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大白杜鹃花化学成分及其抗肿瘤细胞毒活性

来源：花匠小妙招时间：2025-01-10 07:18

摘要:

研究大白杜鹃花的化学成分及其抗肿瘤细胞毒活性. 采用硅胶柱色谱、凝胶柱色谱、反相RP-18柱色谱等方法进行分离纯化，根据理化性质和波谱数据鉴定化合物结构，然后采用CCK-8方法测定化合物的抗肿瘤细胞毒活性. 从乙酸乙酯部位中分离并鉴定20个化合物，分别为大白杜鹃花酮 (1)、confluentin (2)、o-methy-llasiodiplodin (3)、daurichromenes A (4)、arthproliferin B (5)、梫木毒素 Ⅰ (6)、梫木毒素 Ⅳ (7)、(Z)-9,10-dihydroxy-6,10-dimethyl-5-undecen-2-one (8)、8-hydroxy-6,7-dihydrolinalool (9)、(E)-2,6-dimethyl-2,7-octadiene-1,6-diol (10)、9-hydroxy-4,7-megastigmadien-3-one (11)、吐叶醇 (12)、去氢催吐萝芙木醇 (13)、蔷薇酸 (14)、山柰酚 (15)、阿福豆苷 (16)、萹蓄苷 (17)、香树素-3-O-α-L-阿拉伯糖苷 (18)、去甲基丁香色原酮 (19)和东莨菪亭 (20)，以上化合物对A-549、HepG2、Hela-60、MDA-MB-68 细胞均无明显毒性. 化合物1为新的天然产物，化合物1～5，7～20均为首次从该种植物中分离得到.

Abstract:

The chemical constituents and antitumor activity of Rhododendron decorum were studied. Twenty compounds were isolated from the EtOAc extract of this plant by silica gel, sephadex LH-20 and RP-18 column chromatography, and CCK-8 method were used to test the antitumor activity in vitro. They were identified as decorumtone (1), confluentin (2), o-methy-llasiodiplodin (3), daurichromenes A (4), arthproliferin B (5), grayanotoxin-Ⅰ (6), grayanotoxin Ⅳ (7), (Z)-9,10-dihydroxy-6,10-dimethyl-5-undecen-2-one (8), 8-hydroxy-6,7-dihydrolinalool (9), (E)-2,6-dimethyl-2,7-octadiene-1,6-diol (10), 9-hydroxy-4,7-megastigmadien-3-one (11), vomifoliol (12), dehydrovomifoliol (13), euscaphic acid (14), kaempferol (15), afzelin (16), avicularin (17), aromadedrin-3-O-α-L-arabinopyranoside (18), noreugenin (19), scopoletin (20) on the basis of physicochemical properties and spectral data. Those compounds have no significant activity against to the cell lines A-549, HepG2, Hela-60, MDA-MB-68. Compound 1 was a new natural product, Compounds 1−5, 7−20 were isolated from Rhododendron decorum. for the first time.

图 1 化合物1的化学结构与主要HMBC和1H-1H COSY相关信号

Figure 1. Chemical structure and key HMBC and 1H-1H COSY correlations of compound 1

表 1 化合物1的1H NMR（600 MHz）和13C NMR（150 MHz）数据 (CDCl3)

Table 1 1H NMR (600 MHz) and 13C NMR (150 MHz) data for compound 1 (CDCl3)

序号 δC δH 1 155.4 (CH) 9.29 (1H，s) 3 149.7 (CH) 9.08 (1H，s) 4 124.5 (C) 5 164.9 (C) 6 205.1 (C) 7 36.1 (CH2) 2.74 (2H，m) 8 27.3 (CH2) 3.52 (2H，m) 9 133.5 (C) 10 165.3 (C) 11 52.7 (CH3) 4.00 (3H，s) [1] 中国科学院中国植物志编辑委员会. 中国植物志 (第57卷)[M]. 北京: 科学出版社, 1999: 16. Flora of China Editorial Board, Chinese Academy of Sciences. Flora of China (Vol. 57)[M]. Beijing: Science Press, 1999: 16.

Flora of China Editorial Board, Chinese Academy of Sciences. Flora of China (Vol. 57)[M]. Beijing: Science Press, 1999: 16.

