孟春楊，牛德云，周 斌，孟艷林，楊玉春，秦 穎，胡秋芬

(云南民族大學(xué) 民族藥資源化學(xué)國(guó)家民委-教育部重點(diǎn)實(shí)驗(yàn)室，云南 昆明 650031)

玫瑰花中苯丙素和苯乙醇類化學(xué)成分的研究

孟春楊，牛德云，周 斌，孟艷林，楊玉春，秦 穎，胡秋芬

(云南民族大學(xué) 民族藥資源化學(xué)國(guó)家民委-教育部重點(diǎn)實(shí)驗(yàn)室，云南 昆明 650031)

采用硅膠色譜、高效液相制備色譜對(duì)產(chǎn)自云南呈貢的玫瑰花進(jìn)行分離、純化化學(xué)成分，通過(guò)UV、IR、MS、NMR等波譜方法進(jìn)行結(jié)構(gòu)鑒定.分離得到了8個(gè)苯丙素和苯乙醇類已知化合物，分別鑒定為Ferulic acid(1),ω-Hydroxypropioguaiacone(2),(E)-Ferulaldehyde(3),1-Propanone-2-hydroxy-1-(3-methoxy-4-hydroxyphenyl)(4),Evofolin(5),2-(3′-O-β-D-Glucopyranosyl-4′-hydroxyphenyl)-ethanol(6),2-(3-Hydroxy-4-O-D-β-glucopyranosyl)phenyl-ethanol(7),2(3,4-Dihydroxy-phenyl)-ethanol(8).這些化合物均為首次從呈貢玫瑰花中分離得到.

玫瑰花；分離鑒定；苯丙素；苯乙醇

玫瑰(RosaRugosa)為薔薇科(Rosaceae)薔薇屬(Rosa)植物，是多年生灌木[1].玫瑰花是薔薇科植物玫瑰RosaRugosaThunb.的干燥花蕾.玫瑰在全球范圍內(nèi)廣泛種植,但多數(shù)分布于北半球,以保加利亞、土耳其、摩洛哥、法國(guó)、俄羅斯等國(guó)家為主,其中保加利亞是目前世界上玫瑰油產(chǎn)量最高的國(guó)家.玫瑰在我國(guó)的栽培歷史悠久,在全國(guó)各地均有種植,其中以山東、甘肅、北京、江蘇、河南、河北、四川、遼寧、黑龍江、臺(tái)灣、云南、山西和新疆等地為主.

玫瑰花富含氨基酸、蛋白質(zhì)、多糖、淀粉、維生素等各種營(yíng)養(yǎng)成分.花瓣可食用，可泡茶喝；玫瑰花可用來(lái)提取玫瑰油用于制造各種高檔化妝品；從玫瑰花瓣中提取出來(lái)的色素可用作食品中的天然食用色素；玫瑰花的藥用價(jià)值也極高，歷代本草均有玫瑰花在藥用方面的記載.玫瑰花主要含有揮發(fā)油、黃酮類、鞣質(zhì)類、萜類、酚類及多種營(yíng)養(yǎng)成分，具有行氣解郁、抗病毒、清除自由基、抗氧化、抗腫瘤、擴(kuò)張血管、活血止痛、解毒、利膽等功用[2-10].歷代本草均有記載[11].

目前，還未見(jiàn)有關(guān)呈貢玫瑰花化學(xué)成分研究的報(bào)道.本文首次對(duì)呈貢玫瑰花的提取物進(jìn)行了分離和結(jié)構(gòu)鑒定，從中分離得到8個(gè)已知苯丙素和苯乙醇類化合物.

1 材料

1.1 儀器

MS和NMR由中國(guó)科學(xué)院昆明植物研究所代為測(cè)定.儀器分別為VG AUTO Spec-3000質(zhì)譜儀和Bruker AM-400及DRX-500核磁共振儀;Agilent 1100型高效液相色譜儀，色譜柱為Agilent公司的ZORBAX SB-C18(9.4 mm×250 mm)反相柱和凝膠柱、博納艾杰爾科技公司的Venusil HILIC(10 mm×250 mm，5 μm)色譜柱；瑞士Buchi R-210型旋轉(zhuǎn)蒸發(fā)儀、V-700真空泵;EYELA CA-1111冷卻水循環(huán)裝置；流動(dòng)相過(guò)濾裝置，0.45 μm微孔過(guò)濾膜.

