 4.08 | d (10.9) | 72.6 | (t) |
29B | 4.17 | d (10.7) | 4.15 | d (10.7) | 4.16 | d (10.9) | ||||||
30 | 1.12 | s | 30.6 | (q) | 1.11 | s | 30.5 | (q) | 1.11 | s | 30.7 | (q) |
3-OCO | 164.4 | (s) | 170.9 | (s) | 171.0 | (s) | ||||||
1' | 136.3 | (s) | 2.03 | s | 21.3 | (q) | 2.00 | s | 21.3 | (s) | ||
2', 6' | 8.10 | dt (8.9, 2.1) | 130.7 | (d) | ||||||||
3', 5' | 8.20 | dt(8.9,2.1) | 123.8 | (d) | ||||||||
4' | 150.6 | (s) | ||||||||||
29-OCO | 166.9 | (s) | 166.7 | (s) | 166.7 | (s) | ||||||
1'' | 130.8 | (s) | 130.6 | (s) | 130.6 | (s) | ||||||
2'', 6'' | 8.08 | 2H, dd (7.4,2.1) | 129.7 | (d) | 8.08 | 2H, dd (7.4,1.4) | 129.4 | (d) | 8.07 | 2H, dd (8.2, 1.2) | 129.5 | (d) |
3'', 5'' | 7.43 | 2H, tt (7.4,2.1) | 128.6 | (d) | 7.45 | 2H, tt (7.4,1.4) | 128.4 | (d) | 7.45 | 2H, tt (8.2,1.2) | 128.4 | (d) |
4'' | 7.52 | tt (7.4,2.1) | 133.0 | (d) | 7.58 | tt (7.4,1.4) | 132.8 | (d) | 7.56 | tt (8.2,1.2) | 132.8 | (d) |
Compound | IC50 (μM)a | |
---|---|---|
HL-60 | P388 | |
(human leukemia) | (murine leukemia) | |
1 | >100 | >100 |
2 | 25.7 ± 1.1 | 75.1 ± 0.8 |
3 | >100 | >100 |
4 | >100 | >100 |
5 | >100 | >100 |
5-fluorouracil b | 2.3 ± 0.2 | 1.9 ± 0.2 |
Compound | Mean ± S.D. (%) at 10 μM | Mean ± S.D. (%) at 30 μM | Mean ± S.D. (%) at 100 μM | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Melanin content | Cell viability | Melanin content | Cell viability | Melanin content | Cell viability | |||||||||||||
1 | 103.7 | ± | 5.2 | 91.1 | ± | 4.4 | 99.4 | ± | 3.7 | 82.3 | ± | 4.3 | 92.7 | ± | 3.1 | 76.4 | ± | 0.8 |
2 | 73.6 | ± | 1.0 | 87.6 | ± | 0.2 | 69.9 | ± | 4.4 | 69.3 | ± | 1.3 | 31.4 | ± | 2.8 | 32.8 | ± | 2.8 |
3 | 97.3 | ± | 0.9 | 99.4 | ± | 4.0 | 93.5 | ± | 2.5 | 99.4 | ± | 3.8 | 66.9 | ± | 5.0 | 92.5 | ± | 4.3 |
4 | 97.4 | ± | 2.1 | 102.4 | ± | 4.3 | 96.8 | ± | 1.0 | 96.2 | ± | 1.3 | 98.5 | ± | 8.4 | 88.0 | ± | 5.9 |
5 | 102.0 | ± | 9.2 | 100.9 | ± | 1.8 | 101.1 | ± | 6.9 | 99.2 | ± | 9.6 | 92.4 | ± | 4.7 | 97.6 | ± | 6.6 |
arbutinb | 88.9 | ± | 2.3 | 100.0 | ± | 2.7 | 72.3 | ± | 3.1 | 94.4 | ± | 1.2 | 55.3 | ± | 1.0 | 89.9 | ± | 0.3 |
3. Experimental
3.1. General Procedures
3.2. Plant Material
3.3. Isolation Procedure
3.4. Compound 1
3.5. Compound 2
3.6. Compound 3
3.7. Cytotoxicity Assay
3.8. Determination of Cell Proliferation
3.9. Assay of Melanin Content
4. Conclusions
Supplementary Materials
Acknowledgments
Conflicts of Interest
References
- Appendino, G.; Jakupovic, J.; Belloro, E.; Marchesini, A. Multiflorane triterpenoid esters from pumpkin. An unexpected extrafolic source of PABA. Phytochemistry 1999, 51, 1021–1026. [Google Scholar] [CrossRef]
- Appendino, G.; Jakupovic, J.; Belloro, E.; Marchesini, A. Triterpenoid p-aminobenzoate from the seeds of zucchini. Fitoterapia 2000, 71, 258–263. [Google Scholar] [CrossRef]
- Barker, E.C.; Gatbonton-Schwager, T.N.; Han, Y.; Clay, J.E.; Letterio, J.J.; Tochtrop, G.P. Brynolic acid: A large-scale isolation and evaluation of heme oxygenase 1 expression in activated macrophages. J. Nat. Prod. 2010, 73, 1064–1068. [Google Scholar] [CrossRef]
- Wang, D.; Ge, S.; Gao, H.; Cai, H.; Wu, B.; Li, D.; Wu, L.; Deng, X. Structure determination of a cucurbitacin glycoside extracted from Cucurbita pepo cv Dayangua by 2D NMR. Bopuxue Zazhi 2005, 22, 417–422. [Google Scholar]
- Wang, D.; Pan, H.-Y.; Deng, X.-M.; Xiang, H.; Gao, H.; Cai, H.; Wu, L. Cucurbitane and hexanorcucurbitane glycosides from the fruits of Cucurbita pepo cv dayangua. J. Asian Nat. Prod. Res. 2007, 9, 525–529. [Google Scholar] [CrossRef]
- Wang, D.; Xiang, H.; Li, D.; Gao, H.; Cai, H.; Wu, L.-J.; Deng, X.-M. Purine-containing cucurbitane triterpenoids from Cucurbita pepo cv dayangua. Phytochemistry 2008, 69, 1434–1438. [Google Scholar] [CrossRef]
- Ding, Y.; Deng, X.; Cai, Hui.; Wang, F.; Wang, X.; Zhang, Y.; Yang, J. Studies on chemical constituents of Cucurbita pepo cv dayangua. Zhongguo Yaoxue Zazhi 2002, 37, 659–661. [Google Scholar]
