全 文 ：相思子根化学成分研究
———相思子醌 A ,B ,D ,E ,F ,G
宋纯清　胡之璧
(上海中医药大学　上海　200032)
摘要　从民间药用抗肝炎药相思子(Abrus precatorius L.)根中分得 8 个异黄烷醌类化合物 , 即相思子醌
A、B 、D、E 、F、G以及已知化合物 3 , 7-二羟基-6-甲氧基双氢黄酮和 2 , 8-二羟基-3 , 4 , 9 , 10-四甲氧基紫檀
素。用化学转化和光谱学方法包括1H-1H COSY、1H-13C COSY、CD等方法鉴定它们的结构。
关键词　豆科 ,相思子 , 异黄烷醌 ,相思子醌 A、B、D、E 、F、G
ABRUQUINONE A ,B ,D , E ,F AND G FROM THE
ROOT OF ABRUS PRECATORIUS
SONG Chun-Qing　HU Zhi-Bi
(Shanghai University of Traditional Chinese Medicine and Pharmacy , Shanghai 200032)
Abstract　Eight flavonoids have been isolated from the root of Abrus precatorius L.Among them ,
six isoflavanquinones , designated(3R)-abruquinone A , B , D and E , (3S)-abruquinone F and G ,
are characterized by chemical and spectral means including 1H-1H COSY , 1H-13C COSY and CD
methods.
Key words　Leguminosae , Abrus precatorius , isoflavans , isoflavanquinones
Abrus precatorius L.(Leguminosae)grows in tropic and subtropic areas , and mainly dis-
tributes in Fujian , Taiwan , Guangdong , Guangxi and Yunnan provinces in China.It is sweet to
taste and neutral in nature.It is often used as a crude drug for treating throat sore , hepatitis and
bronchitis , and the seeds are used externally for dermatophyte[ 1 ,2] .Lupi et al[ 3] have isolated
abruquinone A , B and C.In the course of our investigation on the constituents of this plant , we
have isolated eight compounds;six new isoflavanquinones , named as(3R)-abruquinone A , B , D
and E , and (3S)-abruquinone F and G;two known compounds—(2R , 3R)-3 , 7-dihydroxy-6-
methoxyflavanone and (6aR , 11aR)-2 ,8-dihydroxy-3 ,4 ,9 ,10-tetramethoxypterocarpan.
RESULTS AND DISCUSSIONS
The chloroform extract of the roots of Abrus precatorius L.was subjected to silica gel column
chromatography from which eight compounds(1 to 6 , 8 to 9)were obtained.UV(290 ～ 293 and
395 ～ 425 nm)and 1H-NMR(including the typic ABMXY system proton signals—O-CH2-CH-CH2)
analyses revealed that compounds 1 to 6 were deduced for isoflavanquinones (Tables 1 , 2)[ 3 ,4] .
Compound 1 having the same MS , UV , and 1H-NMRwas designated as(3S)-abruquinone A , and
2 having the same MS , UV , and 1H-NMR as(3S)-abruquinone B[ 3] ;however both 1 and 2 were
3R configurations according to positive CD curves[ 5 ,6] .The molecular formulae from elementary
UNESCO regional seminar on chemistry of bioactive natural products , Nov.6 , 1991 , Shanghai , China.p.23
Received:1998-01-19　Revised:1998-04-23
植　物　学　报　1998 , 40(8):734～ 739
Acta Botanica Sinica
analyses and mass spectra of compounds 3 to 6 are indicated as:C18H18O7 , C19H20O8 , C18H18O7
and C17H16O7 respectively.
