DOI: 10.11931/guihaia.gxzw202308076
侯萍, 任晨陽, 黃艷, 等, 2024.
紅葉野桐葉中的木脂素類化合物 [J].
廣西植物, 44(6): 1151-1158.
HOU P, REN CY, HUANG Y, et al., 2024.
Lignans from the leaves of Mallotus paxii [J].
Guihaia, 44(6): 1151-1158.
摘" 要:" 為探究紅葉野桐(Mallotus paxii )葉的化學(xué)成分,該研究采用正相硅膠、反相硅膠C18、葡聚糖凝膠Sephadex LH-20、反相半制備高效液相等色譜方法對紅葉野桐葉提取物進(jìn)行分離、純化,利用1H-NMR、13C-NMR、HR-ESI-MS等波譜數(shù)據(jù),結(jié)合參考文獻(xiàn),鑒定化合物的結(jié)構(gòu)。結(jié)果表明:從紅葉野桐葉中分離得到12個(gè)木脂素類化合物,分別是7″,8″-threo-buddlenol D (1)、buddlenol D (2)、7″,8″-threo-buddlenol C (3)、buddlenol C (4)、(+)-丁香脂素 (5)、表松脂醇 (6)、松脂素 (7)、1-acetoxyl-2e,6e-dipiperonyl-3,7-dioxabicyclo-[3,3,0]-octane (8)、刺五加酮(9)、落葉松脂醇-4′-O-β-D-吡喃葡萄糖苷 (10)、rel-(2α,3β)-7-O-methylcedrusin (11)和dihydrodehydrodiconiferyl-alcohol 4′-O-β-D-glucoside(12)。以上木脂素類化合物均為首次從該植物中分離得到,部分木脂素類化合物具有良好的藥理活性如抗菌、抗腫瘤、抗病毒等。該研究結(jié)果表明,紅葉野桐葉中含有豐富且活性良好的木脂素類化合物,說明其良好的藥用價(jià)值可能與這些木脂素類化合物有關(guān)。
關(guān)鍵詞: 野桐屬, 紅葉野桐, (+)-丁香脂素, 刺五加酮, 松脂素
中圖分類號:" Q946
文獻(xiàn)標(biāo)識(shí)碼:" A
文章編號:" 1000-3142(2024)06-1158-08
收稿日期: 2023-11-08
接受日期: 2023-12-14
基金項(xiàng)目:" 國家自然科學(xué)基金(32060097)。
第一作者: 侯萍(1998—),碩士研究生,主要從事天然藥物化學(xué)研究,(E-mail)418002643@qq.com。
*通信作者:" 李俊,博士,教授,博士生導(dǎo)師,主要從事天然產(chǎn)物化學(xué)研究,(E-mail)lijun9593@gxnu.edu.cn。
Lignans from the leaves of Mallotus paxii
HOU Ping1,2, REN Chenyang1,2, HUANG Yan1,2, PAN Liwei1,2,
PENG Liuting1,2, GAN Chunqiu1,2, LI Jun1,2*
( 1. School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, Guangxi, China; 2. State Key Laboratory
for Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University), Guilin 541004, Guangxi, China )
Abstract:" Mallotus paxii is a Euphorbiaceae plant belonging to the genus Mallotus Lour. This genus mainly distributes in tropical and subtropical Asia, and there are about 140 species in the world. There are 36 species in China, including 11 varieties, which mainly grow in Guangxi, Guangdong and Hainan." To study the compounds of Mallotus paxii, twelve lignans were isolated from the leaves of M. paxii" by means of various column chromatographic techniques, including silica gel, ODS, Sephadex LH-20 and preparative RP-HPLC methods. The structures of the isolated lignans were determined on the basis of analyses of spectroscopic methods (1H- and 13C-NMR spectroscopy), high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), and comparison of their spectroscopic data with previously reported data. The lignans were identified as 7″,8″-threo-buddlenol D (1), buddlenol D (2), 7″,8″-threo-buddlenol C (3), buddlenol C (4), (+)-syringaresinol (5), epipinoresinol (6), pinoresinol (7), 1-acetoxyl-2e,6e-dipiperonyl-3,7-dioxabicyclo-[3,3,0]-octane (8), ciwujiatone (9), lariciresinol-4′-O-β-D-glucopyranoside (10), rel-(2α,3β)-7-O-methylcedrusin (11), and dihydrodehydrodiconiferyl-alcohol 4′-O-β-D-glucoside (12). All compounds were isolated from M. paxii" for the first time. Some lignans have good pharmacological activities such as antibacterial, anti-inflammatory, anti-tumor and anti-virus. The results of this study show that the leaves of M. paxii are rich in lignans with good activity, indicating that its good medicinal value may be related to these lignans.
