.Spectroscopic data
Zanthodione (I): orange needles; mp. 254-256 °C;
UV (MeOH) λmax (log E) 239 (sh) (4.49), 249 (4.51), 392 (sh) (3.58), 408 (4.51), 428 (3.58) ñm;
IR (KBr) vmax 3389 (OH); 1660, 1646 (C=0); 1601, 1460 (aromatic ring C=C); 1040, 94°6X(OCH20) cm-1;
1H NMR (CDC13, 600 MHz) δ 6.40 (2H, s, OCH20), 7.73 (1H, br ddd, J = 8.4, 7.2, 1.8 Hz, H-10), 7.77 (1H, dt, J = 7.2, 1.2 Hz, H-9), 8.04 (1H, s, H-7), 8.26 (1H, s, NH exchangeable with D20), 8.29 (1H, dd, J = 7.2, 1.8 Hz, H-8), 9.26 (1H, d, J = 8.4 Hz, H-ll), 11.98 (1H, s, OH exchangeable with D20);
EIMS m/z 307 [M]+ (90);
HRESIMS m/z 307.1481 (caled for C17H9NOs, 307.1480).
Zanthodione (I) was obtained as orange needles. Its molecular formula C17H9NOs was established by EIMS ([M]+, m/z 307) and HRESIMS. The UV spectrum showed absorption máxima at 239 (sh), 240, 249, 392 (sh), 408, 428 nm, that indicated the presence of a 4,5-dioxoaporphine skeleton.11,12 Its IR spectrum indicated the presence of OH/NH (3000—3389 cm-1), two aryl ketone C=0 (1660, 1646 cm-1), one methylenedioxy (1040, 940 cm1) and a six-membered lactam (1587 cm-1) functionalities. The 1H NMR spectrum revealed five aromatic protons, two D20 exchangeable singlets of a H-bonded phenolic hydroxyl [8 11.98 (1H, s)], and an amidocarbonyl proton at 8 8.26 (1H, s), and a methylenedioxy group at 8 6.40 (2H, s). Five aromatic protons of the spectrum closely resembled those of other 7,8,9,10,11-unsubstituted dioxoaporphine.11,12 Therefore, the methylenedioxy group had to be on ring A. The singlet at δ 8.04 (1H, s) was ascribed to H-7 while H-8, H-9, H-10 and H-ll appeared as a complex ABCX coupling system. In agreement with the spectra of other C-11-unsubstituted aporphines, dehydro- and oxoaporphines, the most downfield doublet [δ 9.26 (1H, s)] was characteristic of H-ll, the 2H [δ 7.73 (1H, ddd, J = 8.4, 7.2, 1.8 Hz), 7.77 (1H, dt, J = 7.2, 1.2 Hz)] were assigned to H-10, 9, and another proton at 6 8.29 (1H, dd, J = 7.2, 1.8 Hz) was due to H-8. The correlations of H-7/NH, and H-8/H-7, 9 were also disclosed in the NOESY experiment (Fig. 1) and further supported the position of above assignments. By means of 1H-NMR, 1H,1H-COSY, and NOESY (Fig. 1) data, the structure of zanthodione was shownto be 4-hydroxy-7H-benzo[g][l,3]dioxolo[4',5';4,5 ]benzo[l,2,3-úfe]quinoline-5,6-dione (1).
see...................
http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072008000300019&lng=en&nrm=iso&ignore=.html
J. Chil. Chem. Soc, 53, N° 3 (2008) págs: 1631-1634
CHEMICAL CONSTITUENTS FROM THE STEM BARK OF ZANTHOXYLUM SCANDENS
MING-JEN CHENG1,2,3 CHUAN-FANG LIN1,3 HSUN-SHUO CHANG1, IH-SHENG CHEN1*
1Graduate Institute of Natural Products , College of Pharmacy, Kaohsiung Medical University, Kaohsiung, Taiwan 807, Republic of China.
2M.-J. C. and C.-F. L. contributed equally to the work in this paper.
Bioresource Collection and Research Center (BCRC), Food Industry Research and Development Institute (FIRDI), Hsinchu, Taiwan 300, Republic of China.
