拟螺距翠雀花中的新二萜生物碱

THREE NEW DITERPENOID ALKALOIDS OF DELPHINIUM BULLEYANUM

从拟螺距翠雀花的根中分离、鉴定了六个二萜生物碱成分,其中三个为已知成分,分别为methyllycaconitine(1)、ajacine(2)和delsemine(3);另三个为新二萜生物碱,分别命名为螺翠碱甲(bulleyanitine A)、螺翠碱乙(bulleyanitine B)和螺翠碱丙(bulleyanitine C),纤MS、IR、~1H NMR、^(13)C NMR及DEPT等光谱的解析证明其化学结构分别为(4)、(5)、(6)。

Three new diterpenoid alkaloids, named bullcyanitine A, bulleyanitine B and bulleyanitine C were obtained from the roots of Delphinium bulleyanum Forrest ex Diels. On the basis of the spaetroseopie and chemical evidences, their structures were established as ( 4 ), ( 5 ) and ( 6 ). Three known alkaloids, methy-llycaeonitine ( 1 ), ajacine ( 2 ) and delsemine ( 3 ), were also isolated and identified. Bulleyanitine A(4), C35H47N3O10, amorphous, [α]D12 +57.2 (C, 0.37 acetone), MS(m/z). 669(0.1), 652(4), 638(3), 556(30), 437(20), 406(100), 188 (15). IRCcm-1). 3450-3300(OH and NH), 1715-1650( C = O ). 1H NMR (δ): 1.25(3H, d, J =6Hz, CHCH3), 3.18, 3.42(each 3H, s, 2×OCH3), 3.36(6H, s, 2×OCH3), 3.68(lH, t , J =4.5Hz, C14-βH), 3.83, 3.90 (2H, AB, C18-2H), 5.56 and 6.18(each lH, b.s, CONH2), 7.21 and 7.58(each 1H, t , J = 7Hz, Ar-2H), 8.0, 8.67(cach lH, d, J = 7Hz, Ar-2H), 7.54(lH, b.s HC = N), 11.0(lH, b.s, CO-NH).13C NMR data see table 1. The mixture of a pair of rcgioisomers bulleyanitine B( 5 ) and bulleyanitine C (6), C35H47N3O11, [α]D18+34.9(C, 0.56 acetone). MS(m/z). 572(0.15), 557 (0.4), 539(0.35), 453(0.9), 438(10), 188(100). IR (cm-1): 3450-3300(OH, NH), 1715-1650 (C = O) . 1H NMR(δ). 1.25 and 1.33 (total 3H, d, J = 6Hz, CHCH3), 3.27, 3.34, 3.38, 3.42 (each 3H, s, 4×OCH3), 3.65 (lH, t, J= 4.GHz, C14-βH), 3.93, 3.96(2H, AB, C18-2H), 6.11 and 6.14, 6.61 and 6.55 (each pair 1H, b.s, CONH2), 6.95(111, b.s, CONH), 7.11, 7.55(each 1H, t, J = 7Hz, Ar-2H) , 7.96, 8.68 (each lH, d, J = 7Hz, Ar-2H) , 11.0 and 11.l (total 1H, b.s, CONH). 13C NMR data see table 1. Bulleyanitine B and bulleyanitine C were the first naturally oceuring N-deethyl-oxobascs in C19-diterpenoicl alkaloids. Bulleyanine( 7 ) (N-deethyl-oxolycoctonine), one amino-alcohol given by mild alkaline hydrolysis of the mixture of bulleyanitine B and bulleyanitine C, C23H35NO8, MS(m/z). 453(18), 438(100), 432(18), 422(5), 406(17), 392(24), 388(24), 375(7). IR(em-1): 3450-3300(OH, NH), 1650(HN-CO). 1H NMR(δ): 3.25, 3.34, 3.42 and 3.45 (each 3H, s , 4×OCH3) , 3.65 (lH, t , J =4.5Hz, C14-βH) , 4.0 (1H, s , C6-αH) , 4.14, 4.17 (2H, AB, CI8-2H), 6.53 (lH, b.s, CONH). 13C NMR data see table l.