全 文 ：A Benzofuranoid Neolignan from Magnolia biondii Pamp
LU Yan-hua1 , GAO Yang1 , WANG Zheng-tao2 , LIU Jian-qun2 , and WEI Dong-zhi1＊
(1 .State Key Laboratory of Bioreactor Engineering , New World Institute of Biochemistry , East China University of Science and Technology ,
Shanghai 200237 , China;2.Department of Pharmacognosy , China Pharmaceutical University , Nanjing 210038 , China)
Abstract:Aim 　Isolation and structural elucidation of the constituents from the dried flower buds
of Magnolia biondii Pamp.Methods　Column chromatography and TLC were used to isolate chemical
constituents.Spectroscopic methods were employed for structural elucidation.Results　One benzo-
furanoid neolignan(licarin B)and two bisepoxy lignans(magnolin , fargesin)were isolated and identi-
fied.Conclusion　Licarin B is the first reported benzofuranoid lignan from the family Magnoliaceae.
Key words:Magnolia biondii;licarin B;neolignan
CLC number:R284.1;R284.2　Document code:A　　Article ID:1003-1057(2005)3-137-03
Introduction
The dried flower buds of Magnolia biondii Pamp
(Magnoliaceae)is a traditional Chinese medicine , which
has been used for treatment of nasal congestion and hea-
dache in China.Previous investigation of the species re-
sulted in the isolation and identification of bisepoxy lig-
nans(magnolin , fargesin , etc), and alkaloids(salicifo-
line , magnocurarine , etc)[ 1-3] .This paper deals with the
isolation and structural elucidation of one benzofuranoid
neolignan(licarin B)and two bisepoxy lignans (magno-
lin , fargesin).Licarin B is the first reported benzo-
furanoid lignan from the family Magnoliaceae(Figure 1).
Figure 1　Licarin B
Experimental
All the melting points were determined on an X4 mic-
romelting point apparatus(uncorrected).1H and 13C NMR
spectra were recorded on a Bruker Am-300 spectrometer
Received date:2005-01-17.
Foundat ion item:Key Disciplinary Foundation of Shanghai(03DZ19546).
＊Corresponding author:　Tel 86-21-64252981 , Fax 86-21-64250068,
E-mai l dzhwei@ecust.edu.cn
with tetramethylsilane (TMS)as an internal standard ,
and chemical shifts were expressed in ppm.IR spectra
were taken on a Perkin-Elmer 983 infrared spectrometer.
Silica gel for column chromatography was produced by
Qingdao Ocean Chemicals.All the solvents were of ana-
lytical grade.
Dried flower buds of Magnolia biondii Pamp were
purchased in Shanghai Medicinal Materials Company ,
identified by Dr.Lu Yan-hua , and deposited in the Her-
barium of East China University of Science &Technology.
Extraction and isolation
Dried flower buds of Magnolia biondii Pamp(3 kg)
were first extracted with petroleum ether(3×40 L , 12 h
each)at room temperature to degrease , and then the ma-
terials were extracted with CHCl3(3×40 L , 12 h each)
at room temperature.The extract was concentrated under
reduced pressure to give a residue (304 g), which was
separated by CC(10 cm×100 cm)over silica gel(200-
300 mesh , 1 kg)eluted with a petroleum ether-ethyl ace-
tate gradient(100∶5 to 100∶20)to give 20 fractions(Fr.
1-20).Fraction 6 was recrystallized to give compound 1
(504 mg).Fraction 9 was separated by repeated column
chromatography over silica gel to give compound 3 (168
mg).Fraction 17 was separated by repeated column chroma-
tography to afford compound 2(372 mg).
Structural elucidation
Compound 1 (licarin B)　Colorless needles
(CHCl3), mp 87-88 ℃;ESI-MS m z:325 (M ++
1);UV λmax nm MeOH:273 , 220;IR (KBr)cm-1:
137Journal of Chinese Pharmaceutical Sciences 2005 , 14(3):137-139
1 600 , 1 490 , 1 450 , 1 330 , 1 250 , 1 220 , 1 210 ,
1 130 , 1 140 , 1 035 , 970 , 930;the IR absorption
bands showed that it had no hydroxyl and carboxyl group
(OH , C=O).Compound 1 displayed typical 1H NMR
spectroscopic data of trans-2-aryl-3-methyl-2 , 3-dihydro-
benzofuranoid type neolignans , δ:5.10 (d , J =8.9
Hz , H-2), 1.38(d , J =6.7Hz , 3-Me)[ 5 , 6] , suggest-
ing that 1was a benzofuranoid type lignan.δ6.35(1H ,
br.d , J =15.3 Hz)and 6.10(1H , dq , J =15.3 ,
6.7 Hz)showed the occurrence of unsaturated carbons in
the side chain.The 1H NMR and 13C NMR data of 1were
in agreement with those of lacarin B
[ 4, 7 , 8] .1H NMR
(CDCl3)δ:5.10 (1H , d , J =8.9 Hz , H-2), 3.4
(1H , m , H-3), 1.38 (3H , d , J =6.8 Hz , 3-Me),
6.78(1H , s , H-4), 6.75(1H , s , H-6), 3.89 (3H ,
s , 7-OCH3), 6.35(1H , br.d , J =15.3 Hz , H-8),
6.10(1H , dq , J =15.3 , 6.7 Hz , H-9), 1.87(3H ,
br.d , J =6.7Hz , 1.1 Hz , 10-CH3), 6.93(1H , br.
s , J =1.2 Hz , H-2′), 6.78(1H , d , J =8.0 Hz ,
H-5′), 6.88(1H , br.d , J =8.0 , 1.2 Hz , H-6′),
5.95(2H , s , -O-CH2-O-);13C NMR(CDCl3)δ:94.1
(C-2), 46.4 (C-3), 114.0 (C-4), 135.0 (C-4a),
132.9(C-5), 107.5(C-6), 148.6(C-7), 144.8(C-
7a), 131.6(C-8), 124.1(C-9), 19.0(C-10), 133.8
(C-1′), 108.7(C-2′), 148.3(C-3′), 147.2(C-4′),
110.0(C-5′), 120.8(C-6′), 101.8(OCH2O), 18.6
(3-CH3), 55.0(OCH3).Licarin B is the first reported
benzofuranoid lignan from the Magnoliaceae family.