Key words: Mallotus, Mallotus paxii , (+)-syringaresinol, ciwujiatone, pinoresinol
野桐屬(Mallotus Lour.)屬于大戟科(Euphorbiaceae)植物,全球共約140種,主要分布于東南亞和東亞地區(qū)。我國有36種,其中包括11個(gè)變種,主產(chǎn)于南方地區(qū)如廣西、廣東、湖南等。野桐屬植物根部常入藥,具有清熱、止血、消炎、護(hù)肝、抗菌等功效(中國科學(xué)院中國植物志編輯委員會(huì),1996;廣西中藥資源大典編輯委員會(huì),2022),故常被用于治療慢性肝炎、止血抗菌。野桐屬植物中含有豐富的木脂素類化合物,其中的部分木脂素類化合物具有抗炎、抗菌、抗氧化、抗腫瘤等活性(陳德力等,2014;張艷軍等,2017;Lai et al., 2021;霍曉敏等,2023)。
紅葉野桐(Mallotus paxii),主要分布于廣西、廣東、湖南、湖北等地區(qū)?!吨袊幹矆D鑒》介紹其可“調(diào)整消化功能,治胃潰瘍、十二指腸潰瘍。”紅葉野桐具有抗炎、抗菌等藥用價(jià)值(Zhang et al., 2020)。迄今為止,對紅葉野桐的化學(xué)成分研究鮮有報(bào)道。為了更加深入了解紅葉野桐的化學(xué)成分,對紅葉野桐葉75%乙醇提取物進(jìn)行了分離純化,從中分離得到12個(gè)木脂素類化合物。這些木脂素類化合物均為首次從該植物中分離得到,其結(jié)構(gòu)式如圖1所示。
1" 材料與儀器
1.1 材料
實(shí)驗(yàn)藥材于2021年7月采自廣西欽州,經(jīng)廣西植物研究所黃俞淞研究員鑒定為紅葉野桐(Mallotus paxii),植物標(biāo)本(No. ID20210718)存放于廣西師范大學(xué)化學(xué)與藥學(xué)學(xué)院國家重點(diǎn)實(shí)驗(yàn)室天然產(chǎn)物研究室。
1.2 儀器和試劑
Waters e2695分析型HPLC(美國Waters);Bruker AVANCE 400/600 MHz 核磁共振儀(德國Merch Orugs amp; Biotechnology);Agilent 6545 Q-TOF LC-MS 高分辨質(zhì)譜儀/1260型半制備HPLC (美國Agilent Technologies Inc);柱層析硅膠(37~74 μm)和薄層色譜硅膠板(G254)(青島海洋化工有限公司);ODS填料、Sephadex LH-20填料、MCI填料(德國Merck Drugs amp; Biotechnology)(北京綠百草科技發(fā)展有限公司)。
2" 方法
取干燥紅葉野桐葉15.0 kg,砍碎,室溫下用75%乙醇提取3次 (3 × 50 L),合并提取液,過濾、濃縮,得浸膏1.3 kg。將浸膏分散于H2O中,依次用石油醚、乙酸乙酯、正丁醇萃取,得到相應(yīng)溶劑的萃取物。將乙酸乙酯部分 (300 g)用硅膠 (200~300目)拌樣,經(jīng)硅膠柱層析,以二氯甲烷-甲醇 (100∶0、95∶5、90∶10、85∶15、80∶20、70∶30、50∶50、0∶100,V/V)梯度洗脫,得到Fr.A-Fr.H共8個(gè)部分。
將Fr.E (28 g) 經(jīng)小孔樹脂MCI柱層析,用H2O-CH3OH (100∶0→0∶100,V/V)洗脫,得到Fr.E.1-Fr.E.6共6個(gè)組分。Fr.E.3 (3.5 g)用硅膠 (200~300目)拌樣,經(jīng)硅膠柱層析,用CH2Cl2-CH3OH (100∶0→50∶50,V/V) 進(jìn)行梯度洗脫,得到Fr.E.3.1-Fr.E.3.6 共6個(gè)亞組分。Fr.E.3.1經(jīng)Sephadex LH-20柱層析,利用CH3OH洗脫,得到組分Fr.E.3.1.1-Fr.E.3.1.5。組分Fr.E.3.1.2經(jīng)C18半制備高效液相色譜(HPLC)(H2O-CH3CN" 70∶30,V/V)洗脫,得化合物1 (3.0 mg)、化合物3 (4.5 mg)。組分Fr.E.3.1.3經(jīng)C18半制備HPLC(H2O-CH3CN 70∶30,V/V)洗脫,得化合物2 (3.7 mg)和化合物4 (3.2 mg)。Fr.E.3.4經(jīng)Sephadex LH-20柱層析,利用CH3OH洗脫,得到組分Fr.E.3.4.1-Fr.E.3.4.3。組分Fr.E.3.4.1經(jīng)C18半制備HPLC(H2O-CH3CN 68∶32,V/V)洗脫,得化合物5 (2.3 mg)、化合物8 (2.9 mg)。組分Fr.E.3.4.3經(jīng)C18半制備HPLC(H2O-CH3CN 68∶32,V/V)洗脫,得化合物6 (3.3 mg)、化合物7 (4.7 mg)、化合物9 (1.8 mg)。Fr.E.5 (4.5 g)用硅膠柱 (200~300目)拌樣,經(jīng)硅膠柱層析,用CH2Cl2-CH3OH (100∶0→50∶50,V/V) 進(jìn)行梯度洗脫,得到Fr.E.5.1-Fr.E.5.7共5個(gè)亞組分。