全 文 ：Chem ical constituents from leaves ofCelastrus gemmatus Loes.
FENG W ei-sheng1* , HAO Zhi-you1 , ZHENG X iao-ke1 , KUANG H ai-xue2
(1. Henan University of T rad itiona l ChineseMedicine, Zhengzhou 450008 , China;
2. Heilong jiang University of Traditiona lCh ineseM edicine, Harbin 150040 , China)
Abstract:To study the chem ical constituents from the leaves of Celastrus gemmatus Loes. ,
chromatograph icme thods we re used to isola te and pu rify the chem ical constituents, the ir structures w ere
e lucidated by the physiochem ica l characteristics and spec tral da ta. N ine compounds we re ob tained and
iden tified as ( - )-massoniresinol 3a-O-β-D-g lucopy ranoside (1), ambro sidine (2), iso laric iresino l 9-O-
β-D-g lucopyranoside (3), kaempfe ro l 3-O-β-D-g lucopy ranoside (astraga lin) (4), kaempfero l 3-O-
rutinoside (5), kaempferol 3-O-neohespe ridoside (6), apigenin 7-O-β-D-g lucuronide (7), apigenin 7-O-
β-D-g lucuron ideme thy l este r (8) andD-sorbitol (9). Compound 1 is a new compound , the o thers are
iso lated from th is genus for the first time, and th is is the first time to report lignan compounds from genus
Celastrus.
Key words:Celastrus gemma tus Loes. ;lignan g lycosides;flavono id g lycosides;( -)-massoniresino l
3a-O-β-D-g lucopy ranoside
CLC num ber:R284. 2　　　D ocum ent code:A　　　Artic le ID:0513 - 4870(2007)06 -0625 - 06
Received date:2006-12-29.
Foundat ion item:K ey Project of Ch in ese M in istry of Education
(2003078).
* Correspond ing au thor　Tel:86 -371 - 65575963,
Fax:86 - 371 - 65680011,
E-m ail:fw sh@ hactcm. edu. cn
哥兰叶化学成分的研究
冯卫生1* , 郝志友 1 , 郑晓珂1 , 匡海学 2
(1. 河南中医学院 , 河南 郑州 450008;2. 黑龙江中医药大学 , 黑龙江 哈尔滨 150040)
摘要:为研究哥兰叶(Celastrus gemmatus Loes. )中的化学成分 , 用 Diaion H P-20, Toyopea rlHW-40, silica ge l等柱
色谱方法 , 从其 70%含水丙酮提取物中分离得到化合物 , 并根据理化性质和波谱数据鉴定其结构。共得到 9个化合
物 , 分别为左旋马尾松树脂醇-3a-O-β-D-吡喃葡糖苷(1), am bro sidine(2), 异落叶松脂素-9-O-β-D-吡喃葡糖苷(3),山
柰酚-3-O-β-D-吡喃葡糖苷 (紫云英苷)(4), 山柰酚-3-O-α-L-吡喃鼠李糖基-(1→ 6)-β-D-吡喃葡糖苷(5),山柰酚-3-O-
α-L-吡喃鼠李糖基-(1→ 2)-β-D-吡喃葡糖苷(6), 芹菜素-7-O-β-D-葡糖醛酸苷(7), 芹菜素-7-O-β-D-吡喃葡糖醛酸甲
酯(8), D-山梨醇(9)。化合物 1为新化合物 ,其余化合物为首次从该属植物中分离得到。本文为首次报道该属植物
中的木脂素类化合物。
关键词:哥兰叶;木脂素苷;黄酮苷;左旋马尾松树脂醇-3a-O-β-D-吡喃葡糖苷
There are about 50 species o f genusCelastrus a ll
over the w orld, and abou t 30 of them in China.
