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Triterpenoids of Schisandra sphenanthera
Pergamon
Phymhenwry.
Vol 35. No. 4. pp. 1068-1069. 1994 Q 1994 Elswier Snena Lid Prmkd in Great Britun. All rights reserved ‘YX-9422,%%00+0.00
TRITERPENOIDS
OF SCHISANDRA SPHENANTHERA
JIAN-MIN YuE,*
XU-JUN
and YAO-zu CHEN
Department of Chemistry, Lanzhou University. Lanzhou, China (Receioed in recised/orm
Key Word Index-Schisandra
sphenanthera;
24 May
Schisandraceae;
1993)
triterpenoid;
schisanol;
lignans.
Abstract-From the fruit of Schisandra sphenanthera, we have isolated a new triterpenoid, named schisanol, as well as the four known lignans, wuweizisu A, schisantherin A and D, and (+)-gomisins K,. The structure of schisanol was determined on the basis of spectral data.
INTRODUCIION
Schisandra sphenanthera Rehd. ed Wils has long been used as a tonic in China. It has been shown to be effective in reducing the level of GPT (glutamic-pyruvic transaminase), and it is clinically used as a care for chronic hepatitis and cirrhosis of the liver [1,2]. The chemical constituents of S. sphenanrhera collected at Danfeng county of Shanxi province have been investigated. In addition to the known lignans, wuweizisu A, schisantherin A and D, and (+)-gomisins K,, a new triterpenoid, named schisanol (1) has been isolated and its structure elucidated.
1
Table I.
shifts
RESULTS AND DISCIJ!SlON
‘-‘CNMR anol
The molecular formula of 1, was determined as C,,,H,,O, by HRMS. The IR absorption band at 1715 cm-’ and the “CNMR signals at 6166.6 and 80.6 showed the presence of a lactone ring. The ‘HNMR spectrum exhibited signals at 66.63 (lH, m, H-24), 4.48 (I H, m, H-22), 2.06 (I H, m, H-20), 1.93 (3H, s, H-27) and 1.00 (3H, d, J=6.4 Hz, H-21), indicating that schisanol has the same side chain as schisanlactones A and B [3], which contain an z-methyl-x, P-unsaturated d-lactone unsubstituted at the y-position. The ‘HNMR and 13CNMR (Table 1) spectra showed that schisanol has five quaternary methyl groups and two tertiary methyl groups, as well as a A9.’ *-double bond. Comparision of the spectroscopic data of schisanol with published data showed that schisanol has the same skeleton as schisanlactone D [4]. The ‘H and “C NMR spectra indicated that the only hydroxyl group is attached to C-3. The coupling constant of H-3 (J3..r. = 10.7 Hz, J3a.Zc =4.2 Hz) showed that the hydroxyl group has the /I-
*Author Laboratory
to whom correspondence of Phytochemistry,
The Academy China.
should
Kunming
of Sciences of China,
be addressed at:
Institute
Kunming
of Botany,
650204,
Yunnan,
chemical
and assignments for schis-
C
(I) C
1
36.9
16
26.7
2
21.1
1-l
46.5
3
78.9
18
14.2
4
39.1
19
22.3 39.1
5
52.5
20
6
21.3
21
13.2
I
28.1
22
80.6
8
41.8
23
23.5
9
148.8
24
139.5
10
39.4
25
128.3
11
114.6
26
166.6
12
36.1
27
13
44.8
28
18.6
14
46.6
29
28.2
15
34.0
30
22.2
orientation. The ated as 1. The structures fied on the basis as wuweizisu A (+)-gomisins K,
structure
17.0
of schisanol
was thus elucid-
of the four known lignans were identiof physical constants and spectral data [2], schisantherin A and D [S], and [6].
