桦木属植物化学成分的研究进展
作者：王素娟 裴月湖
单位：沈阳药科大学中药系，沈阳 110015
关键词：桦木属；化学成分；三萜；黄酮；木脂素；二苯基庚烷
沈阳药科大学学报000523 摘 要 桦木属植物主要含有三萜、黄酮、木脂素、二苯基庚烷等酚类.作者总结了近10年来的研究资料,对桦木属植物的化学成分作了综述.
分类号 R932
A Review on the Chemical Constituents of Betula L.
Wang Sujuan, Pei Yuehu
(Department of Chinese Traditional Medicines, Shenyang Pharmaceutical University,Shenyang 110015)
, http://www.100md.com
Abstract On the basis of 18 references in the recent decade, chemical constituents of Betula L. were reviewed in this paper，including triterpenoids, flavonoids, lignans, diarylheptanoids and other phenylics.
Key words Betula L.；chemical constituents；triterpenoids;flavonoids；lignans；diarylheptanoids
Fig.1 Ocotillol series
桦木属(Betula L.)植物在世界上约100种,主要分布于北温带,少数分布至北极区内.我国共有29种,6个变种,全国各地均有分布,植物资源十分丰富.在我国民间,桦木皮及桦木汁用于治疗慢性气管炎等.1987年,N.D.Pokhin〔1〕等人已对桦木属中的三萜类成分作了综述.近年来日本学者又对其境内的桦木属植物的化学成分做了系统研究.作者拟对近年来桦木属植物化学成分的研究进展作一综述.桦木属植物中主要含有三萜、黄酮、木脂素、二苯基庚烷及其他酚性成分.
, 百拇医药
1 三萜
桦木属中的三萜类成分主要存在于树皮和树叶中,主要类型有Ocotollol型(见图1、表1)、达玛烷型(见图2、表2)、羽扇豆烷型和齐墩果烷型(见图3、表3).1～49为以上各类型化合物.日本学者还发现3种开环三萜betula-schmidtoside A(50)、ovalifoliolides A(51)和ovalifoliolides B(52)(见图4),并认为这是桦木属与赤杨属亲缘关系较近的又一佐证〔11,12〕.化合物53为自B.pendula叶中分得的一种降三萜(见图5)〔9〕.化合物54为自B.platyphlla var. japonica的腐烂树皮中得到的betulin的生物降解产物〔13〕(见图6).
Fig.2 Four types of dammarane series
Fig.3 Lupane and oleanane series
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在这几类三萜中,3,11,12,17及25位常有羟基取代,其中3,11,12位羟基常被乙酰化,3位羟基还常被咖啡酸、香豆酸、丙二酸酰化,而其苷的种类较少,均为葡萄糖苷或乙酰葡萄糖苷.日本学者研究了3种白桦〔2，3，6〕,认为B.platyphylla var.japonica叶中具有3α-,12β-羟基的达玛烷型三萜,并可形成丙二酸酯,而B.errmanii叶中具有3β-,11α-羟基达玛烷型三萜,并形成葡萄糖苷.在B.platyphylla var.japonica〔6〕中,达玛烷型三萜存在于叶和根皮,树干部的树皮则没有;叶中的达玛烷型三萜具有3β-,12α-羟基,而树皮中的则只有3β-羟基,缺少12-羟基.
Tab.1 Triterpenoids of ocotollol series No.