Table 1　1H-NMR spectral data of abruquinone 1 to 7＊
1 2 3 4
H-2 4.26dd(11.0 , 2.5) 4.26dd(10.6 ,2.6) 4.25dd(11.0 , 3.0) 4.30dd(11.0 ,3.8)
H-2 3.99dd(11.0 , 5.9) 4.12dd(10.6 ,5.6) 3.99dd(11.0 , 6.0) 4.04dd(11.0 ,5.0)
H-3 3.41m 3.45m 3.41m 3.42m
H-4 3.00dd(16.0 , 6.0) 3.08dd(16.2 ,5.6) 2.99dd(16.0 , 6.0) 3.02dd(16.0 ,6.0)
H-4 2.82dd(16.0 , 8.0) 2.72dd(16.2 ,5.6) 2.82dd(16.0 , 8.0) 2.85dd(16.0 ,8.0)
H-5 6.70s 6.12s 6.70s 6.30s
H-6
H-8 6.45s 6.37s
H-6′ 6.46d(1.5) 6.20bs 6.43d(1.5) 6.43d(1.5)
MeO-6 3.77s 3.81s 3.81s 3.81s
MeO-7 3.82s 3.87s1)
MeO-8 3.89s1)
MeO-3′ 4.02s 4.03s 4.01s 4.03s
MeO-4′ 4.01s 4.02s 4.00s 4.01s
5 6 7
H-2 4.22dd(11.0 , 3.8) 4.14dd(10.5, 3.5) 4.12dd(10.0 , 3.5)
H-2 4.45dd(11.0 , 10.0) 4.28dd(10.5, 10.5) 4.38dd(10.0 , 10.0)
H-3 3.60dddd(12.5, 10.0 , 5.5 , 3.8)
3.55dddd
(12.5 ,10.5, 5.0 ,3.5)
3.48dddd
(12.0 , 10.0 , 5.0 , 3.5)
H-4 3.29dd(16.0 , 12.5) 3.16dd(16.5, 12.5) 3.12dd(15.0 , 12.0)
H-4 2.65dd(16.0 , 5.5) 2.55dd(16.5, 5.0) 2.74dd(15.0 , 5.0)
H-5 6.73d(8.5) 6.49bd(8.0) 6.85bd(8.5)
H-6 6.54d(8.5) 6.44d(8.0) 6.55d(8.5)
H-3′ 5.95s 5.95s 5.95s
MeO-7 3.79s 3.72s 3.80s
MeO-8 3.73s
MeO-4′ 3.86s 3.75s 3.82s
Ac-8 2.35s
Ac-6′ 2.30s
＊400 MHz , measured in acetone-d6 for 1～ 5 , DMSO-d6 for 6 , CDCl3 for 7 , J(Hz)in parentheses.
1)Assignments are interchangeable in each column.
As shown in Fig.1 , the peak at m/ z 194 for both compound 3 and 4 showed that two methoxy
groups were present in ring B , the peak at m/ z 153 showed that one hydroxy and one methoxy group
in ring A of compound 3 , the peak at m/ z 183 showed one more methoxy group in ring A of com-
pound 4;the peak 180 for both compound 5 and 6 showed one hydroxy and one methoxy group in
ring B , the peak 167 showed two methoxy groups in ring A of 5 , the peak 153 showed one less
methoxy group than compound 5 in ring A of compound 6.In addition to the NOE difference in
spectra(Table 3), 1H-13C-NMR long range COSY(Table 4)and comparisons with known com-
pounds—abruquinone A and B , the locations of substituents on the ring A and B were confirmed as
7-hydroxy-3′,4′,6-trimethoxy(3),7-hydroxy-3′, 4′, 6 , 8-tetramethoxy-(4), 6′-hydroxy-4′,7 , 8-
trimethoxy-(5)and 6′, 8-dihydroxy-4′, 7-dimethoxy-(6)isoflavanquinone.
The vicinal proton coupling constants for compounds 1 to 4 are similar and consistent with the
values expected for the half chain conformation (Fig.2)in which the 3-quinonyl substituent occu-
8 期 宋纯清等:相思子根化学成分研究———相思子醌 A , B , D , E , F , G(英) 735　
pies an axial position (J2 ,3 =2.5 ～ 3.0 and 6.0 ～ 6.5 Hz;J3 ,4 =6 and 6.5 Hz);while in
compunds 5 and 6 , 3-quinonyl occupies an equitorial position(J2 ,3=3.5 and 10.5 Hz , J3 ,4=5 ～
5.5 and 12.5Hz)(Fig.2)[ 5] .