1069
Short Reports EXPERIMENTAL
Mp: uncorr.; MS: 70 cV, NMR: ‘H at 400 MHz, ‘“C at 100 MHz. The multiplicities of 13CNh4R spectral data were determined with the aid of 1D Distortionless Enhancement Polarization Transfer (DEPT) spectra. Plant material. Schisandra sphenanthera Rehd. ed Wils was collected at Danfeng county, Shanxi province, China and authenticated by Prof. Ru-neng Zhao in the Department of Pharmacy, Lanzhou Medical College, Lanzhou, China, where the voucher specimen is deposited. Extraction and isolation. The air-dried powdered fruits (2.5 kg) were extracted (x 3) with 95% EtOH at room temp. The extract was evapd to dryness under red. pres. and the residue successively extracted with petrol, EtOAc and MeOH. The EtOAc extract was chromatographed on a silica gel column (200-300 mesh, 400 g, 100 x 4 cm) and successively eluted with petrol-Me&O (8: 1, 6: 1, 3:land2:1)togivefrsEl(6g),E2(4g)andE3(7g).El and E2 were crystallized from n-hexane-Me&O to give wuweizisu A (3.5 g) and schisantherin A (2 g), respectively. E3 was rechromatographed on a silica gel column (200-300 mesh, 150 g, 50x 2.5 cm) and eluted with CHCI, containing increasing amounts of MeOH (2.58%) to afford frs A-C. Frs A and B were further sepd by prep. TLC (silica gel, benzyl-EtOAc, 2: 1) to give schisantherin D (150 mg) and (+)-gomisins K, (50 mg). Fr. C was crystallized from n-hexane-Me&O to afford schisanol (50 mg). Schisanol 1. C,,H,,OJ (HRMS, Found: 454.3449, requires: 454.3447) mp 280-281” (n-hexane-Me,CO), was obtained as crystalline flakes. UV A!:‘” nm: 247.5,299.0; IR YE: cm-‘: 3515 (OH), 1757 (-OCOR); ‘HNMR: 66.63(lH,m,H-24),5.24(lH,m,H-ll),4.48(lH,m,H-22), 3.22 (lH, dd, J,,,,,=lO.7 Hz, JJ,.ze=4.2 Hz, H-3). 206 (lH, m, H-20), 1.93 (3H, s, H-27), 1.00 (3H, d, J=6.4 Hz, H-21), 1.10, 1.01,0.84,0.75 and 0.70 (each 3H, s, H-30, H19, H-29, H-28 and H-18); i3C NMR: Table 1; EIMS m/z: 454 [M]’ (48), 439 [M-Me]’ (65), 421 [M-Me -H,O]+ (58), 313 (30), 173 (35), 111 (85), 55 (100). Wuweizisu A. Mp 113-l 14” (n-hexane-Me&O). IR v!j$cm-*: 1595, 1469 and 1455; ‘HNMR: 66.52 (lH, s,
Ar-H), 6.51 (3H, s, Ar-H), 3.87 (3H, s, -OMe), 3.86 (6H, s, -OMe), 3.84 (3H, s, -OMe), 3.57 (6H, s, -OMe), 1.88 (lH, m), 1.78 (lH, m), 0.98 (3H, d, J=7.1 HI -Me),0.71 (3H, d, J=7.1 Hz,-Me);EIMSm/z:416[M]+(l00),385,370and 235. Schisantherin A. Mp 120- 121’ (n-hexane-Me,CO). IR 6:: cm-‘: 3383 (-OH), 1729 (GCOAr), 1623, 1595 and 1496(-Ar); ‘H NMR: 6 7.55-7.30(18, m), 6.80(lH, s), 6.57 (lH, s, Ar-H), 5.85 (lH, s, =CHOCOPh), 5.78 and 5.63 (each lH, d, J= 