Name
R1
, 百拇医药
R2
R3
R4
Source and literature
1
3-Epiocotillol Ⅱ
α-OH
H
H
H
Leaves of B.maximowicziana〔2〕
, 百拇医药
2
12β-Acetoxy-20(S),24(R)-epoxy-3α,25-dihydoxydammarane
α-OH
H
OAc
H
3
20(S),24(R)-Epoxy-3α,17α,25-trihydroxydammarane
α-OH
H
H
, http://www.100md.com
OH
4
12β-Acetoxy-20(S)-epioxy-3α,17α,25-trihydroxydammarane
β-OH
H
OAc
OH
5
20(S,24(R)-Epioxy-3β,11α,25-trihydroxydammarane
β-OH
OH
, http://www.100md.com
H
H
Leaves of B.errmanii〔3〕
6
Deacetoxypapyriferic acid
α-OCO CH2OH
H
OH
H
Twigs of B.pendula,twigs of B.glandulosa〔4,5〕
, http://www.100md.com 7
Papyriferic acid
α-OCO-CH2OH
H
OAc
H
B.pendula Roth.,twigs of B.glandulosa，leaves B.platyphylla var. japonica〔4,5,6〕
8
3β-Papyriferic acid
β-OCO-CH2OH
, http://www.100md.com
H
OAc
H
Root bark of B.pendula〔7〕
9
20(S),24(R)-Epoxy-3β,11α,25-trihydroxydammarane-3-O-β-D-glucopytanside
β-Glu
OH
H
H
Leaves of B.errmanii〔3〕
, http://www.100md.com
10
20(S),24(R)-Epoxy-3β,11α,25-trihydroxydammarane-3-O-β-D-2-O-Acetyl-glucopyranside
β-2′-O-Acteaylglc
OH
H
H
Leaves of B.errmanii〔3〕
11
11α-Acetyl-20(S),24(R)-epoxy-3β,25-dihydroxydammarane-3-O-β-D-2-O-acetylglucopyranside
, 百拇医药
β-2′-O-Acteaylglc
OAc
H
H
12
Betulamaximobide A
α-Glc
H
OAc
OH
Leaves of B.maximowiziana〔2〕
13
, 百拇医药
Betulamaximobide B
α-6′-O-Acteaylglc
H
OAc
OH
14
Ocotillol Ⅱ 3-O-caffeate
β-O-Caffeoyl
H
H
H
Root bark of B.platyphylla var. japonica〔6〕
, http://www.100md.com
从B.alba〔14〕的叶中得到两种单萜苷betullabuside A(55)和betullabuside B(56).从B.platyphylla var.japonica〔6〕的叶中得到倍半萜caryophyllene oxide(57)(见图7),此化合物具有白桦叶的特殊香气.
2 黄酮
黄酮主要分布在叶和花中,花中的黄酮多被甲基化.二氢黄酮类有柚皮素、刺槐素及其7-O-葡萄糖苷、樱花素；黄烷类有儿茶素及其7-O-木糖苷、二氢金丝桃苷、表儿茶素及5-O-和7-O-葡萄糖苷；黄酮类有芹菜素及-7，4′-二甲基醚、黄芩素及7-O-葡萄糖苷、柳穿鱼素及7-O-葡萄糖苷、cirsimaritin、salvigenin、木犀草素及7-O-芸香糖苷和4′-O-葡萄糖苷；黄酮醇类有山奈酚及其醚类和3-O-(4-乙酰)鼠李糖苷〔2〕、鼠李柠檬素、槲皮素及3-O-和7-O-鼠李糖苷、3-O-阿拉伯糖苷、3-O-(4-乙酰)鼠李糖苷〔2〕、3-O-葡萄糖苷、3-O-槐花糖苷、各种醚类、异槲皮苷、金丝桃苷、异金丝桃苷、异鼠李素及3-O-半乳糖苷、鼠李素、芦丁、杨梅黄素及3-O-半乳糖苷、3-O-二半乳糖苷、3-O-阿拉伯糖苷、杨梅苷.
, 百拇医药
Fig.4 Three seco-triterpenoids from Betula
Tab.2 Triterpenoinds of dammarane series No.
