1
32
Helvetica Chimica Acta – Vol. 95 (2012)
Plant Material. The roots of P. giraldii were collected in September and October 2007, in Mei County,
Shaanxi Province, P. R. China, and authenticated by Prof. Zhen-Hai Wu, Northwest A&F University. A
voucher specimen (S20060811) was deposited with the School of Pharmaceutical Science and
Technology, Tianjin University, P. R. China.
Extraction and Isolation. Fresh roots of P. giraldii (18 kg) were refluxed with 90% and then with 60%
EtOH twice, resp. The extracts were combined and concentrated to give a residue (3 kg), which was
suspended in H O to a final volume of 10 l, and partitioned with petroleum ether (PE), CHCl , AcOEt,
2
3
and BuOH. The AcOEt extract (130 g) was subjected to CC (SiO ; CH Cl /MeOH 98 :2 ! 65 :35) to
2
2
2
give 83 fractions. Frs. 22 – 29 (63.5 g) were combined and further submitted to CC (SiO ; PE/Me CO
2
2
9
:1 ! 5 :5) to give the mixture of 3 – 6 (20 mg) and 2-(4-hydroxyphenyl)acetic acid (100 mg). Frs. 36 – 45
(
24 g) were combined and further purified by CC (SiO ; CH Cl /MeOH 95 :5 ! 85 :15; and Sephadex
2
2
2
LH-20; MeOH) to afford gallic acid (500 mg). Frs. 46 – 64 (42 g) were combined and further purified by
repeated CC (SiO ; CH Cl /MeOH 9 :1 ! 75 :25; RP-18 SiO ; MeOH/H O 5 :5; and Sephadex LH-20;
2
2
2
2
2
MeOH) to afford compound 1 (30 mg), (ꢀ)-epigallocatechin (20 mg), and (ꢀ)-epigallocatechin gallate
(
100 mg).
The BuOH extract (1200 g) was subjected to D101 macroporous resin CC and eluted with H O,
2
followed by increasing concentrations of EtOH in H O (30%, 50%, and 95% EtOH) to yield five
2
fractions. The 30% EtOH eluate (330 g) was then exposed to CC (SiO ; AcOEt/MeOH/H O 96 :4 :2 !
2
2
7
:3 :1) to give 71 fractions. Frs. 25 – 37 (46 g) were combined and further purified by CC (SiO ; CHCl /
2 3
MeOH/H O 75 :25 :2 ! 4 :6 :1) to afford compound 2 (100 mg).
2
Acid Hydrolysis. Compound 2 (10.1 mg) was dissolved in 4 ml of 1m HCl (H O/dioxane 1:1) and
2
heated in a H O bath at 808 for 2 h, then the dioxane was evaporated, and the aglycone was removed by
2
extracting with AcOEt (4 ꢁ 4 ml). The aq. layer was neutralized with Ag CO , centrifuged, and
2
3
evaporated to dryness. The monosaccharides were identified as Xyl and Gal by TLC (SiO ; AcOEt/
2
MeOH/H O/AcOH 13 :3 :4 :2) comparision with authentic sugars.
2
Pteroxygonumnol A (¼ rel-(3S,4R,7S,7aS,7bS,9aR,10S,12S,12aR,12bR,14bR)-3,4,5,5a,6,7,7a,7b,
8
3
,9,10,11,12,12a,12b,13-Hexadecahydro-5,5,7b,12b-tetramethyl-10-(propan-2-yl)-12,9a-(epoxymethano)-
,14b-methanocyclopenta[7,8]phenanthro[1,2-c]oxepine-4,7(1H)-diol; 1). White powder. M.p. 296 – 2978.
2
5
[
a]
D
¼ þ28.2 (c ¼ 0.78, C
5 5
H N). UV (MeOH): 222 (3.12), 268 (2.72). IR (KBr): 3442, 2924, 2347, 1641,
1
13
þ
þ
1
059. H- and C-NMR: Table 1. HR-ESI-MS: 493.3281 ([M þ Na] , C H NaO ; calc. 493.3288).
30
46
4
Myricetin 3-O-b-d-Galactopyranoside 3’-O-b-d-Xylopyranoside (¼2-[3,4-Dihydroxy-5-(b-d-xylo-
pyranosyloxy)phenyl]-5,7-dihydroxy-4-oxo-4H-chromen-3-yl b-d-Galactopyranoside; 2). Yellow pow-
2
5
der. M.p. 194 – 1968. [a] ¼ ꢀ42.9 (c ¼ 0.63, C H N). UV (MeOH): 225 (4.34), 357 (4.33). IR (KBr):
D
5
5
1
13
3
421, 2913, 1657, 1607, 1505, 1351, 1202, 1046. H- and C-NMR: Table 2. HR-ESI-MS: 635.1210 ([M þ
þ þ
Na] , C H NaO ; calc. 635.1219).
26
28
17
Mixture of Phenolic Lipids 1-(2,4,6-Trihydroxyphenyl)henicosan-1-one, 1-(2,4,6-Trihydroxyphenyl)-
tricosan-1-one, 1-(2,4,6-Trihydroxyphenyl)pentacosan-1-one, and 1-(2,4,6-Trihydroxyphenyl)heptacosan-
1
1
6
-one (3 – 6, resp.). White powder. UV (MeOH): 228 (4.10), 286 (4.20). IR (KBr): 3395, 2918, 2849,
1
642, 1467, 1222, 1072. H-NMR (500 MHz, C D N): 13.91 (br. s, HOꢀC(2/6)); 12.67 (br. s, HOꢀC(4));
5
5
.47 (s, HꢀC(3/5)); 3.42 (t, J ¼ 7.5, CH (2’)); 1.89 (quint., J ¼ 7.5, CH (3’)); 1.27 (br. s, ꢀCH ꢀ); 0.85 (t,
2
2
2
13
J ¼ 7.0, Me). C-NMR (125 MHz, C D N): 205.3 (C(1’)); 165.3 (C(4)); 165.0 (C(2/6)); 104.3 (C(1)); 94.8
5
5
(
C(3/5)); 43.1 (C(2’)); 31.0, 28.8 – 28.7, 28.5, 24.2, 21.8 (ꢀCH ꢀ); 13.1 (Me). HR-ESI-MS: 419.3170 ([M ꢀ
2
ꢀ
ꢀ
ꢀ
ꢀ
4
ꢀ
H] , C H O ; calc. 419.3167), 447.3480 ([M ꢀ H] , C H O ; calc. 447.3480), 475.3794 ([M ꢀ H] ,
26
43
4
28 47
ꢀ
ꢀ
ꢀ
C H O ; calc. 475.3493), and 503.4109 ([M ꢀ H] , C H O ; calc. 503.4106), resp.
30
51
4
32 55
4
REFERENCES
[
1] A. R. Li, Z. J. Gao, Z. M. Mao, Y. L. Liu, ꢀFlora Republicae Popularis Sinicaeꢁ, Science Press,
Beijing, China, 1998, Vol. 25, p. 117.
[
[
2] Z. J. Guo, ꢀShaanxi Qi Yaoꢁ, Shaanxi Science and Technology Press, Shaanxi, China, 2003, p. 221.
3] Y.-H. Gao, Y.-F. Su, S.-L. Yan, Z.-H. Wu, X. Zhang, T.-Q. Wang, X.-M. Gao, Nat. Prod. Commun.
2010, 5, 223.