Fr.E.5.1經(jīng)Sephadex LH-20柱層析,利用CH3OH洗脫,得到組分Fr.E.5.1.1-Fr.E.5.1.4。組分Fr.E.5.1.2經(jīng)C18半制備HPLC(H2O-CH3CN 58∶42,V/V)洗脫,得化合物11 (4.8 mg)。組分Fr.E.5.1.4經(jīng)C18半制備HPLC(H2O-CH3CN 55∶45,V/V)洗脫,得化合物10 (3.7 mg)。Fr.E.5.5經(jīng)Sephadex LH-20柱層析,利用CH3OH洗脫,得到組分Fr.E.5.5.1-Fr.E.5.5.4。組分Fr.E.5.5.2經(jīng)C18半制備HPLC(H2O-CH3CN 50∶50,V/V)洗脫,得化合物12 (3.1 mg)。
3" 化合物結(jié)構(gòu)鑒定
化合物1" 淡黃色固體(CH3OH)。α20D-3.0 (c 0.05, CH3OH); IR (KBr) νmax 3 346, 2 939, 2 841, 1 614, 1 519, 1 462, 1 425, 1 326, 1 218, 1 118, 829, 702 cm-1; mp.132~135 ℃。HR-ESI-MS m/z: 645.253 9[M + H]+ (calcd for C33H41O13, 645.254 7)。1H-NMR (600 MHz, CD3OD) δH: 6.65 (2H, d, J=2.4 Hz, H-2, 6), 6.64 (2H, br s, H-2′, H-6′), 6.63 (2H, d, J=3.6 Hz, H-2″, 6″), 4.88 (1H, t, J = 5.4 Hz, H-7″), 4.75 (1H, br d, J=3.0 Hz, H-7′)," 4.69 (1H, br d, J=3.0 Hz, H-7), 4.28 (3H, m, H-9a, 9′a, 8″), 3.90 (3H, m, H-9b, 9′b, 8″), 3.85 (6H, s, 3, 5-OCH3), 3.83 (6H, d, J=0.6 Hz, 3′, 5′-OCH3), 3.81 (6H, d, J=2.4 Hz, 3″, 5″-OCH3), 3.62 (1H, m, H-9″a), 3.30 (1H, overlap, H-9″b), 3.15 (2H, m, H-8, 8′);13C-NMR (150 MHz, CD3OD) δC: 154.5 (C-3, 5), 149.3 (C-3′, 5′),148.9 (C-3″, 5″), 138.9 (C-1), 136.2 (C-4, 4′), 135.8 (C-4″), 133.1 (C-1′), 133.0 (C-1″), 105.2 (C-2″, 6″), 104.5 (C-2′, 6′), 104.2 (C-2, 6), 87.6 (C-7), 87.3 (C-8″), 87.2 (C-7′), 74.3 (C-7″), 73.0 (C-9), 72.9 (C-9′), 61.8 (C-9″), 56.8 (3, 5-OCH3), 56.7 (3′, 5′, 3″, 5″-OCH3), 55.7 (C-8), 55.5 (C-8′)。以上數(shù)據(jù)與文獻(xiàn)(劉祥忠等,2020)報(bào)道的基本一致,故鑒定化合物1為7″,8″-threo-buddlenol D。
化合物2" 淡黃色固體(CH3OH)。α20D-5.0 (c 0.10, CH3OH); IR (KBr) νmax 3 441, 2 939, 2 842, 1 613, 1 519, 1 462, 1 326, 1 218, 1 119, 830, 702 cm-1; mp.142~144℃。HR-ESI-MS m/z: 645.254 1[M + H]+ (calcd for C33H41O13, 645.254 7)。1H-NMR (600 MHz, CD3OD) δH: 6.72 (2H, s, H-2,6), 6.70 (2H, s, H-2′, 6′), 6.67 (2H, s, H-2″, 6″), 4.99 (1H, d, J = 6.7 Hz, H-7″), 4.78 (1H, d, J=4.9 Hz, H-7′), 4.73 (1H, d, J=4.8 Hz, H-7), 4.33 (1H, t, J=8.2 Hz, H-9a), 4.28 (1H, t, J=8.2 Hz, H-9′a), 4.17 (1H, m, H-8″), 3.94 (1H, d, J=8.2 Hz, H-9b), 3.92 (1H, d, J=8.2 Hz, H-9′b), 3.89 (6H, s, 3, 5-OCH3 ), 3.87 (6H, s, 3′, 5′-OCH3 ), 3.83 (6H, s, 3″, 5″-OCH3), 3.80 (1H, ddd, J=11.8, 4.2, 1.2 Hz, H-9″a), 3.43 (1H, ddd, J=11.8, 4.2, 1.2 Hz, H-9″b), 3.13 (2H, m, H-8, 8′);13C-NMR (150 MHz, CD3OD) δC: 154.5 (C-3, 5), 149.3 (C-3′, 5′), 148.8 (C-3″, 5″), 138.9 (C-1), 136.2 (C-4, 4′), 135.8 (C-4″), 133.1 (C-1′), 132.9 (C-1″), 105.2 (C-2″, 6″), 104.6 (C-2′, 6′), 104.1 (C-2, 6), 88.4 (C-8″), 87.6 (C-7), 87.2 (C-7′), 74.4 (C-7″), 73.0 (C-9), 72.9 (C-9′), 61.8 (C-9″), 56.8 (3, 5-OCH3), 56.7 (3′, 5′, 3″, 5″-OCH3), 55.7 (C-8), 55.4 (C-8′)。以上數(shù)據(jù)與文獻(xiàn)(劉祥忠等,2020)報(bào)道的基本一致,故鑒定化合物2為buddlenol D。
化合物3" 淡黃色固體(CH3OH)。α20D-3.0 (c 0.05, CH3OH); IR (KBr) νmax 3 303, 2 962, 1 593, 1 518, 1 463, 1 262, 1 224, 1 113, 1 028, 803 cm-1; mp. 164~166 ℃。HR-ESI-MS m/z: 615.222 7[M + H]+(calcd for C32H9O12, 615.224 2)。1H-NMR (600 MHz, CD3OD) δH: 6.96 (1H, d, J = 1.7 Hz, H-2″), 6.84 (1H, dd, J = 8.2, 1.8 Hz, H-5″), 6.75 (1H, d, J = 8.2 Hz, H-6″), 6.67 (2H, br s, H-2′, 6′), 6.64 (2H, s, H-2, 6), 4.95 (1H, d, J=7.3 Hz, H-7″), 4.73 (1H, d, J =4.4 Hz, H-7), 4.71 (1H, d, J=4.9 Hz, H-7′), 4.29 (2H, m, H-9a, 9′a), 4.10 (1H, m, H-8″), 3.95 (1H, d, J =3.4 Hz, H-9b), 3.92 (1H, d, J =3.4 Hz, H-9′b), 3.88 (6H, s, 3, 5-OCH3), 3.86 (6H, s, 3′, 5′-OCH3), 3.81 (3H, s, 3″-OCH3), 3.77 (1H, ddd, J=12.1, 4.2, 1.8 Hz, H-9″a), 3.34 (1H, ddd, J =12.1, 4.2, 1.8 Hz, H-9″b), 3.12 (2H, m, H-8, 8′); 13C-NMR (150 MHz, CD3OD) δC: 154.5 (C-3, 5), 149.3 (C-3′, 5′), 148.6 (C-3″), 147.1 (C-4″), 139.0 (C-1), 136.7 (C-4′), 136.2 (C-4), 133.4 (C-1″), 133.0 (C-1′), 120.7 (C-6″), 115.8 (C-5″), 111.6 (C-2″), 104.5 (C-2′, 6′), 104.2 (C-2, 6), 88.7 (C-8″), 87.6 (C-7), 87.3 (C-7′), 74.4 (C-7″), 73.0 (C-9), 72.9 (C-9′), 61.8 (C-9″), 56.8 (3, 5-OCH3), 56.7 (3′, 5′-OCH3), 56.3 (3″-OCH3), 55.8 (C-8), 55.4 (C-8′)。以上數(shù)據(jù)與文獻(xiàn)(劉祥忠等,2020)報(bào)道的基本一致,故鑒定化合物3為7″,8″-threo-buddlenol C。
化合物4" 白色無定型粉末(CH3OH)。α20D-5.0 (c 0.10, CH3OH); IR (KBr) νmax 3 450, 2 940, 2 842, 1 593, 1 518, 1 463, 1 425, 1 368, 1 328, 1 273, 1 221, 1 121, 1 059, 1 033, 826, 702 cm-1; mp.118~119 ℃。HR-ESI-MS m/z: 615.223 8[M + H]+ (calcd for C32H39O12, 615.224 2)。