Title 数種の中国産甘草サポニン成分の化学的研究 Author(s) 堀, 一之 Citation Issue Date Text Version ETD URL https://doi.org/10.11501/3070540 DOI 10.11501/3070540 rights

0 0 II C 0 COOR COOK OH HOH COOR 0 OH HOO H H3 16 (licorice-saponin F3) COOK o 20 0H H H02.7 HO OH OH 17 (licorice-saponin G2) COOK OH OH COOR 0 OH0 1.:Rmf HOH COOK COOK 0 20 0H HO Cc7;Fix.H HO OH OH H 19 (licorice-saponin H2) HO OH OH 21 (licorice-saponin J2) COOK COOR 0.1, OOR0 OH HOH C 0 0H HOH 22 OH (licorice-saponin K2) Fig. 1-3 -

Table H 13C NMR Data for 18, 11a, 14a, 16a, 17a, 19a, 21a, and 22a (22.5 MHz, pyridine-d5, 050 ) 1 a 11a 1 4 a 16'a 17a 19a 21a 22a sapogenol C-3 89.2 89.9 89.0 89.9 M 89.9 89.2 89.8 89.8 moiety 0-11 199.0 23.6 198.8 23.6 198.9 199.0 23.7 125.3 0-12 128.7 122.2 129.6 124.8 128.6 128.6 122.2 126.4 0-13 168.7 143.6 164.3 140.6 168.7 168.4 144.3 135.2 0-18 44.5 44.0 44.8 44.1 44.2 44.0 44.0 135.2 C-22 38.1 77.5) 84.0a) 84.3 38.2 37.1 36.2 36.2 C-24 16.5 16.4 16.4 16.3 63.1 16.2 62.8 62.4 C-29 28.4 29.1 28.0 28.0 28.0 178.1 29.1 2.8.1 0-30 176.5 177.2 179.3 180.1 176.5 19.3 177.0 178.2 4:7"7 3-043-D- C-1' 104.5 104.7 104.6 104.7 104.1 104.9 104.0 104.0 glucurono- C-2' 84.0 79.1 83.8a) 79.1 81.9 84.3 81.1 80.8 pyranosyl moiety C-3' C-4' 76.2a) 72.2 76.2a) 72.2a) 76.2b) 72.2) 76.313) 72.2b) 75.2 72.2 76.4a) 72.5b) 76.3a) 72.1 76.6 72.1 C-5' 77.1 77.9c) 77.2 77.9c) 77.2 77.3c) 77.413) 77.7a) C-6' 169.5b) 169.6d) 169.7d) 170.1d) 169.6 170.1d) 169.6 169.8 2'-a3-D- C-1" 106.3 102.4 106.2 102.4 105.5 106.8 104.7 104.5 glucurono- C-2" 75.9a) 78.2 76.1 78.2 76.5a) 76.6a) 76.6a) 76.6 pyranosyl moiety C-3" C-4" 77.1 72.4 76.7a) 42.9b) 77.2 72.5c) 76.6a) 72.8b) 76.8a) 72.2 77.4) 72.9b) 77.0b) 72.1 77.0a) 72.1 0-5" 77.1 77.5 77.2 77.6) 77.2 77.6c) 77.413) 77.4a) 0-6" 169.7b) 169.8d) 169.8d) 169.8d) 169.6 170.2d) 169.6 169.8 2"-0-a-L- C-1"' 101.6 101.6 rhamno- C-2"' 71.9 71.8 pyranosyl moiety C-3"' C-4"' 72.9 73.9 72.8 73.9 C-5"' 69.2 69.1 C-6"' 18.5 18.5 ------------------------------------------------------ a), b), c), d) Assignments may be interchangeable within the same column.

Table IV 13C NMR Data for 23, 23a, 23b, 23c, 23d, 27, 27a, 1, la, is and id (125 MHz, pyridine-d5, Sc) 23 23a 23b 23c 23d 27 27a 1 1 a lc 1 d C-3 88.8 89.1 88.7 89.2 89.2 88.9 89.0 88.9 89.2 89.5 89.2 C-11 199.1 199.4 199.5 199.4 199.4 199.4 199.3 199.3 199.0 199.2 199.3 0-12 128.4 128.7 128.7 128.8 128.7 128.6 128.6 182.8 128.7 128.5 128.6 C-13 169.7 168.9 169.0 169.0 169.0 169.5 168.9 169.4 168.7 168.8 169.7 C-30 178.8 176.8 176.8 176.8 176.8 179.1 176.7 178.8 176.5 176.7 176.8 30-OMe ' - 51.6a) 51.6 51.6a) 51.6a) -- 51.5a) - 51.5a) 51.5a) 51.5a) 00 C-1, 105.4 105.7 105.5 105.6 105.7 105.2 105.1 104.6 104.5 104.7 104.8 C-2' 79.4a) 79.2b) 79.5 80.8 79.3 83.4 83.1 83.9 84.0 85.0 84.1 C-3' 79.0a) 78.1c) 78.5a) 79.3 78.3 77.4 76.6b) 76.2 76.2b) 76.6 77.2 0-4' 73.0 73.0 71.9 73.1 73.0 73.0 72.6 72.7 72.2 72.6b) 72.3b) C-5' 77.8b) 76.8 78.0a) 77.9 77.5 77.4 77.2b) 77.1 77.1 78.0c) 77.2c) C-6' 172.0 170.3 62.8 170.4 170.3 172.3 170.2 172.1a) 169.5c) 170.0 170.0 6'-OMe -- 51.9a) - 52.0a) 51.9a) -- 51.9a) 51.8a) 51.8a) 51.8a) C-1" 110.9 111.2 111.1 109.0 111.5 106.6 106.6 106.2 106.3 104.0 106.2 0-2" 77.6b) 77.7c) 78.0a) 87.2 76.8 73.6 73.5 76.2 75.9b) 80.6 75.7 C-3" 80.1a) 80.4b) 80.4 76.8 85.3 74.1 74.1 77.1 77.1 75.7 86.9 C-4" 75.2 75.5 75.5 75.6 71.7 69.2 68.9 72.7 72.4 72.4b) 71.9b) C-5" 65.3 65.9 66.0 66.0 63.0 66.9 66.8 77.1 77.1 77.8c) 76.4c) C-6"171.78) 169.7c) 169.6 169.7 2"-OMe 58.7 55.0 3"-OMe 52.8a) 60.8 6"-OMe 51.8a) 51.8a) 52.0a) a), b), c) Assignments may be interchangeable within the same column.