Name
R1
R2
R3
R4
Type
Source and literature
15
, 百拇医药
Damar-24-en-3β,11α, 20(S)-triol
β-OH
OH
H
H
I
Leaves of B.errmanii〔3〕
16
Dammarenediol Ⅱ
β-OH
H
H
, 百拇医药
H
Root bark of B.errmanii〔3〕
17
Betulafolienetetraol
α-OH
H
OH
OH
Leaves of B. maximowicziana〔2〕
18
12-Acetylbetulafolienetetraol
, 百拇医药
α-OH
H
OAc
H
19
Dammarenediol Ⅱ 3-caffeate
β-O-Caffeoyl
H
H
H
Root bark of B.maximowicziana, inner bark of B platyphylla var. japonica, root bark of B.errmanii〔2,3,6〕
, 百拇医药
20
12-O-Acetyl-3-O-malonyl-betulafolienetriol
α-O-COCH2-COOH
H
OAc
H
Root bark and leaves of B.pendula, leaves of B.platyphylla var.japonica〔2,7,8〕
21
Dammarenediol Ⅱ3-O-coumarate
, 百拇医药
β-O-p-Coumaroyl
H
H
H
Inner bark of B.platyphylla var.japonica〔6〕
22
Dammar-24-en-3β,11α,20(S)-triol 3-O-β-D-2-O-acetylglucopyranoside
β-O-2-Acetylglc
OH
H
, 百拇医药
H
Leaves of B.errmanii〔3〕
23
Dammar-24-en-12-O-acteyl-3α,12β,17α,20(S)-tetraol 3-O-malonate
α-OCOCH2-COOH
H
OAc
OH
Leaves of B.pendula〔8〕
24
, 百拇医药
Dammar-23(E)en-12-O-acetyl-3α,12β,20(S),25-tetraol 3-O-malonate
α-OCOCH2-COOH
H
OAc
—
Ⅱ
25
Dammar-24-en-3β,20(S),26-triol 3-O-caffeate
α-Caffeoyl
H
, http://www.100md.com
H
—
Ⅲ
Root bark of B.pendula〔2〕
26
Dammar-24-en-3β,20(S),26-triol 3-O-coumarate
β-O-p-Coumaroyl
H
H
—
27
, http://www.100md.com 12β,20(S)-Dihydroxy-dammar-24-en-3-one
=O
H
OH
H
Ⅰ
Leaves of B.platyphylla var.japonica,twigs of B.glandulosa〔3,4〕
28
12-O-Acetyl-betulafolienediolone
=O
, 百拇医药
H
OAc
H
29
12-O-Acetyl-3α,12β,20(S),24(R)-tetrahydroxydammar-25-en-3-yl hydrogen propanedioate
β-OH
H
Ⅳ
Leaves of B.penndula〔9〕
30
12-O-Acetyl-3α,12β,20(S),24(S)-tetrahydroxydammar-25-en-3-yl hydrogen propanedioate
, http://www.100md.com
α-OH
H
—
—
31
12-O-Acetyl-3α,12β,17α,20(S),24(R)-pentahydroxydammar-25-en-3-yl hydrogen propanedioate
β-OH
OH
—
—
Fig.5 A nortriterpenoid
, 百拇医药
from B.pendula
Fig.6 A biodegradation
production of betulin
Fig.7 Monterpenoids and sesquiterpenoids form Betula
3 木脂素、二苯基庚烷及其他酚类
此类化合物主要自内皮和叶中分得.木脂素类化合物(58～62)〔2，3，7，15〕及二苯基庚烷类化合物(63～79)〔2,3,6,16,17〕结构式可见图8.除此之外,尚有苯丁烷类化合物(80～88)〔11,17,18〕,苯乙烷类化合物(89、90)〔8,15〕等,可参见图9.
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桦木属植物的主要活性成分为三萜,尤其是达玛烷型三萜与人参三萜具有很大的类似性,具有广泛的生理活性,如抗癌,保肝,拒食,抗氧化,抗菌作用等.可以预见,桦木属的各种植物具有较好的开发应用前景.而我国虽具有丰富的植物资源,但对桦木属植物的研究开发甚少,因此对桦木属进行系统的研究具有较大的意义.
Tab.3 Triterpenoids of lupane and oleanane No.
Name
R1
R2
R3
Type
Source and literature
, 百拇医药
32
Lupeol
OH
CH3
CH3
Ⅳ
Leaves of B.maximowicziana,outer bark of B.platyphylla var.japonica and B.errmanii〔2,3,6〕
33
Betulin
OH
, http://www.100md.com
CH2OH
CH3
34
Betulinic acid
OH
COOH
CH3
Outer bark of B.platyphylla var.japonica〔6〕
35
Betulone
=O
, http://www.100md.com
CH2OH
CH3
36
Lupeol caffeate
O-Caffeoyl
CH3
CH3
Root bark of B.errmanii〔3〕
37
Betulin caffeate
, 百拇医药 O-Caffeoyl
CH2OH
CH3
Leaves of B.maximowicziana,inner bark of B.platyphylla var.japonica,bark of B.errmanii and B.pubescens〔2,3,6,10〕
38
Pyracrenic acid
O-Caffeoyl
COOH
CH3
, 百拇医药
Bark of B.pubescens<
单位：沈阳药科大学中药系，沈阳 110015
关键词：桦木属；化学成分；三萜；黄酮；木脂素；二苯基庚烷
沈阳药科大学学报000523 摘 要 桦木属植物主要含有三萜、黄酮、木脂素、二苯基庚烷等酚类.作者总结了近10年来的研究资料,对桦木属植物的化学成分作了综述.
