正文 苦石蓮中卡山烷類二萜的化學成分研究(3 / 3)

化合物12 無色針晶(164~165 ℃),易溶於氯仿、甲醇。ESI-MS m/z 399[M+Na]+。1H-NMR(CDCl3,600 MHz)δ:3.65(1H,t,J=2.4 Hz,H-1),5.15(1H,t,J=3.6 Hz,H-6),6.20(1H,d,J=2.4 Hz,H-15),7.23(1H,d,J=2.4 Hz,H-16),1.01(3H,d,J=7.2 Hz,H-17),1.04(3H,H-18),1.24(3H,s,H-19),1.25(3H,s,H-20),2.05(3H,s,6-OCOCH3)。13C-APT(CDCl3,150 MHz) δ:74.5(C-1),26.3(C-2),32.1(C-3),39.5(C-4),77.2(C-5),72.1(C-6),31.3(C-7),30.2(C-8),32.3(C-9),43.7(C-10),21.4(C-11),149.0(C-12),122.4(C-13),31.3(C-14),109.6(C-15),140.4(C-16),17.6(C-17),27.7(C-18),26.1(C-19),16.5(C-20),21.8/170.0(6-OCOCH3)。以上數據與文獻報道caesaldekarin D [12]一致,故將化合物12鑒定為caesaldekarin D。

化合物13 無色針晶(152~153℃),易溶於氯仿、甲醇。ESI-MS m/z 383[M+Na]+。1H-NMR(CDCl3,600 MHz) δ:5.23(1H,t,J=3.6 Hz,H-6),6.19(1H,d,J=1.2 Hz,H-15),7.23(1H,d,J=1.2 Hz,H-16),0.99(3H,d,J=7.2 Hz,H-17),1.01(3H,s,H-18),1.25(3H,s,H-19),1.35(3H,s,H-20),2.07(3H,s,6-OCOCH3)。13C-APT(CDCl3,150 MHz) δ:34.6(C-1),18.6(C-2),38.1(C-3),38.9(C-4),76.2(C-5),72.3(C-6),31.4(C-7),30.4(C-8),37.9(C-9),41.4(C-10),21.7(C-11),149.5(C-12),122.3(C-13),31.1(C-14),109.4(C-15),140.3(C-16),17.6(C-17),27.6(C-18),25.7(C-19),16.5(C-20),21.8/169.9(6-OCOCH3)。以上數據與文獻報道caesaldekarin A [13]一致,故將化合物13鑒定為caesaldekarin A。

化合物14 無色針晶(160~161 ℃),易溶於氯仿、甲醇。ESI-MS m/z 341[M+Na]+。1H-NMR(CDCl3,600 MHz) δ:4.17(1H,t,J=3.6 Hz,H-6),6.19(1H,d,J=1.2 Hz,H-15),7.23(1H,d,J=1.2 Hz,H-16),1.00(3H,d,J=7.2 Hz,H-17),1.03(3H,s,H-18),1.47(3H,s,H-19),1.36(3H,s,H-20)。13C-APT(CDCl3,150 MHz) δ:35.1(C-1),18.1(C-2),38.1(C-3),38.9(C-4),76.6(C-5),71.3(C-6),35.4(C-7),30.4(C-8),38.2(C-9),40.9(C-10),21.7(C-11),149.5(C-12),122.3(C-13),31.1(C-14),109.4(C-15),140.3(C-16),17.6(C-17),27.6(C-18),26.1(C-19),16.5(C-20)。以上數據與文獻報道caesaldekarin b [13]一致,故將化合物14鑒定為caesaldekarin b。