1.5 Hz, -GCH,O-), 3.89 (6H, s, -OMe), 3.57,3.30(each 3H, -OMe), 1.38 (3H, s, -Me), 1.20(3H,d, J =7.1 Hz, -Me); EIMS m/z: 536 [M]’ (78), 414 (70) 343 (loo), 328 (20), 312 (40) and 105 (85). Schisantherin D. Mp 110-l 11”. IR fl& cm-‘: 3480 (-OH), 1715; ‘H NMR: 67.50(3H,d, J=7.4 Hz), 7.31 (2H, f, J=7.3 Hz, Ar-H), 6.03, 5.98 (each lH, d, J= 1.4 Hz), -OCH,O-), 5.76, 5.57 (each lH, J= 1.5 Hz, -OCH,O-), 5.70, 5.57 (each lH, J= 1.5 HZ -OCH,O-), 5.70 (lH, s), 3.81,3.38(each 3H,s,-OMe), 1.37(3H,s, -Me), l.l8(3H,d, J=7.2 Hz, -Me); EIMS m/z: 520 CM]’ (lo), 414,326,285, 105, 77. (+)-Gomisins K,. Mp 99-100” (hexane-Et,O). IR vfP cm- ‘: 3501,3416(-OH); *H NMR: 66.54(1H,s), 6.33 (lH,s, Ar-H), 3.85(12H,s,-OMe), 3.58(3H,s,-OMe),0.98 (3H, d, J=6.6Hz, -Me), 0.71 (3H, d, J=6.6Hz, -Me); EIMS m/z: 402 CM]’ (lOO), 370,356, 316,275 and 243.
REFERENCES
1. Zong, W. Zh. and Tong, Y. Y. (1983) Acta Pharm. Sin. 18, 138.
2. Chen, Y. Y., Shu, Z. B. and Li, L. N. (1976) Scientia Sin. 19, 276. 3. Liu, J. S., Huang, M. F., Bigam, G. and Ayer, W. A. (1983) Tetrahedron Letters 24, 2355. 4. Liu, J. S. and Huang, M. F. (1985) Acta Chim. Sin. 43, 264.
5. Liu, J. S., Huang, M. F., Kao, Y. L. and Hsu, J. Sh. (1978) Scientia Sin. 21, 483. 6. Key, Y., Jaguchi, H. and Yosioka, I. (1980) Chem. Pharm. Bull. 28, 2422.
Phymhenwry.
Vol 35. No. 4. pp. 1068-1069. 1994 Q 1994 Elswier Snena Lid Prmkd in Great Britun. All rights reserved ‘YX-9422,%%00+0.00
TRITERPENOIDS
OF SCHISANDRA SPHENANTHERA
JIAN-MIN YuE,*
XU-JUN
and YAO-zu CHEN
Department of Chemistry, Lanzhou University. Lanzhou, China (Receioed in recised/orm
Key Word Index-Schisandra
sphenanthera;
24 May
Schisandraceae;
1993)
triterpenoid;
schisanol;
lignans.
Abstract-From the fruit of Schisandra sphenanthera, we have isolated a new triterpenoid, named schisanol, as well as the four known lignans, wuweizisu A, schisantherin A and D, and (+)-gomisins K,. The structure of schisanol was determined on the basis of spectral data.
INTRODUCIION
Schisandra sphenanthera Rehd. ed Wils has long been used as a tonic in China. It has been shown to be effective in reducing the level of GPT (glutamic-pyruvic transaminase), and it is clinically used as a care for chronic hepatitis and cirrhosis of the liver [1,2]. The chemical constituents of S. sphenanrhera collected at Danfeng county of Shanxi province have been investigated. In addition to the known lignans, wuweizisu A, schisantherin A and D, and (+)-gomisins K,, a new triterpenoid, named schisanol (1) has been isolated and its structure elucidated.