分类号 R932
A Review on the Chemical Constituents of Betula L.
Wang Sujuan, Pei Yuehu
(Department of Chinese Traditional Medicines, Shenyang Pharmaceutical University,Shenyang 110015)
, http://www.100md.com
Abstract On the basis of 18 references in the recent decade, chemical constituents of Betula L. were reviewed in this paper，including triterpenoids, flavonoids, lignans, diarylheptanoids and other phenylics.
Key words Betula L.；chemical constituents；triterpenoids;flavonoids；lignans；diarylheptanoids
Fig.1 Ocotillol series
桦木属(Betula L.)植物在世界上约100种,主要分布于北温带,少数分布至北极区内.我国共有29种,6个变种,全国各地均有分布,植物资源十分丰富.在我国民间,桦木皮及桦木汁用于治疗慢性气管炎等.1987年,N.D.Pokhin〔1〕等人已对桦木属中的三萜类成分作了综述.近年来日本学者又对其境内的桦木属植物的化学成分做了系统研究.作者拟对近年来桦木属植物化学成分的研究进展作一综述.桦木属植物中主要含有三萜、黄酮、木脂素、二苯基庚烷及其他酚性成分.
, 百拇医药
1 三萜
桦木属中的三萜类成分主要存在于树皮和树叶中,主要类型有Ocotollol型(见图1、表1)、达玛烷型(见图2、表2)、羽扇豆烷型和齐墩果烷型(见图3、表3).1～49为以上各类型化合物.日本学者还发现3种开环三萜betula-schmidtoside A(50)、ovalifoliolides A(51)和ovalifoliolides B(52)(见图4),并认为这是桦木属与赤杨属亲缘关系较近的又一佐证〔11,12〕.化合物53为自B.pendula叶中分得的一种降三萜(见图5)〔9〕.化合物54为自B.platyphlla var. japonica的腐烂树皮中得到的betulin的生物降解产物〔13〕(见图6).
Fig.2 Four types of dammarane series
Fig.3 Lupane and oleanane series
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在这几类三萜中,3,11,12,17及25位常有羟基取代,其中3,11,12位羟基常被乙酰化,3位羟基还常被咖啡酸、香豆酸、丙二酸酰化,而其苷的种类较少,均为葡萄糖苷或乙酰葡萄糖苷.日本学者研究了3种白桦〔2，3，6〕,认为B.platyphylla var.japonica叶中具有3α-,12β-羟基的达玛烷型三萜,并可形成丙二酸酯,而B.errmanii叶中具有3β-,11α-羟基达玛烷型三萜,并形成葡萄糖苷.在B.platyphylla var.japonica〔6〕中,达玛烷型三萜存在于叶和根皮,树干部的树皮则没有;叶中的达玛烷型三萜具有3β-,12α-羟基,而树皮中的则只有3β-羟基,缺少12-羟基.
Tab.1 Triterpenoids of ocotollol series No.