Traditionally, some species of Celastrus we re used to
pro tect plan ts from insect damage. From the 1960s on,
abou t 210 sesquiterpenoids w ith β-dihydroagarofuran
ske leton and som e d ite rpeno ids, triterpenoids,
flavonoids, alkaloids and othe r constituents have been
iso lated from genusCelastrus, but no lignan from th is
genus has been reported be fore. Celastrus gemmatus
Loes. , a tradi tiona l plant insec ticide in Ch ina, e ithe r,
has been also utilized as both w ild vege tab le
[ 1]
and
he rbal medicine
[ 2]
. In particular, it has been p re-
scribed fo r the trea tmen t o f rheuma tic arth ritis, irregu-
larmenstrua tion, and so on. Phy tochem ica l investiga-
625 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(6):625 - 630DOI牶牨牥牣牨牰牬牫牳牤j牣牥牭牨牫牠牬牳牱牥牣牪牥牥牱牣牥牰牣牥牨牨
tions
[ 3 - 5]
ofCelastrus gemmatus have identified several
sesquiterpenoids w ith β-dihyd roagarofuran skele ton. In
th is paper, the isola tion and structure e lucidation of a
new te trahydrofuran lignan and eigh t known compounds
w ere presented.
Results and discussion
Aqueous ace tone (70%) ex tract of leaves of
Celastrus gemma tus was sub jec ted to a series of
chromatographic procedures, including D iaionHP-20,
Toyopearl HW-40C and Silica ge l co lumn chroma to-
graphy, affording 9 compounds (Figure 1). The
struc tures o f these compounds w ere established as a
new tetrahydrofuran lignan, ( - )-m assoniresino l 3a-
O-β-D-g lucopy ranoside ( 1 ), a furo fu ran lignan
glycoside, ambrosidine (2), a arylnaphtha lene lignan
glycoside, iso lariciresino l 9-O-β-D-g lucopy ranoside
(3), five flavono id g lycosides, kaempfe ro l 3-O-β-D-
glucopy ranoside(astragalin) (4), kaempfe ro l 3-O-
rutinoside ( 5 ), kaempfero l 3-O-neohespe ridoside
(6), apigenin 7-O-β-D-g lucuronide (7), apigenin
7-O-β-D-g lucu ronide methy l este r (8), and a po lyo l,
D-so rbito l (9), on the basis of UV , IR , NMR
(1H NMR, 13 C NMR, 1H-1H COSY , DEPT, HSQC
and HMBC) andM S experiments and by comparisons
w ith litera ture data. A ll of these compounds are
repo rted here fo r the first time as components o f
Celastrus gemmatus. E specia lly, this is the first time to
obtain lignan compounds from genusCelastrus.
F igure 2　The keyHMBC co rrela tions of compound 1
Compound 1 was obta ined as a pa le yellow
amo rphous powder, it gave positive ferric chlo ride and
po tassium ferricyanide reactions, indicating that itw as
a phenol compound probably, and showed a v io le t spo t
w ith 5% H2 SO 4 spray reagen t in e thanol on silica ge l
TLC fo llowed by hea ting. The HR-TOF-MS gave a
quasimo lecu lar ion peak atm /z 577.187 9[M +N a] +
(ca lcd forC26H34O13Na:577.188 9). TheUV and IR
spectra show ed absorp tions at 229, 280 nm and 3 387,
1 650, 1 520, 1 053 cm - 1 , revea led the presence o f
F igure 1　Structures of compounds 1 -9
626 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(6):625 - 630
aromatic ring and hydroxy g roup. The
1
H NMR spectra
show ed the presence o f six arom atic pro ton signals at
δ6.71(1H , d, J =8.1 H z), 6.72(1H , dd, J =
1.1, 8.1H z), 6.93(1H , d, J =1.1 Hz) and 6.74
(1H , d, J =8.1 H z), 6.83(1H , dd, J =1.4, 8.1
H z), 7.02 (1H , d, J =1.4 H z), the coup ling
constants suggested that the compound have tw o ABX
aromatic system s. The
1
H NMR also show ed two ary l