Table 2　13C-NMR spectral data of isoflavanquinone 3 to 7
3 4 5 6 7
C-2 68.50t 68.54t 67.86t 66.76t 67.30t
C-3 31.54d 31.68d 30.55d 29.87d 31.34d
C-4 29.67t 29.81t 29.02t 27.74t 28.71t
C-5 113.18d 103.26d 116.98d 118.08d 125.86d
C-6 142.70s 139.89s 105.77d 107.63d 104.23d
C-7 146.64s 137.62s 152.71s 152.85s 150.38s
C-8 103.93d 136.50s 138.59s 134.72s 127.87s
C-4a 111.12s 115.83s 116.98s 115.34s 114.80s
C-8a 148.77s 147.93s 149.23s 145.30s 146.67s
C-1′ 147.23s 147.13s 131.44s 134.72s 134.88s
C-2′ 184.33s 184.31s 187.24s 186.88s 185.17s
C-3′ 146.08s 146.15s 109.04d 105.21d 107.82d
C-4′ 145.44s 145.51s 154.00s 156.17s 157.33s
C-5′ 183.80s 183.80s 179.48s 177.98s 174.40s
C-6′ 131.05d 131.14d 157.29s 156.70s 148.66s
MeO-6 56.53q 56.17q
MeO-7 56.49q 56.26q 56.32q
MeO-8 60.33q 60.21q
MeO-3′ 61.08q 61.11q
MeO-4′ 60.97q 60.98q 56.12q 56.05q 56.12q
Ac- 20.01q
Ac- 20.18q
Ac- 167.68s
Ac- 168.53s
Table 3　NOE difference in spectral relation of 3 to 5 and 7
Compound Saturation Observed(% increase)
3 H-5 MeO-6(8)
4 H-5 MeO-6(18)
H-6′ H-4(14)
5 H-6 MeO-7(10)
H-3′ MeO-4′(12)
7 H-6 MeO-7(6)
H-3′ MeO-4′(10)
The CD curves of compounds 1 to 4 exhibited a positive Cotton effect , and compounds 5 to 6 a
negative Cotton effect in the 260 ～ 300 nm region , according to Kurosawa[ 5 , 6] .We conclude that
the isoflavanquinone 1 to 4 and 5 to 6 have , respectively , the 3R and 3S configurations.So they are
named as 3R-abruquinone A , B , D , E and 3S-abruquinone F and G.Compounds 8 and 9 were
identified as(2R , 3R)-3 , 7-dihydroxy-6-methoxyflavanone and (6aR , 11aR)-2 , 8-dihydroxy-3 , 4 ,
9 ,10-tetramethoxypterocarpan by comparison of their spectra with those have been reported[ 7] .
736　 植　　物　　学　　报 40 卷
1 360 167(R1=H , R2=Me , R3=OMe) 194(R1=OMe , R2=H)
2 390 197(R1=OMe , R2=Me , R3=OMe) 194(R1=OMe , R2=H)
3 348 153(R1=H , R2=H , R3=OMe) 194(R1=OMe , R2=H)
4 378 183(R1= R3=OMe , R2=H) 194(R1=OMe , R2=H)
5 348 167(R1=OMe , R2=Me , R3=H) 180(R1=H , R2=OH)
6 332 153(R1=OH , R2=Me , R3=H) 180(R1=H , R2=OH)
Fig.1　Most important MS peaks generated from ring A and B
Fig.2　Conformations of compounds 1 to 4 and 5 , 6
8 期 宋纯清等:相思子根化学成分研究———相思子醌 A , B , D , E , F , G(英) 737　
EXPERIMENTAL
Mps:uncorrected.IR:KBr or chloroform film.MS:70 eV direct inlet.1H and 13C-NMR:
400MHz , 100 MHz (JEOL FX-400)spectrometer , assignments of 13C-NMR chemical shifts were
made with the aid of DEPT spectra , 1H-1H COSY and 1H-13C heteronuclear COSY.LC:silica gel ,
300 ～ 400 mesh.A voucher specimen was deposited at the Department of Phytochemistry , Shanghai
Institute of Materia Medica , the Chinese Academy of Sciences.