Name
R1
, 百拇医药
R2
R3
R4
Source and literature
1
3-Epiocotillol Ⅱ
α-OH
H
H
H
Leaves of B.maximowicziana〔2〕
, 百拇医药
2
12β-Acetoxy-20(S),24(R)-epoxy-3α,25-dihydoxydammarane
α-OH
H
OAc
H
3
20(S),24(R)-Epoxy-3α,17α,25-trihydroxydammarane
α-OH
H
H
, http://www.100md.com
OH
4
12β-Acetoxy-20(S)-epioxy-3α,17α,25-trihydroxydammarane
β-OH
H
OAc
OH
5
20(S,24(R)-Epioxy-3β,11α,25-trihydroxydammarane
β-OH
OH
, http://www.100md.com
H
H
Leaves of B.errmanii〔3〕
6
Deacetoxypapyriferic acid
α-OCO CH2OH
H
OH
H
Twigs of B.pendula,twigs of B.glandulosa〔4,5〕
, http://www.100md.com 7
Papyriferic acid
α-OCO-CH2OH
H
OAc
H
B.pendula Roth.,twigs of B.glandulosa，leaves B.platyphylla var. japonica〔4,5,6〕
8
3β-Papyriferic acid
β-OCO-CH2OH
, http://www.100md.com
H
OAc
H
Root bark of B.pendula〔7〕
9
20(S),24(R)-Epoxy-3β,11α,25-trihydroxydammarane-3-O-β-D-glucopytanside
β-Glu
OH
H
H
Leaves of B.errmanii〔3〕
, http://www.100md.com
10
20(S),24(R)-Epoxy-3β,11α,25-trihydroxydammarane-3-O-β-D-2-O-Acetyl-glucopyranside
β-2′-O-Acteaylglc
OH
H
H
Leaves of B.errmanii〔3〕
11
11α-Acetyl-20(S),24(R)-epoxy-3β,25-dihydroxydammarane-3-O-β-D-2-O-acetylglucopyranside
, 百拇医药
β-2′-O-Acteaylglc
OAc
H
H
12
Betulamaximobide A
α-Glc
H
OAc
OH
Leaves of B.maximowiziana〔2〕
13
, 百拇医药
Betulamaximobide B
α-6′-O-Acteaylglc
H
OAc
OH
14
Ocotillol Ⅱ 3-O-caffeate
β-O-Caffeoyl
H
H
H
Root bark of B.platyphylla var. japonica〔6〕
, http://www.100md.com
从B.alba〔14〕的叶中得到两种单萜苷betullabuside A(55)和betullabuside B(56).从B.platyphylla var.japonica〔6〕的叶中得到倍半萜caryophyllene oxide(57)(见图7),此化合物具有白桦叶的特殊香气.
2 黄酮
黄酮主要分布在叶和花中,花中的黄酮多被甲基化.二氢黄酮类有柚皮素、刺槐素及其7-O-葡萄糖苷、樱花素；黄烷类有儿茶素及其7-O-木糖苷、二氢金丝桃苷、表儿茶素及5-O-和7-O-葡萄糖苷；黄酮类有芹菜素及-7，4′-二甲基醚、黄芩素及7-O-葡萄糖苷、柳穿鱼素及7-O-葡萄糖苷、cirsimaritin、salvigenin、木犀草素及7-O-芸香糖苷和4′-O-葡萄糖苷；黄酮醇类有山奈酚及其醚类和3-O-(4-乙酰)鼠李糖苷〔2〕、鼠李柠檬素、槲皮素及3-O-和7-O-鼠李糖苷、3-O-阿拉伯糖苷、3-O-(4-乙酰)鼠李糖苷〔2〕、3-O-葡萄糖苷、3-O-槐花糖苷、各种醚类、异槲皮苷、金丝桃苷、异金丝桃苷、异鼠李素及3-O-半乳糖苷、鼠李素、芦丁、杨梅黄素及3-O-半乳糖苷、3-O-二半乳糖苷、3-O-阿拉伯糖苷、杨梅苷.
, 百拇医药
Fig.4 Three seco-triterpenoids from Betula
Tab.2 Triterpenoinds of dammarane series No.