me thoxyl signa ls atδ3.84(3H , s), δ3.85(3H , s),
a benzy lic methy lene atδ2.91(2H , ABq, J =14.0
H z), tw o methy lenes attached to oxygen atoms at
δ4.20(1H , d, J =10.0 H z), 3.71(1H , d, J =
10.0H z) and δ3.22(1H , d, J =9.0 Hz), 3.26
(1H , d, J =9.0 H z), a me th ine bearing an oxygen
function atδ5.12(1H , s). And in 1H NMR spectrum
the p ro ton signa ls of sugar mo iety a tδ3.20 - 4.32
w ere also obse rved. The
13
C NMR spectrum and DEPT
experiment show ed the presence of tw e lve arom atic
carbon signals atδ113.2(CH), 115.3(CH), 115.4
(CH), 115.7(CH ), 122.0(CH ), 124.2(CH),
130.0(C), 131.1(C), 146.2(C), 147.1(C),
148.4(C), 148.5(C);six carbon signals assignab le
to a g lucopy ranosy l at δ104.7(CH ), 74.0(CH),
77.9(CH), 71.7(CH), 78.1(CH), 62.8(CH2);
th ree seconda ry carbons, tw o of which attached to
oxygen atom s at δ75.2 , 72.1, the o ther one at
δ40.2, wh ich attached to an arom atic circle; two
qua te rnary ca rbons a t δ81.4, 82.5; tw o me thoxy l
carbons atδ56.4. The HSQC experiment show ed that
the anomeric carbon o f g lucopy ranosy l (δ104.7) and
δH (4.3, 1H , d, J =8.0 Hz) have co rrela tion
re lationship, wh ich show ed a β-glucose on the basis of
the coupling constan.t A ll of the data above suggest
that this compound is a glucopy ranoside of
monoepoxy lignan, and position 3 (δC 82.5) and 4
(δC 81.4)must carry hydroxy l functions. The glycosy l
unit o f 1 was shown to be attached to C-3a o f the
ag ly cone as demonstra ted by the HMBC co rrela tion
betw een H-1 (δ4.31) o f the g lucopyranosy l portion
and C-3a (δC 72.1) o f the ag lycone.
In addition, the acid hydro ly sis of 1 re leased a
known lignan , ( - )-massonire sinol[ 6] , and glucose,
which w as iden tified by PC and TLC analysis. Thus,
the struc ture of the new monoepoxy lignan g lycoside w as
dete rm ined as ( - )-m assoniresino l 3a-O-β-D-g luco-
pyranoside (Figu re 1, 2). The fu ll assignments o f a ll
the signals o f compound 1 were comp le ted by means of
1
H NMR, 13C NMR, 1H-1H COSY , HSQC , HMBC
and DEPT.
Expermi ental
Melting pointsw ere dete rm ined on a Koflerm icro-
melting point apparatus and uncorrec ted. Optica l
rota tions w ere ob tained using a Perkin-E lmer 341
po larime te r. UV spectra w ere measured w ith a
Shimadzu UV-V IS 2201 spec trophotome te r. IR spectra
w ere measured w ith a Sh imadzu FTIR-8201 PC
spectrometer. The
1
H and
13
C NMR spectra w ere
obtained on a B rukerDPX-400 spectrome ter(400MHz
for
1
H NMR and 100MH z for
13
C NMR)w ith TM S as
interna l re ference. HR-TOF-MS were reco rded on an
APEX II spec tromete r. Co lumn ch roma tog raphy w as
pe rfo rmed on D iaion HP-20 (M itsubishi Chem ica l
C orp. , Japan), silica gel (160 - 200 mesh, Q ingdao
Haiyang Chem ical Co. , Ltd. , Ch ina), Toyopearl
HW-40C ( TOSOH Corp. , Japan ). TLC w as
conducted on se lf-m ade silica ge lG (Q ingdaoH aiy ang
Chem ica l Co. , Ltd. , China) pla tes. The chem ica l
reagents w ere purchased from B eijing Chem ica l P lan t
and Tianjin No. 3 Reagent P lan.t
P lant mater ial 　 Fresh leaves of Celastrus
gemmatus were co llected from X ix ia County, Henan
Province in China, and identified by P ro.f DONG
Cheng-m ing ofHenanUn iversity o f TraditionalCh inese
M edicine. A vouche r specimen have been deposited in
our laboratory.