Compound 2 (magnolin)　Colorless prism crystal
(CHCl3), mp 90-91 ℃, ESI-MS m z:417(M ++1);
UV λmax nm MeOH:208.0 , 230.5 , 278.0;IR (KBr)
cm
-1:1 587 ,1 519 ,1 502 ,1 463 ,1 414 , 1 384 ,1 360 ,
1 331 , 1 298 , 1 287 ,1 267 , 1 253 ,1 210 , 1 186 ,1 165 ,
1 153 ,1 122 , 1 091 , 1 090 , 1 063 ,1 039 ,1 026 ,1 003;
1
H NMR and
13
C NMR data of 2 were in agreement with
those of magnolin
[ 2] .1H NMR(CDCl3)δ:3.11(2H ,
m , H-1 ,H-5), 4.76(2H , m , H-2 , H-6), 4.28(2H ,
m , H-4 , H-8), 3.93(2H , m , H-4 , H-8), 3.90(3H , s ,
H-6), 3.90(3H , s ,OCH3), 3.88(9H , s , OCH3), 3.84
(3H , s , OCH3), 6.8-6.9(3H , m , Ar-H),6.60(2H ,
s , Ar-H);13C NMR(CDCl3)δ:54.1(C-1), 54.4(C-
5), 71.7(C-4), 71.9(C-8), 85.6(C-2), 86.0(C-6),
136.7(C-1′), 102.8(C-2′), 153.3(C-3′), 137.5(C-
4′), 153.3(C-5′), 102.8(C-6′), 136.7(C-1″), 109.2
(C-2″), 149.1(C-3″), 148.5(C-4″), 111.0(C-5″),
118.1(C-6″),55.9(OCH3 ×2), 56.2(OCH3×2), 60.8
(OCH3).
Compound 3 (fargesin)　Colorless prism crystal
(MeOH), mp 130-131 ℃, ESI-MS m z :371(M ++
1);UV λmax nm MeOH:206.0 , 231.5 , 282.5;IR
(KBr)cm-1:1 600 , l 590 , 1 516 ,1 503 ,1 487 ,1 464 ,
1 439 , 1 415 , 1 397 , 1 367 , 1 329 , 1 27l , 1 244 ,
1 233 , 1 190 , 1 158 , 1 14l , 1 107 , 1 052 , 1 028.The
1
H NMR and
13
C NMR data of　3were in agreement with
those of fargesin
[ 2] .1H NMR(CDCl3)δ:3.35 (1H ,
m , H-1 ,H-5), 2.87(1H , m , H-1 ,H-5), 4.86(1H ,
m , H-2 ,H-6), 4.42 (1H , d , H-2 ,H-6), 4.10(1H ,
d , H-4 ,H-8), 3.83 (2H , m , H-4 ,H-8), 3.35(1H ,
m , H-4 ,H-8), 3.91 (3H , s , OCH3), 3.89(3H , s ,
OCH3), 5.95 (2H , s , OCH2O), 6.8-6.9 (6H , m ,
Ar-H);13C NMR(CDCl3)δ:50.2 (C-1), 54.8 (C-
5), 69.8(C-4), 71.7(C-8), 82.1 (C-2), 87.9 (C-
6), 131.1 (C-1′), 109.3 (C-2′), 149.0 (C-3′),
148.2 (C-4′), 111.3 (C-5′), 117.8 (C-6′), 135.3
(C-1″), 106.5(C-2″), 148.0(C-3″), 147.2(C-4″),
108.2 (C-5″), 119.5 (C-6″), 56.0 (OCH3 ×2),
101.0(OCH2O).
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138 Journal of Chinese Pharmaceutical Sciences 2005 , 14(3):137-139
望春花中的一个苯并呋喃类木脂素
卢艳花1 ,高扬1 ,王峥涛2 ,刘建群2 ,魏东芝1
(1.华东理工大学 生物反应器国家重点实验室 , 鲁华生物技术研究所 上海 , 200237;
2.中国药科大学 生药学研究室 , 江苏 南京 , 210038)
摘要:　目的　研究望春花 Magnolia biondii Pamp 花蕾中的化学成分。方法　采用色谱技术进行分离纯化 , 根据理化性质
和现代波谱技术进行结构鉴定。结果　从望春花的花蕾乙醇提取物中分离鉴定出 1个苯并呋喃类新木脂素和 2 个已知木脂
素 , 分别鉴定为利卡灵 B(licarin B)1;木兰脂素(magnolin)2;辛夷脂素(fargesin)3。结论　木兰属植物中木脂素多为双环氧
型 ,苯并呋喃类新木脂素 licarin B 是首次从木兰科植物中分得。
关键词:望春花;licarin B;苯并呋喃木脂素
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139LU Yan-hua, et al:A Benzofuranoid Neolignan from Magnolia biondii Pamp