Name
R1
R2
R3
R4
Type
Source and literature
15
, 百拇医药
Damar-24-en-3β,11α, 20(S)-triol
β-OH
OH
H
H
I
Leaves of B.errmanii〔3〕
16
Dammarenediol Ⅱ
β-OH
H
H
, 百拇医药
H
Root bark of B.errmanii〔3〕
17
Betulafolienetetraol
α-OH
H
OH
OH
Leaves of B. maximowicziana〔2〕
18
12-Acetylbetulafolienetetraol
, 百拇医药
α-OH
H
OAc
H
19
Dammarenediol Ⅱ 3-caffeate
β-O-Caffeoyl
H
H
H
Root bark of B.maximowicziana, inner bark of B platyphylla var. japonica, root bark of B.errmanii〔2,3,6〕
, 百拇医药
20
12-O-Acetyl-3-O-malonyl-betulafolienetriol
α-O-COCH2-COOH
H
OAc
H
Root bark and leaves of B.pendula, leaves of B.platyphylla var.japonica〔2,7,8〕
21
Dammarenediol Ⅱ3-O-coumarate
, 百拇医药
β-O-p-Coumaroyl
H
H
H
Inner bark of B.platyphylla var.japonica〔6〕
22
Dammar-24-en-3β,11α,20(S)-triol 3-O-β-D-2-O-acetylglucopyranoside
β-O-2-Acetylglc
OH
H
, 百拇医药
H
Leaves of B.errmanii〔3〕
23
Dammar-24-en-12-O-acteyl-3α,12β,17α,20(S)-tetraol 3-O-malonate
α-OCOCH2-COOH
H
OAc
OH
Leaves of B.pendula〔8〕
24
, 百拇医药
Dammar-23(E)en-12-O-acetyl-3α,12β,20(S),25-tetraol 3-O-malonate
α-OCOCH2-COOH
H
OAc
—
Ⅱ
25
Dammar-24-en-3β,20(S),26-triol 3-O-caffeate
α-Caffeoyl
H
, http://www.100md.com
H
—
Ⅲ
Root bark of B.pendula〔2〕
26
Dammar-24-en-3β,20(S),26-triol 3-O-coumarate
β-O-p-Coumaroyl
H
H
—
27
, http://www.100md.com 12β,20(S)-Dihydroxy-dammar-24-en-3-one
=O
H
OH
H
Ⅰ
Leaves of B.platyphylla var.japonica,twigs of B.glandulosa〔3,4〕
28
12-O-Acetyl-betulafolienediolone
=O
, 百拇医药
H
OAc
H
29
12-O-Acetyl-3α,12β,20(S),24(R)-tetrahydroxydammar-25-en-3-yl hydrogen propanedioate
β-OH
H
Ⅳ
Leaves of B.penndula〔9〕
30
12-O-Acetyl-3α,12β,20(S),24(S)-tetrahydroxydammar-25-en-3-yl hydrogen propanedioate
, http://www.100md.com
α-OH
H
—
—
31
12-O-Acetyl-3α,12β,17α,20(S),24(R)-pentahydroxydammar-25-en-3-yl hydrogen propanedioate
β-OH
OH
—
—
Fig.5 A nortriterpenoid
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from B.pendula
Fig.6 A biodegradation
production of betulin
Fig.7 Monterpenoids and sesquiterpenoids form Betula
3 木脂素、二苯基庚烷及其他酚类
此类化合物主要自内皮和叶中分得.木脂素类化合物(58～62)〔2，3，7，15〕及二苯基庚烷类化合物(63～79)〔2,3,6,16,17〕结构式可见图8.除此之外,尚有苯丁烷类化合物(80～88)〔11,17,18〕,苯乙烷类化合物(89、90)〔8,15〕等,可参见图9.
, http://www.100md.com
桦木属植物的主要活性成分为三萜,尤其是达玛烷型三萜与人参三萜具有很大的类似性,具有广泛的生理活性,如抗癌,保肝,拒食,抗氧化,抗菌作用等.可以预见,桦木属的各种植物具有较好的开发应用前景.而我国虽具有丰富的植物资源,但对桦木属植物的研究开发甚少,因此对桦木属进行系统的研究具有较大的意义.
Tab.3 Triterpenoids of lupane and oleanane No.
Name
R1
R2
R3
Type
Source and literature
, 百拇医药
32
Lupeol
OH
CH3
CH3
Ⅳ
Leaves of B.maximowicziana,outer bark of B.platyphylla var.japonica and B.errmanii〔2,3,6〕
33
Betulin
OH
, http://www.100md.com
CH2OH
CH3
34
Betulinic acid
OH
COOH
CH3
Outer bark of B.platyphylla var.japonica〔6〕
35
Betulone
=O
, http://www.100md.com
CH2OH
CH3
36
Lupeol caffeate
O-Caffeoyl
CH3
CH3
Root bark of B.errmanii〔3〕
37
Betulin caffeate
, 百拇医药 O-Caffeoyl
CH2OH
CH3
Leaves of B.maximowicziana,inner bark of B.platyphylla var.japonica,bark of B.errmanii and B.pubescens〔2,3,6,10〕
38
Pyracrenic acid
O-Caffeoyl
COOH
CH3
, 百拇医药
Bark of B.pubescens<