1.2 試劑

100～200目硅膠、200～300目硅膠和GF 254(100 mm×100 mm)硅膠板，青島海洋化工廠生產(chǎn)；MCI-gel CHP-20P材料；Sephadex LH-20凝膠；5% H2SO4乙醇溶液顯色劑；工業(yè)用三氯甲烷、甲醇、乙酸乙酯、石油醚；色譜純乙腈、四氫呋喃；超純水.

1.3 材料

實(shí)驗(yàn)用玫瑰花于2012年1月購(gòu)自云南省昆明市斗南花卉市場(chǎng)，經(jīng)云南民族大學(xué)陳毅堅(jiān)教授鑒定為薔薇科(Rosaceae)薔薇屬(Rosa)玫瑰，植物標(biāo)本存放于云南民族大學(xué)民族藥資源化學(xué)國(guó)家民委-教育部重點(diǎn)實(shí)驗(yàn)室.

2 提取分離

取5.0 kg呈貢玫瑰花干花，粉碎后用三氯甲烷-甲醇(2∶1)溶液8 L室溫浸泡3～5天超聲4次(每次30 min)，過(guò)濾，減壓蒸餾回收溶劑，再用回收溶劑反復(fù)常溫浸泡超聲提取5～6次，合并浸膏得到550 g.浸膏用700 g(100～200目)粗硅膠拌樣，烘干，用3.5 kg硅膠(100～200目)柱層析，V(三氯甲烷)∶V(甲醇)分別為1∶0(Ⅰ)、20∶1(Ⅱ)、10∶1(Ⅲ)、5∶1(Ⅳ)、2∶1(Ⅴ)、0∶1(Ⅵ)作梯度洗脫劑洗脫，除去大量雜質(zhì)，將浸膏分成6個(gè)部分.經(jīng)TLC檢測(cè)，Ⅰ部分主要成分是揮發(fā)油和脂肪酸類物質(zhì)；Ⅱ、Ⅲ、Ⅳ、Ⅴ有明顯的主斑點(diǎn)；Ⅵ部分沒(méi)有主斑點(diǎn).粗略對(duì)比Ⅱ、Ⅲ、Ⅳ、Ⅴ部分，選定Ⅳ進(jìn)行分離.Ⅱ?yàn)閂(三氯甲烷)∶V(甲醇)=5∶1洗脫劑洗脫下來(lái)的部分，經(jīng)甲醇溶解，采用0.45 μm微孔過(guò)濾膜過(guò)濾后,用Agilent公司的ZORBAX SB-C18(9.4 mm×250 mm)反相柱，以50%[V(甲醇)∶V(水)]作流動(dòng)相，流速為3.5 mL/min劃分為6段.經(jīng)調(diào)配流動(dòng)相比例，用ZORBAX SB-C18反相柱對(duì)以上6段進(jìn)行分析，第1段為雜質(zhì)，化合物主要在后5段中.調(diào)節(jié)流動(dòng)相配比，用HPLC對(duì)后5段進(jìn)行分離、純化得到化合物1(11.3 mg),2(8.9 mg),3(12.1 mg),4(11.7 mg),5(9.7 mg),6(20.1 mg),7(13.2 mg),8(14.6 mg),結(jié)構(gòu)見(jiàn)圖1.

3 結(jié)構(gòu)鑒定

化合物1白色粉末.1H NMR(Pyridine,400 MHz)δ:7.34(1H,d,J=2.0 Hz,H-2),7.19(1H,d,J=6.9 Hz,H-5),8.10(1H,d,J=15.9 Hz,H-6),7.28(1H,dd,J=2.0,6.9 Hz,H-7),6.86(1H,d,J=15.9 Hz,H-8),3.95(3H,s,OMe-3);13C NMR(Pyridine,100 MHz)δ:126.9(s,C-1),111.5(d,C-2),150.8(s,C-3),145.0(s,C-4),116.9(d,C-5),117.2(d,C-6),149.0(d,C-7),116.9(d,C-8),169.7(s,C-9),55.9(q,OMe-3).以上數(shù)據(jù)與文獻(xiàn)[12]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物1為Ferulic acid.