Extraction and isola tion　D ried leaves (10 kg)
o fCelastrus gemma tus were extracted by 70% aqueous
ace tone tw ice a t room temperature, and concentrated
under reduced pressure to afford a dark-brown residue
(1 892 g), and w as suspended in sm all excess o f
H2O. The suspension w as extrac ted by e ther, ethy l
ace tate, n-bu tano l, separately. The extract of the n-
bu tano l part (95 g)was chromatog raphied on a D iaion
HP-20 co lumn w ith aqueousM eOH (0 - 80%), and
the 30%M eOH partw as then successfu lly sub jected to
a Toyopearl HW-40C co lumn w ith aqueous M eOH
(0 - 50%) to g ive 160 frac tions, the fractions 31 - 48
w ere rechromatograph ied on a silica ge l co lumn w ith
E tOAc-E tOH-H2O (15 ∶2 ∶1, v /v /v) to affo rd
compound 1 (10.5 mg), the fractions 100 - 160 w ere
rechrom atog raphied on a silica ge l column w ith E tOA c-
E tOH-H2O (20∶2∶1, v /v /v) to afford compound 5
(26.4 mg ), and the fractions 22 - 30 w ere
rechrom atog raphied on a silica ge l column w ith E tOA c-
E tOH-H2O (15∶2∶1, v /v /v), and then purified on a
Toyopearl HW-40C co lumn w ith M eOH to affo rd
compound 2 (18.3mg). The 20% MeOH part of the
D iaion HP-20 co lumn y ie lded compound 3 (15.7
627 FENG W ei-sheng, e t al:Chem ical constituents from leave s ofCelastrus gemmatus Loes.
mg), and the 40% MeOH part y ie lded compound 7
(8.2mg) and 8 (25.9mg)w ith the sim ilarme thods
of chroma tography and recry sta llization.
The ex tract of the ethy l aceta te part(86 g) was
chromatographied on a Diaion HP-20 column w ith
aqueousM eOH (0 -80%), and the 40%M eOH part
w as then successfu lly sub jected to a silica gel co lumn
and e lu ted w ith CHC l3-MeOH-H2O (4∶1∶0.1, v /v /v)
to g ive 150 fractions, the fractions 34 - 88 w ere
rechromatographied on a silica gel co lumnw ith E tOAc-
E tOH-H2O (40∶2∶1 , v /v /v), and then purified on a
Toyopearl HW-40C co lumn w ith M eOH to afford
compound 4 (12.2mg), the fractions 110 - 115 w ere
rechromatographied on a silica gel co lumnw ith E tOAc-
E tOH-H2O (30∶2∶1, v /v /v) to affo rd compound 6
(20.6 mg). F rom the 50% M eOH part compound 9
(13.7mg)was obta ined w ith the sim ilarme thods.
Acid hydrolysis of compound 1　HC l(3mL, 1
mo l L -1) was added to 3 mL M eOH solution of 1
(3.4mg). Them ix tu re w as heated under re flux fo r 4
h. The solution w as ex tracted w ith E tOA c. The E tOA c
solution w as subjected to a silica ge l (1.5 g) co lumn
and e luted w ith CHC l3-MeOH-H2O (7∶1∶0.1, v /v /
v). Amorphous powder (1.5 mg) was obtained and
identified to be ( - )-m assoniresino l ( 1′) by
comparing the
1
H , 13 C NMR and CD spec tra ldata w ith
the reference
[ 6]
. The wa ter laye rw as neutra lized, and
glucose w as identified by PC and silica ge l TLC w ith
authentic sample.
Identification
( -)-Massoniresinol 3a-O-β-D-glucopyranoside
(1)　Pale yellow amo rphous powde r;mp 209 -
211℃;[ α] 25D =- 11.1°(c 0.53, MeOH);UV λmax
(MeOH) nm ( log ε):211(2.72), 229(1.75), 280
(1.45);IR(KB r)υmax cm -1:3 387, 2 923, 1 605,
1 520 , 1 275, 1 075, 1 053;The 1H NMR (400
MH z, CD3OD) and 13 C NMR (100 MH z, CD3OD)
spectra l data see Table 1; HR-TOF-MS m /z:
577.187 9 (calcd fo rC26H34O13Na:577.188 9).
( - )-Massoniresinol (1′)　White amo rphous
powder;[ α] 25D - 30.7°(c 0.36, M eOH );1H NMR
(400MH z, CD3OD) δ:6.8 - 7.2(6H , m , arom atic
pro tons), 4.97(1H , s, H-2), 3.86(6H , s, 2 ×
OM e), 3.6 - 4.0(4H , m , H-3a, H-5), 2.88(2H ,
s, H-4a);13C NMR (100 MH z, CD3OD) δ:148.3
(C-3′, 3″), 146.8(C-4′), 146.3(C-4″), 131.0(C-1′),
130.2(C-1″), 123.8(C-6″), 121.3(C-6′), 115.7
(C-5′), 115.5(C-5″), 115.2(C-2″), 112.9(C-2′),
86.1(C-2), 82.2(C-4), 81.8(C-3), 74.7(C-5),
64.2(C-3a), 56.5(3′-OM e, 3″-OM e), 40.1(C-4a);
CD(MeOH , c 7.5×10-4):Δξ25 0(305), +2.06(285),
+0.24(254), +5.76(235), +0.36(220), +2.27
(207), 0(202), - 0.24(198). These data w ere
consisten tw ith those of the reference
[ 6]
.