1H-NMR (600 MHz, CD3OD) δH: 6.96 (1H, dd, J = 4.2 Hz, H-2″), 6.75 (1H,br d, J = 7.8 Hz, H-5″), 6.72 (1H, dd, J=7.8, 1.8 Hz, H-6″), 6.67 (2H, br s, H-2′, 6′), 6.64 (2H, s, H-2, 6), 4.95 (1H, d, J=4.3 Hz, H-7″), 4.73 (1H, d, J =2.4 Hz, H-7), 4.71 (1H, d, J=3.5 Hz, H-7′), 4.29 (3H, m, H-8″, 9a, 9′a), 3.93 (1H, m, H-9″a), 3.90 (2H, m, H-9b, 9′b), 3.87 (6H, s, 3, 5-OCH3), 3.84 (9H, s, 3′, 5′, 3″-OCH3), 3.55 (1H, dt, J =12.0, 1.8 Hz, H-9″b), 3.14 (2H, m ,H-8, 8′); 13C-NMR (150 MHz, CD3OD) δC: 154.5 (C-3, 5), 149.3 (C-3′, 5′), 148.5 (C-3″), 147.0 (C-4″), 138.9 (C-1), 136.3 (C-4′), 136.2 (C-4), 133.6 (C-1″), 133.0 (C-1′), 120.7 (C-6″), 115.7 (C-5″), 111.5 (C-2″), 104.4 (C-2′, 6′), 104.3 (C-2, 6), 87.6 (C-7), 87.3(C-8″), 87.2 (C-7′), 74.2 (C-7″), 73.0 (C-9), 72.9 (C-9′), 61.9 (C-9″), 56.8 (3, 5-OCH3), 56.7 (3′, 5′-OCH3), 56.3 (3″-OCH3), 55.7 (C-8), 55.5 (C-8′)。以上數(shù)據(jù)與文獻(xiàn)(劉祥忠等,2020)報(bào)道的基本一致,故鑒定化合物4為buddlenol C。
化合物5" 無色膠狀物(CH3OH)。α20D+4.7 (c 0.10, CHCl3); IR (KBr) νmax 3 400, 1 610, 1 505 cm-1; mp.180~182 ℃。HR-ESI-MS m/z: 441.152 1[M + Na]+ (calcd for C22H26NaO8, 441.152 5)。1H-NMR (600 MHz, CD3OD) δH: 6.63 (4H, s, H-2′, 6′, 2″, 6″), 4.69 (2H, d, J=4.1 Hz, H-2, 6), 4.24 (2H, dd, J = 9.0, 6.8 Hz, H-4a, 8a), 3.85 (2H, dd, J=9.2, 3.3 Hz, H-4b, 8b), 3.82 (12H, s, 3′, 5′, 3″, 5″-OCH3), 3.12 (2H, m, H-1, 5); 13C-NMR (150 MHz, CD3OD) δC: 149.3 (C-3′, 5′, 3″, 5″), 136.1 (C-4′, 4″), 133.1 (C-1′, 1″), 104.4 (C-2′, 6′, 2″, 6″), 87.6 (C-2, 6), 72.7 (C-4, 8), 57.8 (3′, 5′, 3″, 5″-OCH3), 55.5 (C-1, 5)。以上數(shù)據(jù)與文獻(xiàn)(Hyun et al., 2009)報(bào)道的基本一致,故鑒定化合物5為(+)-丁香脂素。
化合物6" 黃色無定型粉末(CH3OH)。α20D-118.9 (c 0.10, CH3OH); IR (KBr) νmax 3 324, 1 595, 1 501 cm-1; mp. 141~142 ℃。HR-ESI-MS m/z: 359.149 1[M + H]+ (calcd for C20H23O6, 359.149 5)。1H-NMR (600 MHz, CD3OD) δH: 6.95 (1H, d, J=1.8 Hz, H-2), 6.93 (1H, d, J=1.9 Hz, H-2′), 6.78 (2H, m, H-5, 6), 6.75 (2H, m, H-5′, 6′), 4.83 (1H, d, J=6.0 Hz, H-7), 4.39 (1H, d, J=7.0 Hz, H-7′), 4.08 (1H, d, J=9.2 Hz, H-9′b), 3.84 (3H, s, 3-OCH3 ), 3.82 (1H, m, H-9′a), 3.77 (2H, m, H-9), 3.36 (1H, m, H-8), 2.92 (1H, m, H-8); 13C-NMR (150 MHz, CD3OD) δC: 149.3 (C-4′), 148.9 (C-4), 147.6 (C-3′), 146.8 (C-3), 133.8 (C-1′), 131.5 (C-1), 120.2 (C-6′), 119.5 (C-6), 116.1 (C-5′), 116.0 (C-5), 110.9 (C-2″), 110.6 (C-2), 89.5 (C-7′), 83.7 (C-5), 72.1 (C-9′), 70.8 (C-9), 56.5 (3,3′-OCH3), 55.8 (C-8′), 51.4 (C-8)。以上數(shù)據(jù)與文獻(xiàn)(申海艷等,2012)報(bào)道的基本一致,故鑒定化合物6為表松脂醇。
