化合物10 白色無定形粉末;[α]29D-52.5°(c 0.100,MeOH);ESI-MS m/z 911 [M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.28(2H,d,J=8.5 Hz,H-2′,6′),7.26(2H,d,J=8.5 Hz,H-2,6),7.01(2H,d,J=8.5 Hz,H-3′,5′),7.00(2H,d,J=8.5 Hz,H-3,5),5.06(1H,d,J=12.5 Hz,Hb -7′),4.98(2H,d,J=12.5 Hz,Ha-7′,Hb-7),4.89(1H,d,J=12.5 Hz,Ha-7),4.85(2H,d,J=7.5 Hz,H-1″,1″″ ),4.66(1H,d,J=7.5 Hz,H-1″),3.68(2H,dd,J=12.0,3.0 Hz,Hb-6″,Hb-6″″),3.50(1H,dd,J=12.0,5.0 Hz,Hb-6″),3.45(2H,dd,J=12.0,6.0 Hz,HA-6″,Ha-6″″),3.40(1H,dd,J=12.0,6.0 Hz,Ha-6″),3.09(1H,d,J=18.0 Hz,Hb-3),2.97(1H,d,J=18.0 Hz,Ha-3),3.33~2.88(12H,m,H-2″,3″,4″,5″,H-2″″,3″″,4″″,5″″,H-2″,3″,4″,5″),1.73(1H,m,Hb-5),1.69(1H,m,H-6),1.67(1H,m,Ha-5),0.83(3H,d,J=6.5 Hz,H-8),0.77(3H,d,J=6.5 Hz,H-7);13C-NMR(DMSO-d6,125 MHz)δ:172.1(C-1),79.5(C-2),41.6(C-3),169.9(C-4),46.1(C-5),23.1(C-6),23.7(C-7),24.2(C-8),128.9(C-1′),129.9(C-2′),116.2(C-3′),157.3(C-4′),116.2(C-5′),129.9(C-6′),66.2(C-7′),100.3(C-1″),73.2(C-2″),76.6(C-3″),69.7(C-4″),77.0(C-5″),60.7(C-6″),128.8(C-1),129.8(C-2),116.1(C-3),157.3(C-4),116.1(C-5),129.8(C-6),65.7(C-7),100.3(C-1″″),73.2(C-2″″),76.6(C-3″″),69.7(C-4″″),77.0(C-5″″),60.7(C-6″″),98.3(C-1″),73.8(C-2″),76.5(C-3″),69.6(C-4″),76.9(C-5″), 60.7(C-6″)。以上數據與文獻[31]報道基本一致,故鑒定該化合物為dactylorhin A。
化合物11 白色無定形粉末;ESI-MS m/z 309 [M+Na]+。1H-NMR(DMSO-d6,500 MHz) δ:7.20(2H,d,J=8.5 Hz,H-2,6),6.96(2H,d,J=8.5 Hz,H-3,5),4.80(1H,d,J=7.5 Hz,H-1′),4.40(2H,br s,H-7),3.67(1H,d,J=12.0 Hz,Hb-6′),3.44(1H,dd,J=12.0,5.5 Hz,Ha-6′),3.30~3.12(4H,m,H-2′,3′,4′,5′);13C-NMR(DMSO-d6,125 MHz)δ:135.8(C-1),127.7(C-2),115.9(C-3),156.3(C-4),115.9(C-5),127.7(C-6),62.5(C-7),100.5(C-1′),73.2(C-2′),77.0(C-3′),69.7(C-4′),76.6(C-5′),60.7(C-6′)。以上數據與文獻[31]報道基本一致,故鑒定該化合物為天麻苷。
4 結果與討論
本研究從中藥山慈菇的主要來源之一——獨蒜蘭P. bulbocodioides幹燥假鱗莖的具有抗癡呆活性部位中分離得到11個化合物,包括10個丁二酸苄酯苷類化合物和1個苄醇糖苷類化合物。張丹等[29-30]研究發現,由以丁二酸苄酯苷類化合物loroglossin,dactylorhin A,dactylorhin B,millitarine等為主要成分組成的長苞凹舌蘭乙醇提取物(Coeloglossum. viride var. bracteatum extract,CE)具有改善能量代謝障礙和抑製單胺類遞質失調的作用,能改善D-Gal+NaNO2所致衰老小鼠的學習記憶障礙,具有抗凋亡、促智、延緩衰老的作用。本文分離得到的化合物包括了loroglossin(1),millitarine(9),dactylorhin A(10)這些活性成分,此外還有7個丁二酸苄酯苷類化合物和1個苄醇糖苷類化合物。
以上研究豐富了獨蒜蘭化學成分的研究內容,為獨蒜蘭抗癡呆活性這一非傳統藥用功效的深入研究以及進一步開發利用奠定了物質基礎。
[參考文獻]
[1] 中國藥典. 一部[S]. 2010:31.
[2] 董海玲,郭順星,王春蘭,等. 山慈菇的化學成分和藥理作用研究進展[J]. 中草藥,2007,38(11):1734.
[3] 王曉娟,崔保鬆,王超,等. 雲南獨蒜蘭的化學成分研究[J]. 中國中藥雜誌,2014,39(5):851.
[4] 劉量,葉靜,李萍,等. 杜鵑蘭假鱗莖化學成分研究[J]. 中國中藥雜誌,2014,39(2):250.
[5] 王超,韓少偉,崔保鬆,等. 獨蒜蘭的化學成分研究[J]. 中國中藥雜誌,2014,39(3):442.
[6] Liu L,Li J,Zeng K W,et al. Three new phenanthrenes from Cremastra appendiculata(D. Don) Makino [J]. Chin Chem Lett,2013,24:737.
