海南油楠葉的化學(xué)成分

張軍鋒， 陳祎平， 梁振益， 嵇莎莎， 林昭華

(海南大學(xué)材料與化工學(xué)院，海南?？?570228)

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海南油楠葉的化學(xué)成分

張軍鋒， 陳祎平*， 梁振益， 嵇莎莎， 林昭華

(海南大學(xué)材料與化工學(xué)院，海南海口 570228)

摘要[目的]明確海南油楠葉的化學(xué)成分。[方法]采用硅膠柱色譜對(duì)海南油楠葉的正己烷提取物和醋酸乙酯提取物進(jìn)行分離，根據(jù)理化性質(zhì)及波譜分析確定結(jié)構(gòu)。[結(jié)果]分離得到9個(gè)化合物，鑒定為木栓酮(1)、3β-3-壬氧基-12-齊墩果烯(2)、8R,9R-環(huán)氧-β-石竹烯(3)、蒲公英萜醇(4)、豆甾烷-5烯-3-醇(5)、麥角甾-5-烯-3-醇(6)、2α,3β,-二羥基-24-去甲基-4(23)-12-齊墩果烯(7)、齊墩果酸(8)和鄰苯二甲酸二戊酯(9)。[結(jié)論]化合物1～9均為首次從該植物的樹(shù)葉中分離得到。

關(guān)鍵詞油楠；化學(xué)成分；分離；木栓酮

油楠(SindoraglabraMerr.ex De Wit.)是蘇木科蚌殼樹(shù)屬植物，又名蚌殼樹(shù)、曲腳楠、科楠、脂樹(shù)等。油楠分布于東南亞的越南、泰國(guó)、馬來(lái)西亞、菲律賓等國(guó)和中國(guó)的海南島，同屬的植物廣泛分布于亞洲、非洲的熱帶地區(qū)的熱帶雨林中[1]。

油楠是熱帶、亞熱帶的能源樹(shù)種，高大喬木，高在3 m以上，胸徑可長(zhǎng)至1.5 m，生長(zhǎng)在山地海拔700 m以下的溝谷旁和山坡上的雜木林中。油楠在我國(guó)主要分布于海南島的樂(lè)東、陵水、東方、白沙、昌江、儋州和三亞等地。其樹(shù)干木質(zhì)內(nèi)含有一種豐富的淡棕色可燃性油質(zhì)液體，氣味清香，顏色如同煤油，可燃性能與柴油相似，經(jīng)過(guò)濾后可直接供柴油機(jī)使用，可作為柴油的代用品。油楠油還可用來(lái)做食用香料，油楠的種子可治療皮膚病。目前，國(guó)內(nèi)外關(guān)于油楠化學(xué)成分的研究已有報(bào)道，主要是脂肪酸和揮發(fā)油的成分分析，而關(guān)于海南油楠葉化學(xué)成分的研究國(guó)內(nèi)外鮮見(jiàn)報(bào)道。鑒于此，筆者研究了海南油楠葉的化學(xué)成分，以期為油楠的進(jìn)一步研究與開(kāi)發(fā)提供參考。

1材料與方法

1.1材料

1.1.1儀器與試劑。Bruker AM-400 型核磁共振波譜儀，TMS 為內(nèi)標(biāo); 薄層色譜硅膠板(山東煙臺(tái)化工廠生產(chǎn))，200～300目柱色譜硅膠(山東青島海洋化工廠) ，溶劑為西隴化工股份有限公司產(chǎn)品。

1.1.2供試植物。海南油楠葉采自海南省中部山區(qū)，由海南省林業(yè)科學(xué)研究所高級(jí)工程師李大周鑒定為SindoraglabraMerr.ex De Wit.(油楠)。樣品存放于熱帶島嶼資源先進(jìn)材料教育部重點(diǎn)實(shí)驗(yàn)室。