化合物7" 黃色無定型粉末(CH3OH)。α20D-28.5 (c 0.10, CH3OH); IR (KBr) νmax 3 327, 1 598, 1 507 cm-1; mp.119~120 ℃。HR-ESI-MS m/z: 359.134 2[M-H]- (calcd for C20H21O6, 359.133 8)。1H-NMR (600 MHz, CD3OD) δH: 6.93 (2H, d, J=1.8 Hz, H-2, 20), 6.78 (2H, dd, J=8.4, 2.0 Hz, H-6, 6′), 6.75 (2H, d, J=8.4 Hz, H-5, 5′), 4.69 (2H, d, J=4.4 Hz, H-7, 7′), 4.20 (2H, dd, J=9.2, 6.8 Hz, H-9a, 9′a), 3.84 (6H, s, 3, 3′-OCH3), 3.75 (2H, dd, J=9.2, 6.3 Hz, H-9b, 9′b), 3.11 (2H, m, H-8, H-8′); 13C-NMR (150 MHz, CD3OD) δC: 149.1 (C-3, 3′), 147.3 (C-4, 4′), 133.8 (C-1, 1′), 120.1 (C-6, 6′), 116.1 (C-5, 5′), 110.9 (C-2, 2′), 87.5 (C-7, 7′), 72.6 (C-9, 9′), 56.4 (3,3′-OCH3), 55.4 (C-8, 8′)。以上數(shù)據(jù)與文獻(xiàn)(In et al., 2015)報(bào)道的基本一致,故鑒定化合物7為松脂素。
化合物8" 白色晶體(CH3OH)。α20D+34.5 (c 0.47, CHCl3); IR (KBr) νmax 3 076, 2 992, 2 931, 2 877, 2 798, 1 855, 1 746, 1 608, 1 503, 1 488, 1 446, 1 364, 1 256, 1 241, 1 206, 1 039, 1 014, 934, 882, 811, 785, 744 cm-1; mp.168~193 ℃。HR-ESI-MS m/z: 413.125 7[M + H]+ (calcd for C22H21O8, 413.123 6)。1H-NMR (500 MHz, CDCl3) δH: 6.92 (1H, d, J=1.2 Hz, H-2″), 6.86~6.74 (5H, m, H-2′, 6′, 6″, 5′, 5″), 5.97 (2H, s, H-7′), 5.94 (2H, d, J=1.0 Hz, H-7″), 5.03 (1H, s, H-2b), 4.72 (1H, d, J=5.0 Hz, H-6b), 4.41 (2H, dd, J=14.1, 7.2 Hz, H-4a, 8a ), 4.22 (1H, d, J=10.8 Hz, H-8b), 3.76 (1H, dd, J=9.4, 4.8 Hz, H-4b), 3.28 (1H, dt, J=7.6, 4.9 Hz, H-5a), 1.75 (3H, s, -O=C-CH3); 13C-NMR (125 MHz, CDCl3) δC: 169.5 (C=O), 148.2 (C-4″), 147.7 (C-3″), 147.5 (C-3′, 4′), 134.1 (C-1″), 130.3 (C-1′), 122.4 (C-6′), 120.0 (C-6″), 109.0 (C-2′), 108.3 (C-5″), 108.1 (C-5′), 106.9 (C-2″), 101.3 (C-7″), 101.2 (C-7′), 97.3 (C-1), 86.9 (C-2), 85.9 (C-6), 75.3 (C-8), 70.0 (C-4), 59.1 (C-5), 21.1 (-CH3-C=O)。以上數(shù)據(jù)與文獻(xiàn)(Jiang et al.,2000)報(bào)道的基本一致,故鑒定化合物8為1-acetoxyl-2e,6e-dipiperonyl-3,7-dioxabicyclo-[3,3,0]-octane。
化合物9" 淡黃色粉末(CH3OH)。α20D+34.5 (c 0.47, CH3OH); IR (KBr) νmax 3 322, 1 737 cm-1; mp.112~114 ℃。HR-ESI-MS m/z: 435.156 3[M + H]+ (calcd for C22H26O9, 435.157 7)。1H-NMR (600 MHz, CD3OD) δH: 7.38 (2H, s, H-2, H- 6), 6.71 (2H, s, H-2′, 6′), 4.63 (1H, d, J=8.2 Hz, H-7′), 4.23 (1H, m, H-8), 4.22 (1H, dd, J=8.6, 4.7 Hz, H-9a), 4.17 (1H, t, J=8.4 Hz, H-9b), 3.91 (6H, s, 3, 3′-OMe), 3.84 (6H, s, 5, 5′-OMe), 3.66 (2H, dd, J=12.8, 4.9 Hz, H-9′), 2.63 (1H, m, H-8′); 13C-NMR (150 MHz, CD3OD) δC: 200.4 (C-7), 149.2 (C-3, C-5), 149.1 (C-3′, C-5′), 142.3 (C-4), 136.3 (C-4′), 132.9 (C-1′), 128.7 (C-1), 107.7 (C-2, 6), 105.1 (C-2′, 6′), 85.5 (C-7′), 71.6 (C-9), 61.4 (C-9′), 56.9 (3, 3′, 5, 5′-OMe), 55.2 (C-8′), 50.1 (C-8)。以上數(shù)據(jù)與文獻(xiàn)(賈自立等,2022)報(bào)道的基本一致,故鑒定化合物9為刺五加酮。