1
Table I.
shifts
RESULTS AND DISCIJ!SlON
‘-‘CNMR anol
The molecular formula of 1, was determined as C,,,H,,O, by HRMS. The IR absorption band at 1715 cm-’ and the “CNMR signals at 6166.6 and 80.6 showed the presence of a lactone ring. The ‘HNMR spectrum exhibited signals at 66.63 (lH, m, H-24), 4.48 (I H, m, H-22), 2.06 (I H, m, H-20), 1.93 (3H, s, H-27) and 1.00 (3H, d, J=6.4 Hz, H-21), indicating that schisanol has the same side chain as schisanlactones A and B [3], which contain an z-methyl-x, P-unsaturated d-lactone unsubstituted at the y-position. The ‘HNMR and 13CNMR (Table 1) spectra showed that schisanol has five quaternary methyl groups and two tertiary methyl groups, as well as a A9.’ *-double bond. Comparision of the spectroscopic data of schisanol with published data showed that schisanol has the same skeleton as schisanlactone D [4]. The ‘H and “C NMR spectra indicated that the only hydroxyl group is attached to C-3. The coupling constant of H-3 (J3..r. = 10.7 Hz, J3a.Zc =4.2 Hz) showed that the hydroxyl group has the /I-
*Author Laboratory
to whom correspondence of Phytochemistry,
The Academy China.
should
Kunming
of Sciences of China,
be addressed at:
Institute
Kunming
of Botany,
650204,
Yunnan,
chemical
and assignments for schis-
C
(I) C
1
36.9
16
26.7
2
21.1
1-l
46.5
3
78.9
18
14.2
4
39.1
19
22.3 39.1
5
52.5
20
6
21.3
21
13.2
I
28.1
22
80.6
8
41.8
23
23.5
9
148.8
24
139.5
10
39.4
25
128.3
11
114.6
26
166.6
12
36.1
27
13
44.8
28
18.6
14
46.6
29
28.2
15
34.0
30
22.2
orientation. The ated as 1. The structures fied on the basis as wuweizisu A (+)-gomisins K,
structure
17.0
of schisanol
was thus elucid-
of the four known lignans were identiof physical constants and spectral data [2], schisantherin A and D [S], and [6].
1069
Short Reports EXPERIMENTAL
Mp: uncorr.; MS: 70 cV, NMR: ‘H at 400 MHz, ‘“C at 100 MHz. The multiplicities of 13CNh4R spectral data were determined with the aid of 1D Distortionless Enhancement Polarization Transfer (DEPT) spectra. Plant material. Schisandra sphenanthera Rehd. ed Wils was collected at Danfeng county, Shanxi province, China and authenticated by Prof. Ru-neng Zhao in the Department of Pharmacy, Lanzhou Medical College, Lanzhou, China, where the voucher specimen is deposited. Extraction and isolation. The air-dried powdered fruits (2.5 kg) were extracted (x 3) with 95% EtOH at room temp. The extract was evapd to dryness under red. pres. and the residue successively extracted with petrol, EtOAc and MeOH. The EtOAc extract was chromatographed on a silica gel column (200-300 mesh, 400 g, 100 x 4 cm) and successively eluted with petrol-Me&O (8: 1, 6: 1, 3:land2:1)togivefrsEl(6g),E2(4g)andE3(7g).El and E2 were crystallized from n-hexane-Me&O to give wuweizisu A (3.5 g) and schisantherin A (2 g), respectively. E3 