1.2試驗(yàn)方法將新采的海南油楠葉在室內(nèi)風(fēng)干，粉碎得新鮮的油楠葉(1 500.00 g),在室溫下用無(wú)水乙醇浸泡，濾過(guò)、濃縮，得濃縮液500 mL。濃縮液依次用正己烷、乙酸乙酯、正丁醇萃取得正己烷、乙酸乙酯和正丁醇提取物。取正己烷提取物(13.10 g)用硅膠柱色譜分離。洗脫液用石油醚-乙酸乙酯9∶1、7∶3、1∶1、2∶8進(jìn)行洗脫，得到19個(gè)組分(S1～S19)；S2經(jīng)一次硅膠柱色譜分離后重結(jié)晶得化合物 1 (37 mg)；S3經(jīng)一次硅膠柱色譜分離后得化合物 2(15 mg)和 3(10 mg)；S5經(jīng)一次硅膠柱色譜分離后重結(jié)晶得化合物4(10 mg)；S6經(jīng)一次硅膠柱色譜分離后重結(jié)晶得化合物5(36 mg)；S3經(jīng)一次硅膠柱色譜分離后得化合物 6(10 mg)和 7(10 mg)。取乙酸乙酯提取物(12.00 g)用硅膠柱色譜分離。洗脫液用石油醚-乙酸乙酯8∶2、1∶1、2∶8進(jìn)行洗脫，得到20個(gè)組分(J1～J20)；J3進(jìn)行重結(jié)晶得到化合物8(12 mg)；J7進(jìn)行柱色譜分離后得到化合物9(20 mg)。

2結(jié)果與分析

2.1化合物1白色固體。ESI-MSm/z：425.73 [M-H];1H-NMR (400 MHz,CDC13) 顯示有8個(gè)單峰甲基δ： 1.17 (3H,s,Me-28),1.05 (3H,s,Me-27),0.98 (6H,s,Me-26,30),0.94 (3H,s,Me-29),0.86 (3H,d,J= 6.8 Hz,Me-23),0.85 (3H,s,Me-25),0.72 (3H,s,Me-24);13C-NMR (100 MHz,CDC13) δ： 22.1 (C-1),41.4 (C-2),213.0 (C-3),58.0 (C-4),42.0 (C-5),41.1 (C-6),18.0 (C-7),52.9 (C-8),37.3 (C-9),59.3 (C-10),35.5 (C-11),30.3 (C-12),39.5 (C-13),38.1 (C-14),32.3 (C-15),35.9 (C-16),29.8 (C-17),42.6 (C-18),35.2 (C-19),28.0 (C-20),32.6 (C-21),39.1 (C-22),6.7 (C-23),14.5 (C-24),17.8 (C-25),20.1 (C-26),l8.5 (C-27),32.0 (C-28),34.9 (C-29),31.7 (C-30)。以上數(shù)據(jù)與文獻(xiàn)[2]報(bào)道的數(shù)據(jù)基本一致，故確定為木栓酮。