[7] Dong H L,Liang H Q,Wang C L,et al. Shancigusins E-I, five new glucosides from the tubers of Pleione yunnanensis [J]. Magn Reson Chem,2013,51:371.
[8] Wang Y,Guan S H,Meng Y H,et al. Phenanthrenes, 9,10-dihydrophenanthrenes, bibenzyls with their derivatives, and malate or tartrate benzyl ester glucosides from tubers of Cremastra appendiculata [J]. Phytochemistry,2013,94:268.
[9] Dong H L,Wang C L,Li Y,et al. Complete assignments of 1H and 13C NMR data of three new dihydrophenanthrofurans from Pleione yunnanensis [J]. Magn Reson Chem,2010,48:256.
[10] Liu X Q,Guo Y Q,Gao W Y,et al. Two new phenanthrofurans from Pleione bulbocodioides [J]. J Asian Nat Prod Res,2008,10(5):453.
[11] Liu X Q,Yuan Q Y. A new dibenzyl from Pleione bulbocodioides [J]. Asian J Chem,2013,25(6):3519.
[12] 劉新橋,萬定榮,袁橋玉. 中藥獨蒜蘭的化學成分[J]. 中國醫院藥學雜誌,2011,31(19):1649.
[13] 劉新橋,袁橋玉,邵群梅. 土家族藥獨蒜蘭的化學成分研究[J]. 中南民族大學學報:自然科學版,2011,30(3):54.
[14] Dong H L,Wang C L,Guo S X,et a1. New bibenzyl derivatives from the tubers of Pleione yunnanensis [J]. Chem Pharm Bull,2009,57(5):513.
[15] Liu X Q,Yuan Q Y,Guo Y Q. Two new stilbenoids from Pleione bulbocodioides [J]. J Asian Nat Prod Res,2009,11(2):116.
[16] Liu X Q,Yuan Y Q,Gao Y Q. A new bibenzyl derivative from Pleione bulbocodioides [J]. Chin Chem Lett,2008,19:559.
[17] 張金超,申勇,朱國元,等. 杜鵑蘭Cremastra appendiculata化學成分研究[J]. 河北大學學報:自然科學版,2007,27(3):262.
[18] Liu X Q,Guo W Y,Gao Y Q,et al. Two new α,β-unsaturated butyrolactone derivatives from Pleione bulbocodioides [J]. Chin Chem Lett,2007,18:1075.
[19] Li S,Xue Z,Wang S J,et al. Terpenoids from the tuber of Cremastra appendiculata [J]. J Asian Nat Prod Res,2008,10(7):677.
[20] 林冰,周英. 山慈菇化學成分研究(Ⅰ)[J]. 中國中醫藥資訊,2011,3(5):183.
[21] 秦新英,申勇. 杜鵑蘭Cremastra appendiculata化學成分的分離[J]. 河北大學學報:自然科學版,2011,31(4):393.
[22] 劉淨,於誌斌,葉蘊華,等. 山慈菇的化學成分[J]. 藥學學報,2008,43(2):181.
[23] 袁橋玉,劉新橋. 獨蒜蘭化學成分研究[J]. 中藥材,2012,35(10):1602.
[24] 張堯,黃波,趙致,等. 山慈菇乙酸乙酯部位化學成分研究[J]. 中藥材,2011,34(12):1882.
[25] 林冰,周英. 山慈菇化學成分研究(Ⅱ)[J]. 中國中醫藥資訊,2011,3(14):402.
[26] Wang Y,Guan S H,Feng R H,et al. Elution-extrusion counter-current chromatography separation of two new benzyl ester glucosides and three other high-polarity compounds from the tubers of Pleione bulbocodioides [J]. Phytochem Anal,2013,24:671.
[27] 崔保鬆,宋傑,李帥,等. RP-HPLC同時測定山慈菇藥材中dactylochin A和militarine的含量[J]. 中國中藥雜誌,2013,38(24):4347.
[28] 李敏,王亞芳,馬波,等. 藏藥旺拉提取物對東莨菪堿致動物學習記憶障礙的改善作用及其機製研究[J].藥學學報,2009,44(5):468.
[29] Zhang D,Liu G T,Shi J G,et al. Coeloglossum viride var. bracteatum extract attenuates D-galactose and NaNO2 induced memory impairment in mice [J]. J Ethnopharmacol,2006,104:250.
[30] Zhang D,Liu G T,Shi J G,et al. Effects of Coeloglossum viride var. bracteatum extract on memory deficits and pathological changes in senescent mice [J]. Basic Clin Pharmacol Toxicol,2006,98:55.
[31] 黃勝陽,石建功,楊永春,等. 長苞凹舌蘭化學成分研究[J]. 藥學學報,2002,37(3):199 .
[32] Poolsak S,Chulabhorn M,Wannaporn D,et al. Glucopyranosyloxybenzyl derivatives of(R)-2-benzylmalic acid and(R) - eucomic acid,and an aromatic glucoside from the pseudobulbs of Grammatophyllum speciosum [J]. Tetrahedron,2013,69:1031.
[33] Zi J C,Li S,Liu M T,et al. Glycosidic constituents of the tubers of Gymnadenia conopsea [J]. J Nat Prod,2008,71:799.
[34] Li Y M,Zhou Z L and Hong Y F. New phenolic derivatives from Galeolafaberi [J]. Planta Med,1993,59:363.
[35] Toshio M,Haihui X,Hisashi M,et al. Glucosyloxybenzyl 2-isobutylmalates from the tubers of Gymnadenia conopsea [J]. J Nat Prod,2008,69:881.
[責任編輯 丁廣治]