was rechromatographed on a silica gel column (200-300 mesh, 150 g, 50x 2.5 cm) and eluted with CHCI, containing increasing amounts of MeOH (2.58%) to afford frs A-C. Frs A and B were further sepd by prep. TLC (silica gel, benzyl-EtOAc, 2: 1) to give schisantherin D (150 mg) and (+)-gomisins K, (50 mg). Fr. C was crystallized from n-hexane-Me&O to afford schisanol (50 mg). Schisanol 1. C,,H,,OJ (HRMS, Found: 454.3449, requires: 454.3447) mp 280-281” (n-hexane-Me,CO), was obtained as crystalline flakes. UV A!:‘” nm: 247.5,299.0; IR YE: cm-‘: 3515 (OH), 1757 (-OCOR); ‘HNMR: 66.63(lH,m,H-24),5.24(lH,m,H-ll),4.48(lH,m,H-22), 3.22 (lH, dd, J,,,,,=lO.7 Hz, JJ,.ze=4.2 Hz, H-3). 206 (lH, m, H-20), 1.93 (3H, s, H-27), 1.00 (3H, d, J=6.4 Hz, H-21), 1.10, 1.01,0.84,0.75 and 0.70 (each 3H, s, H-30, H19, H-29, H-28 and H-18); i3C NMR: Table 1; EIMS m/z: 454 [M]’ (48), 439 [M-Me]’ (65), 421 [M-Me -H,O]+ (58), 313 (30), 173 (35), 111 (85), 55 (100). Wuweizisu A. Mp 113-l 14” (n-hexane-Me&O). IR v!j$cm-*: 1595, 1469 and 1455; ‘HNMR: 66.52 (lH, s,
Ar-H), 6.51 (3H, s, Ar-H), 3.87 (3H, s, -OMe), 3.86 (6H, s, -OMe), 3.84 (3H, s, -OMe), 3.57 (6H, s, -OMe), 1.88 (lH, m), 1.78 (lH, m), 0.98 (3H, d, J=7.1 HI -Me),0.71 (3H, d, J=7.1 Hz,-Me);EIMSm/z:416[M]+(l00),385,370and 235. Schisantherin A. Mp 120- 121’ (n-hexane-Me,CO). IR 6:: cm-‘: 3383 (-OH), 1729 (GCOAr), 1623, 1595 and 1496(-Ar); ‘H NMR: 6 7.55-7.30(18, m), 6.80(lH, s), 6.57 (lH, s, Ar-H), 5.85 (lH, s, =CHOCOPh), 5.78 and 5.63 (each lH, d, J= 1.5 Hz, -GCH,O-), 3.89 (6H, s, -OMe), 3.57,3.30(each 3H, -OMe), 1.38 (3H, s, -Me), 1.20(3H,d, J =7.1 Hz, -Me); EIMS m/z: 536 [M]’ (78), 414 (70) 343 (loo), 328 (20), 312 (40) and 105 (85). Schisantherin D. Mp 110-l 11”. IR fl& cm-‘: 3480 (-OH), 1715; ‘H NMR: 67.50(3H,d, J=7.4 Hz), 7.31 (2H, f, J=7.3 Hz, Ar-H), 6.03, 5.98 (each lH, d, J= 1.4 Hz), -OCH,O-), 5.76, 5.57 (each lH, J= 1.5 Hz, -OCH,O-), 5.70, 5.57 (each lH, J= 1.5 HZ -OCH,O-), 5.70 (lH, s), 3.81,3.38(each 3H,s,-OMe), 1.37(3H,s, -Me), l.l8(3H,d, J=7.2 Hz, -Me); EIMS m/z: 520 CM]’ (lo), 414,326,285, 105, 77. (+)-Gomisins K,. Mp 99-100” (hexane-Et,O). IR vfP cm- ‘: 3501,3416(-OH); *H NMR: 66.54(1H,s), 6.33 (lH,s, Ar-H), 3.85(12H,s,-OMe), 3.58(3H,s,-OMe),0.98 (3H, d, J=6.6Hz, -Me), 0.71 (3H, d, J=6.6Hz, -Me); EIMS m/z: 402 CM]’ (lOO), 370,356, 316,275 and 243.
REFERENCES
1. Zong, W. Zh. and Tong, Y. Y. (1983) Acta Pharm. Sin. 18, 138.
2. Chen, Y. Y., Shu, Z. B. and Li, L. N. (1976) Scientia Sin. 19, 276. 3. Liu, J. S., Huang, M. F., Bigam, G. and Ayer, W. A. (1983) Tetrahedron Letters 24, 2355. 4. Liu, J. S. and Huang, M. F. (1985) Acta Chim. Sin. 43, 264.
5. Liu, J. S., Huang, M. F., Kao, Y. L. and Hsu, J. Sh. (1978) Scientia Sin. 21, 483. 6. Key, Y., Jaguchi, H. and Yosioka, I. (1980) Chem. Pharm. Bull. 28, 2422.