Ambrosid ine (2 ) 　 Pale ye llow amorphous
powde r;1H NMR (400MHz, CD3OD)δ:7.13(1H ,
d, J =8.4 Hz, H-5′), 7.11(1H , d, J =1.6H z, H-2′),
7.03(1H , d, J =2.0 H z, H-2″), 6.93(1H , dd, J =
1.6, 8.4Hz, H-6′), 6.83(1H , dd, J =2.0, 8.0H z,
H-6″), 6.76(1H , d, J =8.0Hz, H-5″), 5.01(1H ,
s, H-6), 4.97(1H , s, H-2), 4.89(1H , H-1 ),
4.12(1H , d, J =9.6Hz, H-4a o rH-8a), 4.11(1H ,
d, J =9.6H z, H-8a orH-4a), 3.97(2H , d, J =9.6
Hz, H-4b /8b), 3.87(3H , s, H-3′OM e), 3.85(H-3″
OM e);13C NMR(100MHz, CD3OD) δ:150.4(C-3′),
148.7(C-3″), 147.7(C-4″), 147.5(C-4′), 133.2
(C-1′), 129.5(C-1″), 121.6(C-6″), 121.4(C-6′),
117.5(C-5′), 115.6(C-5″), 113.5(C-2′), 112.9
(C-2″), 89.3(C-2), 89.1(C-1, C-5), 88.8(C-6),
76.8(C-4 or C-8), 76.7(C-8 or C-4), 56.7(C-3′
OM e), 56.4(C-3″OM e), glc(C-1 - C-6):102.9,
74.9, 77.8, 71.4, 78.2, 62.5. These data w ere
consisten tw ith those of the reference
[ 7]
.
Isolariciresinol 9-O-β-D-glucopyranoside (3)
Pa le ye llow amorphous powde r;1H NMR (400 MH z,
CD 3OD) δ:6.78(1H , d, J =1.8 H z, H-2), 6.73
(1H , d, J =8.1 H z, H-5), 6.64(1H , s, H-2′),
6.62(1H , dd, J =1.8, 8.1Hz, H-6), 6.17(1H , s,
H-5′), 4.10(1H , d, J =7.8H z, H-1″), 4.07(1H ,
m , H-8), 4.06(1H , m , H-9a), 3.80(3H , s, H-3′
OM e o r H-3OM e), 3.79(3H , s, H-3OM e or H-3′
OM e), 3.75(2H , m , H-9′), 3.23(1H , m , H-9b),
2.82(2H , m , H-7′), 2.08(1H , m , H-8′), 1.85
(1H , m , H-7);13 C NMR (100 MHz, CD3OD) δ:
148.9(C-3′), 147.2(C-3), 145.9(C-4′), 145.2
(C-4), 138.7(C-6′), 134.4(C-1), 129.2(C-1′),
123.2(C-6), 117.4(C-5′), 116.1(C-5), 114.4
(C-2), 112.4 (C-2′), 69.5(C-9), 65.2(C-9′),
56.5(C-3OM e or C-3′OM e), 56.4(C-3′OM e o r C-3
OM e), 47.9(C-8), 45.9(C-7), 39.6(C-8′), 33.9
(C-7′), g lc(C-1 -C-6):102.2, 75.2, 77.9, 71.7,
78.2, 62.8. These data w ere consistent w ith those o f
the refe rence
[ 8]
.