化合物2淡黃色粉末.positive ESI-MSm/z(%):415[2M+Na]+(2),314(29),219[M+Na]+(100);1H NMR(500 MHz,CD3OD)δ:7.52(1H,d,J=2.2 Hz,H-2),6.85(1H,d,J=8.3 Hz,H-5),7.55(1H,dd,J=2.2,8.3 Hz,H-6),3.14(2H,t,J=6.3 Hz,H-8),3.93(2H,t,J=6.3 Hz,H-9),3.89(3H,s,MeO);13C NMR(125 MHz,CD3OD)δ:130.6(s,C-1),111.9(d,C-2),153.3(s,C-3),149.0(s,C-4),115.8(d,C-5),124.7(d,C-6),199.8(s,C-7),41.6(t,C-8),58.9(t,C-9),56.4(q,OMe).以上數(shù)據(jù)與文獻(xiàn)[13]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物2為ω-Hydroxypropioguaiacone.

化合物3白色粉末.1H NMR(400 MHz,CD3OD)δ:7.25(1H,d,J=2.5 Hz,H-2),6.84(1H,d,J=10.0 Hz,H-5),7.16(1H,dd,J=2.5,10.0 Hz,H-6),7.57(1H,d,J=19.5 Hz,H-7),6.64(1H,dd,J=9.8,19.5 Hz,H-8),9.56(1H,d,J=9.8 Hz,H-9),3.89(3H,s,MeO);13C NMR(100 MHz,CD3OD)δ:127.6(s,C-1),112.1(d,C-2),151.7(s,C-3),149.5(s,C-4),116.6(d,C-5),125.2(d,C-6),156.3(d,C-7),126.7(d,C-8),196.2(s,C-9),56.4(q,OMe).以上數(shù)據(jù)與文獻(xiàn)[14]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物3為(E)-Ferulaldehyde.

化合物4白色固體.13C NMR(100 MHz,CD3OD)δ:126.9(s,C-1),112.4(d,C-2),153.8(s,C-3),148.9(s,C-4),116.1(d,C-5),124.7(d,C-6),201(s,C-7),69.7(d,C-8),22.5(q,C-9),55.8(q,MeO-3).以上數(shù)據(jù)與文獻(xiàn)[15]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物4為1-Propanone-2-hydroxy-1-(3-methoxy-4-hydroxyphenyl).

化合物5淡黃色油狀物.Positive FAB MS:m/z318 [M]+;1H NMR(400 MHz,C5D5N)δ:7.57(1H,d,J=2.0 Hz,H-2),6.82(1H,d,J=8.3 Hz,H-5),6.82(1H,dd,J=2.0,8.3 Hz,H-6),4.76(1H,dd,J=8.3,5.2 Hz,H-8),4.82(1H,dd,J=10.2,5.2 Hz,H-9),6.97(1H,d,J=2.0 Hz,H-2′),6.71(1H,d,J=8.0 Hz,H-5′),6.79(1H,dd,J=2.0,8.0 Hz,H-6′),3.67(each 3H,s,2×OCH3);13C NMR(100 MHz,C5D5N)δ:129.9(s,C-1),112.5(d,C-2),148.7(s,C-3),153.4(s,C-4),115.3(d,C-5),124.8(d,C-6),198.5(s,C-7),55.2(d,C-8),65.6(t,C-9),129.7(s,C-1′),112.8(d,C-2′),149.0(s,C-3′),147.6(s,C-4′),116.9(d,C-5′),123.3(d,C-6′),55.8(q,2×OCH3).以上數(shù)據(jù)與文獻(xiàn)[16]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物5為Evofolin.

化合物6無(wú)色膠狀物.1H NMR(Pyridine,500 MHz)δ:5.43(1H,d,J=7.5 Hz,H-1′),3.95-4.28(H-2′,H-3′,H-4′,H-5′),4.30 and 4.50(2H,AB system,J=12.5,2.2,4.4 Hz,H-6′),2.93(2H,t,J=7.0 Hz,H-7),4.30(2H,t,J=7.0 Hz,H-8),6.15-7.06(Phenyl);13C NMR(Pyridine,125 MHz)δ:131.7(s,C-1),125.5(d,C-2),148.1(s,C-3),146.6(s,C-4),121.3(d,C-5),117.1(d,C-6),105.5(d,C-1′),79.0(d,C-2′),75.1(d,C-3′),71.2(d,C-4′),78.4(d,C-5′),62.3(t,C-6′),39.7(t,C-7),63.7(t,C-8).以上數(shù)據(jù)與文獻(xiàn)[17-18]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物6為2-(3′-O-β-D-Glucopyranosyl-4′-hydroxyphenyl)-ethanol.