Table V 13C NMR Data for Licorice-saponin L3 (28), 30, Soyasaponin II (31), and Ucorice-saponin D3 trimethyl ester (11a, sapogenol moiety only) (pyridine-d5 + D20, 8c) 28a) 30a) 31 b) 11ac) sapogenol C-1 38.7 38.5 38.6 39.3 moiety C-2 26.3d) 28.2 25.5 26.3f) C-3 91.0 80.8 90.9 89.9 C-4 44.0 43.2 43.8 44.0 0-5 56.1 56.4 56.0 55.7 0-6 18.8 19.1 18.7 20.7 C-7 32.9 33.6 33.2 32.5 0-8 40.1 39.8 39.8 40.0 C-9 47.7 48.0 47.7 47.6 C-10 36.2 36.1 36.3 35.9 C-11 24.0 23.6 24.0 23.6 0-12 124.7 125.2 122.3 122.2 0-13 144.1 144.2 144.7 143.6 0-14 41.9 42.8 42.3 41.6 0-15 26.6d) 26.5 26.3 26.1f) 0-16 27.8 27.5 28.6 28.1 0-17 37.5 37.1 37.9 37.6 C-18 44.2 45.2 44.8 44.0 C-19 40.8 42.8 46.6 40.7 0-20 29.8 32.1 30.8 29.8 0-21 41.7 42.7 42.3 41.6 0-22 78.1 80.2 75.5 77.9 0-23 22.9 23.6 22.8 22.9 0-24 63.4 64.0 63.3 16.4 C-25 15.7 15.8 15.6 15.3 0-26 16.8 16.9 16.9 16.7 0-27 26.3e) 26.5 25.5 26.3 0-28 26.6e) 26.5 28.1 26.3 0-29 29.8 28.4 33.0 29.1 0-30 179.4 172.4 21.0 177.2 acetyl 170.3, 21.4 170.1, 21.0 3-0-(3-D- 0-1' 105.4 105.1 glucurono- C-2' 78.1 77.8 pyranosyl C-3' -4' 75.8 72.6 75.5 72.3 C-5' 77.6 77.3 C-6' 172.2 172.2 2'-O-a-L- C-1" 102.2 101.7 arabino- C-2" 78.1 77.2 pyranosyl C-3" -4" 76.7 70.7 76.8 70.0 C-5" 66.8 66.5 2"-O-a-L- C-1-101.8 101.7 rhamno- C-2-72.3 71.9 pyranosyl C-3- -4-73.9 74.4 73.4 74.1 C-5-69.4 69.0 C-6-18.5 18.5 Measured at a) 125 MHz, b) 67.8 MHz, and c) 22.5 MHz. d e, f) Assignments may be interchangeable within the same column. - 38 -

Fig. 8 samples A D: commercial glycyrrhizin - 41 -

Conditions Chromatograph : Shimadzu LC-6A or JASCO. TRI ROTAR VI Column : YMC-PACK AQ-312 ( ODS 6mmtp X 150 mm ) Column Temp : 40 C Mobile phase : 100 % 0 % 70 min. 20 A CH3CN 50 min. 1 % aq.- AcOH 5 min. ( lineargradient ) 20% 0% 100% Flow rate : 1.0 ml / min. Detector : Shimadzu UV-VIS detector SPD-6A Detection or JASCO UVIDEC 100-VI : UV 254 nm Preparaticin of Sample Licorice-Root ( powder, 5 g ) i) 90 % aq. Me0H (50 ml), reflux. for 1 hr 3 ii) filt. and evap. in vacuo Me0H ext. / 50 % aq. EtOH (50 ml) ( 10 ml ) times i) evap. in vacuo ii) AcOEt(20 ml) / H20(20 ml), 2 times H2O phase AcOEt phase 1 i) ii) evap. dissolve. vacuo in 50% aq. sample (5 µl) EtOH (50 ml) Chart 22-43 -

Glycyrrhiza inflata (Xinjiang) 4:b,A. Fig. 9 1: glycyrrhizin, 2: licorice-saponin A3, 7: licorice-saponin C2 14: liccorice-saponin E2, 17: licorice-saponin G2, 19: licorice-saponin 112 23: apioglycyrrhizin, 27: araboglycyrrhizin