Kaempferol 3-O-β-D-glucopyranoside (astra-
galin) (4)　 Ye llow cry stals (MeOH );1H NMR
(400MHz, CD3OD) δ:8.04(2H , d, J =8.8 H z,
H-2′, 6′), 6.87(2H , d, J =8.8 Hz, H-3′, 5′),
628 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(6):625 - 630
6.39(1H , d, J =1.3H z, H-8), 6.19(1H , d, J =
1.3H z, H-6), 5.24(1H , d, J =7.2 Hz, H-1″);
13
C NMR(100MHz, CD3OD) δ:179.5(C-4), 166.2
(C-7), 163.3(C-5), 161.6(C-4′), 159.1(C-2),
158.5(C-9), 135.4(C-3), 132.3(C-2′, 6′), 122.8
(C-1′), 116.1 (C-3′, 5′), 105.7 (C-10), 99.9
(C-6), 94.8(C-8), g lc(C-1 - C-6):104.1, 75.7,
78.0, 71.4, 78.4, 62.6. The se data w e re consistent
w ith those o f the re ference
[ 9]
.
Table 1　1H NMR and 13C NMR data of compound
1 (CD3OD)
Position　 δC　 δH(J, H z) DEPT
2 86. 5　 5.12 (1H , s) CH
3 82. 5 C
3a 72. 1 4.20 (1H , d, J =10. 0H z) CH2
3.71 (1H , d, J =10. 0H z)
4 81. 4 C
4a 40. 2 2.91(2H , ABq, J =14. 0 H z) CH2
5 75. 2 3.22(1H , d, J =9. 0 H z) CH2
3.26(1H , d, J =9. 0 H z)
1′ 131. 1 C
2′ 113. 2 7.02(1H , d, J =1. 4 H z) CH
3′ 148. 4* C
4′ 147. 1 C
5′ 115. 7 6.74(1H , d, J =8. 1 H z) CH
6′ 122. 0 6.83(1H , dd , J=8. 1, 1. 4 H z) CH
1″ 130. 0 C
2″ 115. 3 6.93(1H , d, J =1. 1 H z) CH
3″ 148. 5* C
4″ 146. 2 C
5″ 115. 4 6.71(1H , d, J =8. 1 H z) CH
6″ 124. 2 6.72(1H , dd, J =8. 1, 1. 1 H z) CH
3′-OM e 56. 4 3.85 (3H , s)* CH3
3″-OM e 56. 4 3.84 (3H , s)* CH3
G lc-1 104. 7 4.31(1H , d, J =8. 0 H z) CH
G lc-2 74. 0 3.90(1H , m) CH
G lc-3 77. 9 3.36(1H , m) CH
G lc-4 71. 7 3.30(1H , m) CH
G lc-5 78. 1 3.29(1H , m) CH
G lc-6 62. 8 3.66(1H , m), 3. 90(1H , m) CH2
* Signa ls m aybe reve rsed
Kaempferol 3-O-rutinoside (5)　Ye llow amo r-
phous powder;1H NMR (400MH z, CD3OD)δ:8.05
(2H , d, J =8.8 H z, H-2′, 6′), 6.88(2H , d, J =8.8
H z, H-3′, 5′), 6.41(1H , d, J =1.6 Hz, H-8),
6.21(1H , d, J =1.6 H z, H-6), 5.12(1H , d, J =7.3
H z, H-1″), 4.50(1H , br s, H-1 ), 1.12(3H , d, J =
6.2H z, H-6 );13 C NMR (100 MH z, CD3OD) δ:
179.4(C-4), 166.1(C-7), 163.1(C-5), 161.5(C-4′),
159.4(C-2), 158.6(C-9), 135.5(C-3), 132.4
(C-2′, 6′), 122.8(C-1′), 116.1(C-3′, 5′), 105.7
(C-10), 99.9(C-6), 94.9(C-8), g lc(C-1 - C-6):
104.6 , 75.8, 78.1, 72.3, 77.3, 68.6. rha(C-1 -
C-6):102.4, 71.4, 72.1, 73.9 , 69.7, 17.9. These
data w ere consistentw ith tho se o f the re ference
[ 10]
.