2.2化合物2 色粉末狀固體。ESI-MSm/z： 553.5 [M+H];1H-NMR (400 MHz,CDC13) δ： 0.85 (3H,s,H-9′),0.87 (1H,d,J= 11.5 Hz,H-5)，0.88 (1H,m,H-7),0.90 (1H,m,H-15),0.93 (1H,m,H-16),0.95 (3H,s,H-28),0.98 (1H,m,H-1),0.99 (3H,s,H-29),1.00 (3H,s,H-26),1.04 (3H,s,H-24),1.09 (3H,s,H-30),1,10 (1H,m,H-22),1.12 (1H,m,H-21),1.14 (3H,s,H-25),1.16 (3H,s,H-23),1.25 (3H,s,H-27),1.26 (1H,m,H-7),1.26 (2H,m,H-6′),1.27 (2H,m,H-7′),1.29 (2H,m,H-4′),1.29 (1H,m,H-6),1.30 (2H,m,H-5′),1.31 (2H,m,H-3′),1.35 (2H,m,H-8′),1.40 (1H,m,H-6),1.44 (1H,m,H-16),1.45 (2H,m,H-2′),1.48 (1H,m,H-15),1.59 (1H,m,H-2),1.59 (1H,m,H-9),1.65 (1H,m,H-19),1.68 (1H,m,H-22),1.69 (1H,m,H-21),1.76 (1H,m,H-11),1.89 (1H,m,H-19),1.95 (1H,m,H-18),2.01 (1H,m,H-2),2.01 (1H,m,H-11),3.46 (1H,t-like,J= 3.6 Hz,H-3),3.64 (3H,t,J= 4.4 Hz,H-1′),5.62 (1H,t,J= 3.5 Hz,H-12);13C-NMR (100 MHz,CDC13) δ： 38.98 (C-1),27.84 (C-2),77.21 (C-3),38.97 (C-4),49.74 (C-5),18.41 (C-6),32.39 (C-7),37.87 (C-8),47.48 (C-9),36.10 (C-10),23.67 (C-11),122.05 (C-12),141.65 (C-13),40.84 (C-14),25.75 (C-15),27.84 (C-16),32.85 (C-17),47.48 (C-18),47.48 (C-19),30.37 (C-20),34.87 (C-21),36.05 (C-22),28.26 (C-23),14.10 (C-24),16.20 (C-25),16.20 (C-26),25.75 (C-27),28.26 (C-28),33.15 (C-29),23.67 (C-30),63.12 (C-1′),27.84 (C-2′),25.75 (C-3′),29.44 (C-4′),29.44 (C-5′),29.36 (C-6′),31.93 (C-7′),22.67 (C-8′),14.10 (C-9′)。以上數(shù)據(jù)與文獻(xiàn)[3]報(bào)道的數(shù)據(jù)基本一致，故鑒定為β-3-壬氧基-12-齊墩果烯。

2.3化合物31H-NMR (400 MHz,CDC13) δ： 2.62 (1H,dt,J= 10.0,9.5 Hz,H-2),1.62 (1H,t,J= 10.0 Hz,H-3),1.69 (1H,dd,J= 10.0,8.0 Hz,H-3),1.76 (1H,t,J= 10.0 Hz,H-5),1.43 (1H,m,H-6),1.65 (1H,m,H-6),0.97 (1H,m,H-7),2.09 (1H,m,H-7),2.87 (1H,dd,J= 11.0,4.0 Hz,H-9),1.32 (1H,m,H-10),2.25 (1H,m,H-10),2.11 (1H,m,H-11),2.25 (1H,m,H-11),4.86 (1H,d,J= 1.0 Hz,H-12),4.97 (1H,d,J= 1.0 Hz,H-12),1.01 (1H,s,H-13),0.98 (1H,s,H-14),1.20 (1H,s,H-15)。以上數(shù)據(jù)與文獻(xiàn)[4]數(shù)據(jù)一致，故確定化合物3為8R,9R-環(huán)氧-β-石竹烯。

2.4化合物4無(wú)色雪花狀晶體。 ESI-MSm/z：427.7 [M+H];1H-NMR (400 MHz,CDC13) δ： 5.54 (1H,dd,J= 8.0,3.0 Hz,H-15),3.20 (1H,dd,J= 11.0,4.0 Hz,H-3),2.04 (1H,dt,J= 13.0,3.5 Hz,H-16b),1.92 (1H,dd,J= 15.0,3.0 Hz,H-16a),1.09 (3H,s,H-26),0.98 (3H,s,H-23),0.95 (3H,s,H-28),0.93 (3H,s,H-25),0.91 (3H,s,H-27),0.91 (3H,s,H-30),0.82 (3H,s,H-28),0.80 (3H,s,H-24);13C-NMR (100 MHz,CDC13) δ： 37.7 (C-1),27.1 (C-2),79.1 (C-3),38.8 (C-4),55.5 (C-5),18.8 (C-6),41.3 (C-7),39.0 (C-8),49.3 (C-9),38.0 (C-10),17.5 (C-11),33.7 (C-12),37.6 (C-13),158.1 (C-14),116.9 (C-15),37.7 (C-16),35.8 (C-17),48.7 (C-18),36.7 (C-19),28.8 (C-20),33.1 (C-21),35.1 (C-22),28.0 (C-23),15.4 (C-24),15.4 (C-25),25.9 (C-26),21.3 (C-27),29.8 (C-28),33.3(C-29),29.9 (C-30)。以上數(shù)據(jù)與文獻(xiàn)[5]報(bào)道的數(shù)據(jù)基本一致，故鑒定該化合物為蒲公英萜醇。