[2] 陈新涛, 吕光辉, 陈黎. 大白杜鹃中萜类化学成分研究[J]. 中国现代中药, 2018, 20(11): 1347 - 1350 . DOI: 10.13313/j.issn.1673-4890.20180615006. Chen X T, Lv G H, Chen L. Terpenoids Isolated from Rhododendron decorum[J]. Modern Chinese Medicine, 2018, 20(11): 1347 - 1350 .

Chen X T, Lv G H, Chen L. Terpenoids Isolated from Rhododendron decorum[J]. Modern Chinese Medicine, 2018, 20(11): 1347-1350. doi: 10.13313/j.issn.1673-4890.20180615006

[3]

Zhang W D, Jin H Z, Chen G, et al. A new grayanane diterpenoid from Rhododendron decorum[J]. Fitoterapia, 2008, 79(7): 602 - 604 . DOI: 10.1016/j.fitote.2008.04.009.

[4] 杜秀宝, 张常麟, 颜松民, 等. 大白花杜鹃有毒成分的研究[J]. 中草药, 1992, 23(9): 456 - 458 . Du X B, Zhang C L, Yan S M, et al. Studies on the toxic constituents of Rhododendron decorum[J]. Chinese Traditional and Herbal Drugs, 1992, 23(9): 456 - 458 .

Du X B, Zhang C L, Yan S M, et al. Studies on the toxic constituents of Rhododendron decorum[J]. Chinese Traditional and Herbal Drugs, 1992, 23(9): 456-458.

[5] 潘胜利. 百花食谱之二十八: 杜鹃花[J]. 园林, 2008(5): 72 - 73 . DOI: 10.3969/j.issn.1000-0283.2008.05.030. Pan S L. The hundred flowers recipe ⅩⅩⅧ Rhododendron[J]. Garden, 2008(5): 72 - 73 .

Pan S L. The hundred flowers recipe ⅩⅩⅧ Rhododendron[J]. Garden, 2008(5): 72-73. doi: 10.3969/j.issn.1000-0283.2008.05.030

[6]

Ohba M, Izuta R. Effect of copper(Ⅱ) triflate on intramolecular Diels-Alder reaction of oxazole-olefins[J], Heterocycles, 2001, 55(5): 823-826. DOI: 10.3987/com-01-9159.

[7]

Iwata N, Wang N L, Yao X S, et al. Structures and histamine release inhibitory effects of prenylated orcinol derivatives from Rhododendron dauricum[J]. Journal of Natural Products, 2004, 67(7): 1106 - 1109 . DOI: 10.1021/np0303916.

[8]

Rudiyansyah, Garson M J. Secondary metabolites from the wood bark of Durio zibethinus and Durio kutejensis[J]. Journal of Natural Products, 2006, 69(8): 1218 - 1221 . DOI: 10.1021/np050553t.

[9]

Yang B, Long J Y, Pang X Y, et al. Structurally diverse polyketides and phenylspirodrimanes from the soft coral-associated fungus Stachybotrys chartarum SCSIO41201[J]. The Journal of Antibiotics, 2020, 74(3): 190 - 198 . DOI: 10.1038/s41429-020-00386-y.

[10]

Nankai H, Miyazawa M, Kameoka H. Biotransformation of (2Z, 6Z)-farnesol by the plant pathogenic fungus Glomerella cingulata[J]. Phytochemistry, 1998, 47(6): 1025 - 1028 . DOI: 10.1016/s0031-9422(98)80065-4.

[11]

Ishikawa T, Kondo K, Kitajima J. Water-soluble constituents of coriander[J]. Chemical & Pharmaceutical Bulletin, 2003, 51(1): 32 - 39 .

[12]

Knapp H, Straubinger M, Fornari S, et al. (S)-3, 7-dimethyl-5-octene-1, 7-diol and related oxygenated monoterpenoids from petals of Rosa damascena Mill[J]. Journal of Agricultural and Food Chemistry, 1998, 46(5): 1966 - 1970 . DOI: 10.1021/jf970987x.

[13]

D’Abrosca B, DellaGreca M, Fiorentino A, et al. Structure elucidation and phytotoxicity of C13 nor-isoprenoids from Cestrum parqui[J]. Phytochemistry, 2004, 65(4): 497 - 505 .