Isolation of the constituents of A.precatorius　The powdered roots(1 kg)were successively ex-
tracted with n-hexane , chloroform and methanol yielding extracts 8.1 g , 26.8 g and 72.9 g respec-
tively.The chloroform extract was subjected to silica gel column repeatedly eluting with benzene-
acetone(5∶1 , 5∶2V/V)and eight compounds(1 to 6 , 8 ,9)were obtained.(3R)-Abruquinone A(1)　Orange crystals(500 mg), mp 110 ～ 111 ℃;(found:C , 63.26;H ,
5.54.C19H20O7 requires:C , 63.50 , H , 5.29%).[α] D-112.18°(CHCl3 , c 1.06).UVλmax nm
(logε):270(4.15), 290(sh), 395(3.23).IRνmax cm-1:1655 , 1600 , 1510 , 1450.MS m/ z:
360(M+ , 100), 345(M+-CH3 , 42), 194(25), 167(38), 165(28.6), 86(34), 84(56).13C-
NMR(acetone-d6 , δ):184.31(C-2′), 183.84(C-5′), 149.80(C-7), 148.69(C-8a), 147.24
(C-1′), 146.14(C-3′),145.51(C-4′), 144.50(C-6), 131.14(C-6′), 111.20(C-4a), 111.07(C-5), 101.69(C-8), 68.51(C-2), 61.10(C-3′-OMe), 60.95(C-4′-OMe), 56.51(C-6-OMe),
55.77(C-7-OMe), 31.56(C-3),29.03(C-4).CD(MeOH)nm (Δε):290(+2.0), 258(-5.
4).
Table 4　1H-13C NMR long range COSY of 3 to 7
Compound H C
3 H-2 C-4 , C-8a , C-1′
H-5 C-6, C-7 , C-8a
H-6′ C-4′, C-5′
4 H-2 C-8a , C-1′
H-4 C-5
H-5 C-7 , C-8a
HO-7 C-6
H-6′ C-4′, C-5′
5 H-2 C-4
H-5 C-7 , C-8a
H-6 C-4a , C-5 , C-8
H-3′ C-5′, C-6′
7 H-2 C-8a
H-4 C-4a
H-5 C-4a , C-7 , C-8a
H-6 C-4a , C-8
H-3′ C-1′, C-5′
(3R)-Abruquinone B(2)　Amorphous(400
mg), Found:C , 61.48;H , 5.71.C20H22O8
requires:C , 61.53;H , 5.68%).[ α] D -
101.30(CHCl3 , c 1.91).UVλmax nm(logε):
268(4.03), 290(sh), 395(3.01).IR νmax
cm
-1:1655 , 1600 , 1490.CD(MeOH)nm
(Δε):288(+2.5), 257(-6.6).MS m/ z:
390(M+ , 100), 375(43.9), 197(63), 194
(26), 165(38), 86(35), 84(56).
(3R)-Abruquinone D(3)　Amorphous(30
mg), MS m/z:Found 346.1003;C18H18O7re-
quires 346.1052.[ α] D -77.76°(MeOH , c
1.5).UV λmax nm (log ε):294(4.16), 400
(3.23).IRνmax cm-1:3540 , 1655 , 1600.CD(MeOH) nm (Δε):300 (+0.6), 257
(-2.5).
(3R)-Abruquinone E(4)　Amorphous(35 mg), MS m/ z:Found 376.1116 , C19H20O8 requires
376.1158.[α] D -67.62°(MeOH , c 2.46).UV λmax nm (log ε):270(4.16), 290(sh), 390
(3.23).IRνmax cm-1:3530 , 1655 , 1600.MS m/ z:376(M+ , 50), 361(11), 196(19),195
(100), 194(23), 183(18), 179(10), 165(17), 91(12).CD(MeOH)nm(Δε):287(+0.3),
255(-3.2).
(3S)-Abruquinone F(5)　Red crystals , mp 197 ～ 198 ℃.MS m/ z:Found 346.1023 ,
C18H18O7 requires 346.1052.[α] D +23.7°(MeOH , c 0.93).UVλmax nm(log ε):295(3.78),
410(2.71).IRνmax cm-1:3250 , 1660.MS m/ z:346(100), 331(40), 193(17),192(30),
738　 植　　物　　学　　报 40 卷
181(37), 180(34), 168(23), 167(95), 151(22).CD(MeOH)nm(Δε):285(-0.4), 245
(-0.4).