2.5化合物5無(wú)色針狀結(jié)晶。EI-MSm/z： 414[M]+;1H-NMR (400 MHz,CDC13) δ： 0.65 (3H,s,C-18),0.79 (3H,d,J= 7.0 Hz,C-27),0.82 (3H,d,J= 7.0 Hz,C-26),0.88 (3H,t,J= 7.0 Hz,C-29),0.96 (3H,d,J= 6.6Hz,C-21),0.99(3H,s,C-19),3.49 (1H,m,H-3 ),5.32 (1H,m,H-6 );13C-NMR (100 MHz，CDC13) δ： 11.9 (C-18),12.1 (C-29),18.8 (C-21),19.1 (C-27),19.5 (C-19),19.9 (C-26),21.2 (C-11)，23.1 (C-28 ),24.4 (C-15 ),26.2(C-23),28.3 (C-16),31.7 (C-2),32.0 (C-7)，34.0 (C-22)，37.3 (C-1),39.9 (C-12),42.4 (C-4),16.0 (C-24),16.4 (C-25),32.0 (C-8),36.2(C-20)，50.2 (C-9),56.1 (C-17),56.9 (C-14),71.9 (C-3),121.8 (C-6),36.6 (C-10),42.4 (C-13),140.8 (C-5)。以上波譜數(shù)據(jù)與文獻(xiàn)[6]一致，故鑒定為豆甾烷-5烯-3-醇。

2.6化合物61H-NMR(400 MHz,CDCl3) δ： 0.677 (3H,s,C-18),0.819 (3H,d,J= 7.0 Hz,C-27),0.842 (3H,d,J= 7.0 Hz,C-26),0.910 (3H,t,J= 7.0 Hz,C-29),0.926 (3H ,d,J = 6.6 Hz,C-21),1.006 (3H,s,C-19),3.551(1H,m,H-3),5.356(1H,m,H-6);13C-NMR (100 MHz,CDCl3) δ： 37.29 (C-1),31.71 (C-2),71.83 (C-3),42.36 (C-4),140.78 (C-5),121.70 (C-6),23.12 (C-7),31.95 (C-8),50.19 (C-9),36.21 (C-10),21.11 (C-11),39.82 (C-12),42.355 (C-13),56.12 (C-14),24.32 (C-15),28.25 (C-16),56.86 (C-17),11.87 (C-18),19.40 (C-19),36.16 (C-20),19.06 (C-21),140.78 (C-22),121.701 (C-23),45.90 (C-24),29.23 (C-25),19.40(C-26),19.81 (C-27),23.12(C-28)。 以上數(shù)據(jù)與文獻(xiàn)[7]基本一致，故確定該化合物為麥角甾-5-烯-3-醇。

2.7化合物7白色針狀晶體。ESI-MS：m/z427.6 [M+H];13C-NMR(100 MHz,CDCl3) δ： 44.48 (C-1),50.41 (C-2),56.86 (C-3),147.51 (C-4),44.67 (C-5),