化合物10" 白色無定形粉末(CH3OH)。α20D-19.3 (c 0.60, CH3OH); IR (KBr) νmax 3 312, 1 598, 1 515 cm-1; mp.161~162 ℃。HR-ESI-MS m/z: 545.200 1" [M+Na]+(calcd for C26H34O11Na, 545.199 9)。1H-NMR (400 MHz, CD3OD) δH: 6.98 (1H, d, J=3.6 Hz, H-2), 6.82 (1H, dd, J=7.8, 3.6 Hz, H-6), 6.79 (1H, d, J=7.8 Hz, H-5), 6.55 (1H, d, J=1.8 Hz, H-2″), 6.39 (1H, d, J=1.8 Hz, H-6′), 4.94 (1H, d, J=7.2 Hz, H-1″), 4.87 (1H, d, J=7.2 Hz, H-7), 4.07~4.04 (1H, m, H-8), 3.77 (3H, s, 3-OMe), 3.65 (1H, d, J=12.0 Hz, H-6″b), 3.54 (1H, dd, J=12.0, 4.2 Hz, H-9b), 3.47 (1H, dd, J=12.0, 6.6 Hz, H-6″a), 3.39 (2H, t, J=6.6 Hz, H-9′a, 9′b), 3.33 (1H, dd, J=12.0, 4.2 Hz, H-9a), 3.30~3.27 (1H, m, H-3″), 3.26~3.24 (2H, m, H-2″, 5″), 3.19~3.16 (1H, m, H-4″), 2.48~2.45 (2H, m, H-7′), 1.68~1.65 (2H, m, H-8′); 13C-NMR (100 MHz, CD3OD) δC: 150.7 (C-3′), 148.9 (C-3), 147.2 (C-4′), 145.9 (C-4), 138.7 (C-1′), 133.0 (C-1), 122.2 (C-6), 119.5 (C-6′), 117.9 (C-5′), 116.2 (C-5), 113.4 (C-2), 111.2 (C-2′), 102.7 (C-1″), 83.8 (C-7′), 78.1 (C-3″), 77.8 (C-5″), 74.9 (C-2″), 73.7 (C-9), 71.3 (C-4″), 62.6 (C-6″), 59.0 (C-9′), 56.7 (3′-OMe), 56.5 (3-OMe), 54.2 (C-8′), 45.5 (C-8), 35.4 (C-7)。以上數(shù)據(jù)與文獻(xiàn)(Sugiyama amp; Bailleul, 1993)報(bào)道的基本一致,故鑒定化合物10為落葉松脂醇-4′-O-β-D-吡喃葡萄糖苷。
化合物11" 白色粉末(CH3OH)。α20D-21.4 (c 0.10, CH3OH); IR (KBr) νmax 3 308, 2 948, 1 716, 1 645 cm-1; mp.119~120 ℃。HR-ESI-MS m/z: 361.167 5" [M+H]+(calcd for C20H25O6, 361.165 1)。1H-NMR (400 MHz, CD3OD) δH: 6.95 (1H, d, J=1.8 Hz, H-2′), 6.82 (1H, dd, J=8.2, 1.8 Hz, H-6′), 6.76 (1H, d, J=8.1 Hz, H-5′), 6.72 (2H, s, H-4, 6), 5.49 (1H, d, J=6.3 Hz, H-7′), 3.85 (3H, s, 3-OMe), 3.81 (3H, s, 3′-OMe), 3.58 (1H, t, J=6.5 Hz, H-9), 3.47 (1H, dt, J=6.3, 6.2 Hz, H-8′), 2.62 (1H, t, J=7.7 Hz, H-7), 1.81 (1H, tt, J=7.7, 6.5 Hz, H-8); 13C-NMR (100 MHz, CD3OD) δC: 149.1 (C-3′), 147.5 (C-4′), 147.4 (C-4), 145.2 (C-3), 136.9 (C-1), 134.9 (C-1′), 129.8 (C-5), 119.7 (C-6′), 117.7 (C-6), 116.2 (C-5′), 114.1 (C-2), 110.5 (C-2′), 88.8 (C-7′), 64.9 (C-9′), 62.2 (C-9), 56.7 (7-OMe), 56.4 (3′-OMe), 55.4 (C-8′), 35.7 (C-8), 32.9 (C-7)。以上數(shù)據(jù)與文獻(xiàn)(Seidel et al., 2000)報(bào)道的基本一致,故鑒定化合物11為rel-(2α, 3β)-7-O-methylcedrusin。