(3S)-Abruquinone G(6)　Red crystals , mp 228 ～ 230 ℃(MeOH).Found:C , 61.41;H ,
4.86 , C17H16O7 requires:C , 61.45 , H , 4.82%.[ α] D +46.7°(MeOH , c 0.34).UVλmax nm
(log ε):292(4.03), 425(2.51).IRνmax cm-1:3530 , 3260 , 2830 , 2815 , 1660 , 1450 , 1070.
MS m/ z:332(M+ , 100), 317(27), 180(30), 165(6), 153(33), 151(9).CD(MeOH)nm
(Δε):290(-0.6), 239(+0.3).
Acetylation of G(7)　Compound G(30 mg)was treated with pyridine-Ac2O in the usual manner
and obtained the diacetate (20 mg), mp 172 ～ 173 ℃.[ α] D +23.8°(MeOH , c 0.46).IRνmax
cm-1:1770 ,1660 , 1370.
(2R , 3R)-3 , 7-Dihydroxy-6-methoxyflavanone(8)　Colourless crystals , mp 225 ～ 226 ℃.
Found:C , 67.28;H , 4.92.C16H14O5 requires:C , 67.13;H , 4.89%.UV λmax nm:240 ,
280 , 345.IRνmax cm-1:3400 , 1650 , 1612 , 1610 , 1510 , 1420 , 1290 , 1110 , 1025 , 985 , 900 ,
780 , 690.MS m/z:286(M+ ,11), 257(19), 179(3), 168(3), 167(33), 166(8), 151(2),
140(2), 123(1), 120(4), 91(5).1H-NMR(acetone-d6 , δ):7.32(1H , s , H-5), 6.53(1H ,
s , H-8), 5.18(1H , d , J=12 Hz , H-2), 4.63(1H , J=12.0 Hz , H-3), 4.50(1H , bs , HO-
2), 9.00(1H , bs , HO-7), 3.93(3H , MeO-6).On irridiating at the signalδ3.95 , the protonδ
7.32 get 11.8%NOE increasement.CD(MeOH)nm(Δε):340(+3.5), 280(+6.0).
(6aR , 11aR)-2 ,8-Dihydroxy-3 ,4 ,9 ,10-tetramethoxypterocarpan(9)　Colourless crystals(30
mg), mp 193 ～ 194 ℃(MS m/ z found:376.1182 , C19H20O8 requires 376.1158).[ α] D -193°
(MeOH).UVλmax nm:297(4.03).IRνmax cm-1:3320 , 3240 , 1600 , 1510 , 1500 , 1470.MS
m/ z:376(M+ , 100), 361(86), 194(16), 179(12), 91(32).1H-NMR(acetone-d6 , δ):3.65
(1H , m , H-3), 3.70(1H , dd , J=11.0 , 11.0Hz , Hax-6), 4.36(1H , dd , J=11.0 , 3.5 Hz ,
Heq-6), 5.54(1H , d , J=6.5 Hz , H-11), 6.68(1H , s , H-7), 6.69(1H , s , H-1), 7.47(1H ,
br.s , HO-8), 7.74(1H , br.s , HO-2), 3.81(3H , s , MeO-4), 3.83(3H , s , MeO-9), 3.84
(3H , s , MeO-3), 3.94(3H , s , MeO-10).CD(MeOH)nm(Δε):291(0), 298(+2.8), 314
(0).
Acknowledgement　The authors are grateful to Prof.U.Sankawa and Prof.Y.Ebizuka for their
encouragement and helpful discussion.We are also indebted to Dr.H.Noguchi , Faculty of Phar-
maceutical Sciences , Tokyo University , Japan for some NMR spectral measurements.Thanks should
also be given to Prof.SUN Chun-Yi for CD measurements in the Department of Analysis , Shanghai
Institute of Materia Medica , the Chinese Academy of Sciences.
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8 期 宋纯清等:相思子根化学成分研究———相思子醌 A , B , D , E , F , G(英) 739