20.23(C-6),34.21 (C-7),40.83 (C-8),44.67 (C-9),38.65 (C-10),25.45 (C-11),121.96 (C-12),147.51 (C-13),40.83 (C-14),27.77 (C-15),25.45 (C-16),31.57 (C-17),44.67 (C-18),44.48 (C-19),31.57 (C-20),34.67 (C-21),37.96 (C-22),111.33 (C-23),111.20 (C-24),15.21 (C-25),18.08 (C-26),25.45 (C-27),27.77 (C-28),32.93 (C-29)。以上核磁數(shù)據(jù)與文獻(xiàn)[8]對(duì)照，確定該化合物為2α,3β,-二羥基-24-去甲基-4(23)-12-齊墩果烯。

2.8化合物8白色粉末狀固體。mp： 237.1～239.2 ℃。13C-NMR光譜數(shù)據(jù)與齊墩果酸的數(shù)據(jù)[9-10]一致，故鑒定為齊墩果酸。

2.9化合物9白色粉末。1H-NMR (400 MHz,CDC13) δ： 7.71 (2H,dd,J= 6.0,3.2 Hz),7.52 (2H,dd,J= 6.0,3.2 Hz),4.30 (1H,t,J= 6.8 Hz),1.73 (4H,m),1.58 (4H,m),0.96 (4H,m),0.88 (4H,m),0.83 (3H,t,J= 6.4 Hz)。以上數(shù)據(jù)與SDBS數(shù)據(jù)庫(kù)標(biāo)準(zhǔn)圖譜對(duì)照確定為鄰苯二甲酸二戊酯。

3結(jié)論

從海南油楠葉中共分離得到9個(gè)化合物，鑒定為木栓酮、3β-3-壬氧基-12-齊墩果烯、8R,9R-環(huán)氧-β-石竹烯、蒲公英萜醇、豆甾烷-5烯-3-醇、麥角甾-5-烯-3-醇、2α,3β,-二羥基-24-去甲基-4(23)-12-齊墩果烯、齊墩果酸和鄰苯二甲酸二戊酯，其中這9個(gè)化合物均為首次從該植物的樹(shù)葉中分離得到。

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基金項(xiàng)目海南省教育廳資助項(xiàng)目(Hjkj2013-04)。

作者簡(jiǎn)介張軍鋒(1976- )，男，河南鄧州人，副教授，從事天然產(chǎn)物化學(xué)研究。*通訊作者，教授，從事天然產(chǎn)物化學(xué)及應(yīng)用研究。

收稿日期2016-04-05

中圖分類號(hào)S 727.4

文獻(xiàn)標(biāo)識(shí)碼A

文章編號(hào)0517-6611(2016)13-017-02

Research on the Chemical Constituents in Leaf ofSindoraglabraMerr.ex De Wit.

ZHANG Jun-feng, CHEN Yi-ping*, LIANG Zhen-yi et al

(Materials and Chemical Engineering Institute，Hainan University，Haikou, Hainan 570228)

Abstract[Objective] The chemical constituents in Sindora glabra Merr.ex De Wit.leaf was analyzed.[Method] The Hexane and ethyl acetate extracted from the leaves were isolated and purified with silica gel column chromatography and the structure of the extracts was elucidated based on their physicochemical property and spectroscopic analysis.[Result] Nine compounds： friedelin,3β-3-nonyloxy-12-oleanen,8R,9R-epoxy-β-carophyllene, Taraxero, stigmastane-5-ene-3-ol, ergosta -5-ene-3-ol, 2α, 3β, -dyhydroxyl -24- methyl-4(23)-12-oleanen,oleanolic acid and diamyl phthalate,were isolated.[Conclusion] The compounds： friedelin, 3β-3-nonyloxy-12-oleanen, 8R, 9R-epoxy-β-carophyllene, taraxero, stigmastane-5-ene-3-ol,ergosta-5-ene-3-ol, oleanolic acid, and diamyl phthalate are firstly isolated from Sindora glabra Merr. ex De Wit.

Key wordsSindora glabra Merr.ex De Wit；Chemical Constituent; Isolation; Friedelin