化合物15 白色粉末,易溶於氯仿、甲醇。ESI-MS m/z 425[M+Na]+。1H-NMR(CDCl3,600 MHz) δH:4.53(1H,dd,J=10.8,4.2 Hz,H-3),5.53(1H,d,J=9.6 Hz,H-6),6.18(1H,d,J=1.2 Hz,H-15),7.22(1H,d,J=1.2 Hz,H-16),1.08(3H,d,J=7.2 Hz,H-17),1.12(3H,s,H-18),1.02(3H,s,H-19),1.02(3H,s,H-20),2.17(3H,s,3-OCOCH3),2.18(3H,s,6-OCOCH3)。13C-APT(CDCl3,150 MHz) δ:37.3(C-1),23.3(C-2),80.5(C-3),37.5(C-4),57.2(C-5),71.8(C-6),38.9(C-7),35.1(C-8),44.6(C-9),37.5(C-10),22.7(C-11),149.2(C-12),122.3(C-13),30.7(C-14),109.6(C-15),140.9(C-16),17.2(C-17),30.8(C-18),17.2(C-19),15.5(C-20)。21.8/170.1(3-OCOCH3),21.1/170.8(6-OCOCH3)。以上數據與文獻報道3β,6α-diacetoxyvouacapane [14]一致,故將化合物15鑒定為3β,6α-diacetoxyvouacapane。

[參考文獻]

[1] 胡劍波,何順誌,陳龍珠,等.中國雲實屬藥用植物產藏量及生境調查[J].中國中藥雜誌, 1999, 24( 3):134.

[2] 廣西壯族自治區衛生廳.廣西中藥材標準[S].南寧:廣西科學技術出版社, 1992:631.

[3] 許娜. 苦石蓮的化學成分研究[D]. 北京:中國協和醫科大學,2010.

[4] 郭建軍,周英,王華林,等.苦石蓮的化學成分研究[J].中國實驗方劑學雜誌,2013, 19(6):117.

[5] Che C T, Mcpherson D D, Cordell G A,et al. Pulcherralpin, a new diterpene ester from caesalpinia pulcherrima [J].J Nat Prod, 1986, 49(4):561.

[6] Kalauni S K, Awale S, Tezuka Y, et al. New cassane-type diterpenes of Caesalpinia crista from Myanmar [J]. Chem Pharm Bull, 2005, 53(2):214.

[7] Barba B, Diaz J G, Goedken V L, et al. Unusual cassanes from a Chamaecrzsta species [J]. Tetrahedron, 1992, 48(23):4725.

[8] Mendoza D T, Gonzalez L D U, Barria E O, et al. Novel cassane and cleistanthane diterpenes from Myrospermum frutescens:absolute stereochemistry of the cassane diterpene series [J]. J Nat Prod, 2004, 67(10):1711.

[9] Li D M, Ma L, Liu G M,et al. Cassane diterpene-lactones from the seed of Caesalpinia minax [J]. Chem Biodiver, 2006, 3(11):1260.

[10] Cheng Y, Ma L,Xu X D, et al. A new cassane diterpenoid lactone from the seed of Caesalpinia minax [J]. Chin Chem Lett, 2009, 20(4):444.

[11] Pranithanchai W, Karalai C, Ponglimanont C, et al. Cassane diterpenoids from the stem of Caesalpinia pulcherrima [J]. Phytochemistry, 2009, 70(2):300.

[12] Kitagawa I, Simanjuntak S, Mahmud T, et al. Indonesian medicinal plants XIII. Chemical structures of caesaldekarins c, d, and e, three additional cassane-type furanoditerpenes from the roots of Caesalpinia major(Fabaceae). Several interesting reaction products of caesaldekarin a provided by N-bromosuccinimide treatment [J]. Chem Pharm Bull, 1996, 44(6):1157.

[13] Kitagawa I, Simanjuntak P, Watano T, et al. Indonesian medicinal plants XI. Chemical structures of caesaldekarins a and b, two new cassane-type furanoditerpenes from the roots of Caesalpinia major (Fabaceae) [J]. Chem Pharm Bull, 1994, 42(9):1798.

[14] Mendes F N P, Silveira E R. Fatty acids, sesqui- and diterpenoids from seeds of Dipteryx lacunifera [J]. Phytochemistry, 1994, 35(6):1499.

[責任編輯 丁廣治]