化合物7無(wú)色膠狀物.1H NMR(Pyridine,500 MHz)δ:6.15(1H,d,J=8.0 Hz,H-2),7.04(1H,d,J=8.0 Hz,H-5),6.66(1H,dd,J=8.0,2.0 Hz,H-6),5.36(1H,d,J=7.5 Hz,H-1′),3.97-4.25(H-2′,H-3′,H-4′,H-5′),4.30 and 4.50(2H,AB system,J=12.5,2.2,4.4 Hz,H-6′),2.93(2H,t,J=7.0 Hz,H-7),4.29(2H,t,J=7.0 Hz,H-8);13C NMR(Pyridine,125 MHz)δ:105.8(d,C-1′),75.1(d,C-2′),79.0(d,C-3′),71.3(d,C-4′),78.4(d,C-5′),62.4(t,C-6′),137.0(s,C-1),123.5(d,C-2),145.1(s,C-3),149.6(s,C-4),118.2(d,C-5),120.5(d,C-6),40.0(t,C-7),63.6(t,C-8).以上數(shù)據(jù)與文獻(xiàn)[18]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物7為2-(3-Hydroxy-4-O-D-β-glucopyranosyl)phenyl-ethanol.

化合物8無(wú)色膠狀物.1H NMR(Pyridine,500MHz)δ:7.20(1H,d,J=8.0 Hz,H-2),7.32(1H,d,J=8.0 Hz,H-5),6.88(1H,dd,J=8.0,1.0 Hz,H-6),3.03(2H,t,J=7.0 Hz,H-7),4.10(2H,J=7.0 Hz,H-8);13C NMR(Pyridine,100 MHz)δ:131.7(s,C-1),120.6(d,C-2),145.5(s,C-3),147.2(s,C-4),117.6(d,C-5),116.5(d,C-6),40.0(t,C-7),64.1(t,C-8).以上數(shù)據(jù)與文獻(xiàn)[18]報(bào)道的數(shù)據(jù)基本一致，故鑒定化合物8為2(3,4-Dihydroxy-phenyl)-ethanol.

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(責(zé)任編輯 王 琳)

Phenylpropanoids and phenylethanoids from theRosarugosa

MENG Chun-yang,NIU De-yun,ZHOU Bin,MENG Yan-lin,YANG Yu-chun,QIN Ying,HU Qiu-fen

(Key Laboratory of Chemistry in Ethnic Medicinal Resources,State Ethnic Affairs Commission and Ministry of Education of China,Yunnan Minzu University,Kunming 650031,China)

The research aimed to study the chemical constituents fromRosarugosain Chenggong of Yunnan province. The constituents were isolated and purified by the silica column chromatography and HPLC. Their structures were elucidated by spectroscopy. Eight phenylpropanoids and phenylethanoids were obtained and identified as follows: Ferulic acid(1),ω-Hydroxypropioguaiacone(2),(E)-Ferulaldehyde(3), 1-Propanone-2-hydroxy-1-(3-methoxy-4-hydroxyphenyl)(4),Evofolin(5),2-(3′-O-β-D-Glucopyranosyl-4′-hydroxyphenyl)-ethanol(6),2-(3-Hydroxy-4-O-D-β-glucopyranosyl) phenyl-ethanol(7),and 2(3,4-Dihydroxy-phenyl)-ethanol(8). These compounds are obtained from this plant for the first time.

Rosarugosa; isolate and identify; phenylpropanoids; phenylethanoids

2014-11-24.

國(guó)家自然科學(xué)基金(21265025).

孟春楊(1987-)，女，碩士研究生.主要研究方向:分析化學(xué).

胡秋芬(1978-)，女，博士，教授，碩士生導(dǎo)師.主要研究方向:分析化學(xué).

S685.12;R284.1

A

1672-8513(2015)02-0108-04