[14]

Siddiqui B S, Nadeem Kardar M, Tariq Ali S, et al. Two new and a known compound from Lawsonia inermis[J]. Helvetica Chimica Acta, 2003, 86(6): 2164 - 2169 . DOI: 10.1002/hlca.200390174.

[15]

Kisiel W, Michalska K, Szneler E. Norisoprenoids from aerial parts of Cichorium pumilum[J]. Biochemical Systematics and Ecology, 2004, 32(3): 343 - 346 . DOI: 10.1016/j.bse.2003.08.005.

[16] 梁梦琳, 李清, 龙勇兵, 等. 刺梨的化学成分鉴定及其抗菌活性[J]. 贵州农业科学, 2019, 47(5): 10 - 13 . Liang M L, Li Q, Long Y B, et al. Identification of chemical constituents of Rosa roxbunghii and their antibocterial activities[J]. Guizhou Agricultural Sciences, 2019, 47(5): 10 - 13 .

Liang M L, Li Q, Long Y B, et al. Identification of chemical constituents of Rosa roxbunghii and their antibocterial activities[J]. Guizhou Agricultural Sciences, 2019, 47(5): 10-13.

[17] 周兴栋, 程淼, 余绍福, 等. 锡叶藤的化学成分研究[J]. 中草药, 2015, 46(2): 185 - 188 . DOI: 10.7501/j.issn.0253-2670.2015.02.006. Zhou X D, Cheng M, Yu S F, et al. Chemical constituents from Tetracera asiatica[J]. Chinese Traditional and Herbal Drugs, 2015, 46(2): 185 - 188 .

Zhou X D, Cheng M, Yu S F, et al. Chemical constituents from Tetracera asiatica[J]. Chinese Traditional and Herbal Drugs, 2015, 46(2): 185-188. doi: 10.7501/j.issn.0253-2670.2015.02.006

[18] 马雪, 李小双, 李银, 等. 酢浆草的化学成分研究(Ⅱ)[J]. 中药材, 2020, 43(4): 853 - 857 . DOI: 10.13863/j.issn1001-4454.2020.04.013. Ma X, Li X S, Li Y, et al. Chemical constituents of Oxalis corniculata(Ⅱ)[J]. Journal of Chinese Medicinal Materials, 2020, 43(4): 853 - 857 .

Ma X, Li X S, Li Y, et al. Chemical constituents of Oxalis corniculata(Ⅱ)[J]. Journal of Chinese Medicinal Materials, 2020, 43(4): 853-857. doi: 10.13863/j.issn1001-4454.2020.04.013

[19]

Marzouk M S, Soliman F M, Shehata I A, et al. Flavonoids and biological activities of Jussiaea repens[J]. Natural Product Research, 2007, 21(5): 436 - 443 . DOI: 10.1080/14786410600943288.

[20] 王静, 陆维丽, 张义龙, 等. 老鹰茶的化学成分研究[J]. 安徽医科大学学报, 2014, 49(4): 479 - 483 . DOI: 10.19405/j.cnki.issn1000-1492.2014.04.015. Wang J, Lu W L, Zhang Y L, et al. Chemical constituents from Litsea Coreana L.[J]. Acta Universitatis Medicinalis Anhui, 2014, 49(4): 479 - 483 .

Wang J, Lu W L, Zhang Y L, et al. Chemical constituents from Litsea Coreana L.[J]. Acta Universitatis Medicinalis Anhui, 2014, 49(4): 479-483. doi: 10.19405/j.cnki.issn1000-1492.2014.04.015

[21] 饶高雄, 戴云华, 王立新, 等. 蕨叶藁本的化学成分[J]. 云南植物研究, 1991(2): 233 - 236 . Ran G X, Dai Y H, Wang L X, et al. Chemical constituents from Ligusticum pteridophyllum[J]. Acta Botanica Yunnanica, 1991(2): 233 - 236 .

Ran G X, Dai Y H, Wang L X, et al. Chemical constituents from Ligusticum pteridophyllum[J]. Acta Botanica Yunnanica, 1991(2): 233-236.

[22]

Wu Y B, Zheng C J, Qin L P, et, al. Antiosteoporotic activity of anthraquinones from Morinda officinalis on osteoblasts and osteoclasts[J]. Molecules, 2009, 14(1): 573 - 593 . DOI: 10.3390/molecules14010573.