Kaempferol 3-O-neohesperidoside (6)　Yellow
amo rphous powder;1H NMR (400MHz, CD3OD)δ:
8.03(2H , d, J =8.7 Hz, H-2′, 6′), 6.87(2H , d,
J =8.7Hz, H-3′, 5′), 6.35(1H , br s, H-8), 6.16
(1H , br s, H-6), 5.73(1H , d, J =7.5Hz, H-1″),
5.22(1H , b r s, H-1 ), 0.94(3H , d, J =6.2 H z,
H-6 );13 C NMR (100 MH z, CD 3OD) δ:179.3
(C-4), 166.4(C-7), 163.1(C-5), 161.3(C-4′),
158.5(C-9), 158.4 (C-2), 134.4 (C-3), 132.1
(C-2′, 6′), 123.2(C-1′), 116.1(C-3′, 5′), 105.8
(C-10), 99.9(C-6), 94.7(C-8), g lc(C-1 - C-6):
100.3 , 80.1, 79.0, 71.8, 78.4, 62.6. rha(C-1 -
C-6):102.6, 72.3, 72.4, 74.1, 69.9, 17.5. The
data o f
13
C NMR were consistent w ith those of the
reference
[ 11]
.
Ap igenin 7-O-β-D-glucuronide (7)　 Yellow
amo rphous powder;1H NMR (400 MH z, DMSO-d6)
δ:7.91(2H , d, J =8.3 H z, H-2′, 6′), 6.91(2H ,
d, J =8.3Hz, H-3′, 5′), 6.83(1H , s, H-3), 6.80
(1H , br s, H-8), 6.42(1H , br s, H-6), 5.10(1H ,
d, J =7.1H z, H-1″);13C NMR (100MH z, DMSO-
d6) δ:181.8(C-4), 164.1(C-2), 162.8(C-7),
161.5(C-5), 160.9(C-4′), 156.8(C-9), 128.4
(C-2′, 6′), 120.7(C-1′), 115.9(C-3′, 5′), 105.2
(C-10), 102.9(C-3), 99.4(C-6), 94.6(C-8),
g lcA(C-1 - C-6):99.4, 72.8 , 74.1, 71.8, 76.3,
172.6. The da ta o f 1H NMR and 13C NMR were
consisten tw ith those of the reference
[ 12]
.
Ap igenin 7-O-β-D-glucuronide m ethyl ester
(8)　Pa le ye llow needles cry sta ls(M eOH);1H NMR
(400MHz, DMSO-d6) δ:7.96(2H , d, J =8.8H z,
H-2′, 6′), 6.94(2H , d, J =8.8 Hz, H-3′, 5′),
6.88(1H , s, H-3), 6.86(1H , d, J =2.2 , H-8),
6.47(1H , d, J =2.2, H-6), 5.33(1H , d, J =
7.33, H-1″), 3.67 (3H , s, H-OM e);13C NMR
(100 MH z, DMSO-d6 ) δ: 181.9 (C-4), 164.2
(C-2), 162.3(C-7), 161.3(C-5), 161.1(C-4′),
156.9 (C-9), 128.5 (C-2′, 6′), 120.9 (C-1′),
115.9(C-3′, 5′), 105.4(C-10), 103.1(C-3), 99.2
(C-6), 94.5(C-8), 51.9(C-OM e), g lcA (C-1 -
C-6):99.0 , 72.6, 75.1, 71.2, 75.3, 169.1. The
data o f
1
H NMR and
13
C NMR were consistent w ith
those of the refe rence
[ 12]
.
D-Sorb itol (9) 　White amorphous powde r;
1
H NMR (400 MH z, D2O ) δ:3.4 - 3.8(8H );
629 FENG W ei-sheng, e t al:Chem ical constituents from leave s ofCelastrus gemmatus Loes.
13
C NMR (100 MHz, D2O) δ:74.3(C-5), 72.4
(C-2), 72.3(C-4), 71.0(C-3), 64.2(C-6), 63.8
(C-1). The data o f 13C NMR were consistent w ith
those o f the re ference
[ 13]
.
Acknow ledgem ents:W e thank P ro .f DONG Cheng-m ing
(H enan Un ive rsity o f T rad itional Ch ineseM edicine, Ch ina) for
m ak ing the o rig ina l leaved co llec tions from X ixia county o f
H enan province and fo r the p lant identifica tion. W e a lso thank
P ro .f KANG Jian-xun and P ro .f ZHU W ei-guo (Zhengzhou
University, China) for the NM R spectra expe rim en ts, thank
P ro f. X IN B in (Zheng zhou University, China) for theH R-TOF-
M S spectra experim ents, L IU Le and D ING Ha i-jie (Henan
University o f T raditiona l Chine seM edicine, China) for UV and
IR experim ents.
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