化合物12" 白色粉末(CH3OH)。α25D+78.4 (c 0.19, CH3OH); IR (KBr) νmax 3 303, 2 961, 1 706, 1 648, 1 514, 1 449, 1 259, 1 076, 1 032 cm-1; mp.144~145 ℃。HR-ESI-MS m/z: 523.216 6" [M+H]+(calcd for C26H35O11, 523.217 9)。1H-NMR (400 MHz, CD3OD) δH: 7.15 (1H, d, J=8.4 Hz, H-5′), 7.00 (1H, d, J=1.8 Hz, H-2′), 6.92 (1H, dd, J=8.4, 1.8 Hz, H-6′), 6.73(1H, s, H-2), 6.71 (1H, s, H-6), 5.57 (1H, d, J=5.9 Hz, H-7′), 4.84 (1H, d, J=7.2 Hz, H-1″), 3.85 (3H, s, 7-OMe), 3.82 (3H, s, 3-OMe), 2.62 (2H, dd, J=8.1, 7.3 Hz, H-7), 1.83 (2H, m, H-8); 13C-NMR (100 MHz, CD3OD) δC: 150.8 (C-3′), 147.6 (C-4′), 147.5 (C-4), 145.1 (C-3), 138.3 (C-1′), 137.1 (C-5), 129.5 (C-1), 119.5 (C-5′), 117.9 (C-6, 6′), 114.1 (C-2), 111.1 (C-2′), 102.6 (C-1″), 88.5 (C-7′), 78.1 (C-3″), 77.7 (C-5″), 74.8 (C-2″), 71.2 (C-4″), 64.9 (C-9′), 62.4 (C-6″), 62.2 (C-9), 56.7 (7-OMe), 56.5 (3-OMe), 55.5 (C-8′), 35.7 (C-8), 32.9 (C-7)。以上數(shù)據(jù)與文獻(xiàn)(Xiang et al., 2004)報(bào)道的基本一致,故鑒定化合物12為dihydrodehydrodiconiferyl-alcohol 4′-O-β-D-glucoside。
4" 討論與結(jié)論
本研究對紅葉野桐葉75%乙醇提取物的乙酸乙酯部位的化學(xué)成分進(jìn)行分離純化,得到12個(gè)木脂素類化合物,這些化合物均為首次從該植物中分離得到。這些化合物都具有良好的降血脂、抗病毒、抗腫瘤、抗骨質(zhì)疏松、抗氧化、抗炎等活性。其中,表松脂醇(6)可以顯著增強(qiáng)由高密度脂蛋白(HDL)介導(dǎo)的膽固醇流出,能夠顯著抑制RAW264.7細(xì)胞由氧化低密度脂蛋白(ox-LDL)誘導(dǎo)的膽固醇累積,同時(shí)還能夠顯著抑制膽固醇的流入,并且可以上調(diào)過氧化物增殖激活受體γ(PPARγ)、肝X受體α(LXRα)、ATP結(jié)合盒轉(zhuǎn)運(yùn)子A1(ABCA1)和ATP結(jié)合盒轉(zhuǎn)運(yùn)子G1(ABCG1)基因mRNA的水平,下調(diào)清道夫受體A1(SR-A1)和A2(SR-A2)基因mRNA的水平,在防治動(dòng)脈粥樣硬化方面具有潛在作用(王帥等,2015);落葉松脂醇-4′-O-β-D-吡喃葡萄糖苷(10)對甲型流感病毒誘導(dǎo)的MDCK細(xì)胞病變有明顯抑制作用,可以降低流感病毒誘導(dǎo)的IL-6、TNF-α、MCP-1、IP-10、IL-8和IFN-α的表達(dá)(Li et al., 2015);松脂素(7)與(+)-丁香脂素(5)都對Hela細(xì)胞有較好的抑制作用(張寶等,2023);刺五加酮(9)對宮頸癌細(xì)胞、人肝癌細(xì)胞、小鼠乳腺癌細(xì)胞、人肺癌細(xì)胞都具有一定的抑制活性(尹偉等,2018);松脂素(7)可以通過促進(jìn)OPG分泌或通過抑制RANKL表達(dá)來促進(jìn)成骨細(xì)胞的增殖和分化以達(dá)到抗骨質(zhì)疏松的作用(胡倩影等,2018);(+)-丁香脂素(5)可以通過抗氧化應(yīng)激、修復(fù)線粒體功能及DNA損傷等通路來降低谷氨酸鈉誘導(dǎo)的神經(jīng)細(xì)胞凋亡以達(dá)到對谷氨酸鈉誘導(dǎo)的SH-SY5Y神經(jīng)細(xì)胞的興奮性損傷的保護(hù)作用(嚴(yán)秋霞等,2019)。紅葉野桐葉中含有豐富且活性良好的木脂素類化合物,說明其良好的藥用價(jià)值可能與這些木脂素類化合物有關(guān)。
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(責(zé)任編輯" 鄧斯麗)