- Shibuya, M. Biosynthesis of sterols and triterpenes in higher plants. Nat. Med. 2001, 55, 1–6. [Google Scholar]
- Shibuya, M.; Adachi, S.; Ebizuka, Y. Cucurbitadienol synthase, the first commited enzyme for cucurbitacin biosynthesis, is a distinct enzyme from cycloartenol synthase for phytosterol biosynthesis. Tetrahedron 2004, 60, 6995–7003. [Google Scholar] [CrossRef]
- Ma, Y.-P.; Li, N.; Gao, J.; Fu, K.-L.; Qin, Y.; Li, G.-Y.; Wang, J.-H. A new peroxy-multiflorane triterpene ester from the processed seeds of Trichosanthes kirilowii. Helv. Chim. Acta 2011, 94, 1881–1887. [Google Scholar] [CrossRef]
- Parry, R.; Nishino, S.; Spain, J. Naturally-occurring nitro compounds. Nat. Prod. Rep. 2011, 28, 152–167. [Google Scholar]
- Al-Zereini, W.; Schumann, I.; Laatsch, H.; Helmke, E.; Anke, H. New aromatic nitro compounds from Salegentibacter sp. T436, an Arctic sea ice bacterium: Taxonomy, fermentation, isolation and biological activities. J. Antibiotics 2007, 60, 301–308. [Google Scholar]
- Ohmori, T.; Hagiwara, S.-I.; Ueda, A.; Minoda, Y.; Yamada, K. Production of pyoluteorin and its derivatives from n-paraffin by Pseudomonas aeruginosa S10B2. Agric. Biol. Chem. 1978, 42, 2031–2036. [Google Scholar] [CrossRef]
- Zlatopolskiy, B.D.; Loscha, K.; Alvermann, P.; Kozhushkov, S.I.; Nikolaev, S.V.; Zeeck, A.; de Meijere, A. Final elucidation of the absolute configuration of the signal metabolite hormaomycin. Chem. Eur. J. 2004, 10, 4708–4717. [Google Scholar] [CrossRef]
- Hoeksema, H.; Mizak, S.A.; Bacznskyj, L.; Pschigoda, L.M. Structure of rubradirin. J. Am. Chem. Soc. 1982, 104, 5173–5181. [Google Scholar] [CrossRef]
- Alston, T.A.; Mela, L.; Bright, H.J. 3-Nitropropionate, the toxic substance of Indigofera, is a suicide inactivator of succinate dehydrogenase. Proc. Natl. Acad. Sci. USA 1977, 74, 3767–3771. [Google Scholar] [CrossRef]
- Palermo, J.A.; Rodriguez Brasco, M.F.; Spagnuolo, C.; Seldes, A.M. Illudalane sesquiterpenoids from the soft coral Alcyonium paessleri: The first natural nitrate esters. J. Org. Chem. 2000, 65, 4482–4486. [Google Scholar] [CrossRef]
- Yamada, T.; Muroga, Y.; Jinno, M.; Kajimoto, T.; Usami, Y.; Numata, A.; Tanaka, R. New class azaphilone produced by a marine fish-derived Chaetomium globosum. The stereochemistry and biological activities. Bioorg. Med. Chem. 2011, 19, 4106–4113. [Google Scholar] [CrossRef]
- Akihisa, T.; Seino, K.; Kaneko, E.; Watanabe, K.; Tochizawa, S.; Fukatsu, M.; Banno, N.; Metori, K.; Kimura, Y. Melanogenesis inhibitory activities of iridoid-, hemiterpene-, and fatty acid-glycosides from the fruits of Morinda citrifolia (Noni). J. Oleo Sci. 2010, 59, 49–57. [Google Scholar] [CrossRef]
- Sample Availability: Not available.
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Tanaka, R.; Kikuchi, T.; Nakasuji, S.; Ue, Y.; Shuto, D.; Igarashi, K.; Okada, R.; Yamada, T. A Novel 3a-p-Nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate and Two New Triterpenoids from the Seeds of Zucchini (Cucurbita pepo L). Molecules 2013, 18, 7448-7459. https://doi.org/10.3390/molecules18077448
Tanaka R, Kikuchi T, Nakasuji S, Ue Y, Shuto D, Igarashi K, Okada R, Yamada T. A Novel 3a-p-Nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate and Two New Triterpenoids from the Seeds of Zucchini (Cucurbita pepo L). Molecules. 2013; 18(7):7448-7459. https://doi.org/10.3390/molecules18077448
Chicago/Turabian StyleTanaka, Reiko, Takashi Kikuchi, Saori Nakasuji, Yasuhiro Ue, Daisuke Shuto, Keishi Igarashi, Rina Okada, and Takeshi Yamada. 2013. "A Novel 3a-p-Nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate and Two New Triterpenoids from the Seeds of Zucchini (Cucurbita pepo L)" Molecules 18, no. 7: 7448-7459. https://doi.org/10.3390/molecules18077448