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Di- and triterpenoids of Salvia pomifera
744
G. TOPW et al. Table I. “C NMR (CDCI,) spectral data of germanicone (7) and 23-hydroxygermanicone (4)
R’
R*
R3
1
OH
OH
Me
la
OAc
OAc
Me
2
H
OH
Me
3
H
H
CH20Ac
R’
R*
R3
4
Me
0
CH20H
s
COOH
0
Me
6
CHzOH
B-0H.H
Me
7
Me
0
Me
shift was typical for olean-1%ene without an acid group at C-28 [6]. In case of the presence of a substituent other than a methyl group at C-28, the H-19 signal shifts ca 5.15-5.20 as we have observed for moronic acid (5) [2] and moradiol (6) [3,4], and as given in the literature [6] for similar triterpenes. Other ‘H NMR signals were at fi3.6l(lH,d.J=11 Hz,H-23)and4.17(1H,d,J=11Hz, H-23) which indicated the presence of an hydroxymethylene group at C-23. The chemical shifts of these two signals showed that they were dcshielded by the 0x0 group at C-3. The “C NMR spectrum of 4 was compared to that of germanicone (7) (Table 1) [7] and all signals were more or less similar except for the signals for C-4, C-23 and C24. Instead ofa methyl signal at 626.9, the appearance of a signal at 76.2 confirmed the presence of the hydroxymethylene group at C-23 and this was supported by the downfield shift of the C-24 methyl signal to 6 15.4. Due to
C
7
4
I 2 3 4 6 7 8 9 10 II 12 13 14 I6 17 18 19 20 21 22 23 24 2s 26 27 ‘8 29 30
39.9 34.0 217.8 47.2 19.7 34.0 40.7 50.6 37.0 21.7 26.3 38.6 27 6 37.7 34.4 142.6 130.4 32.4 33.4 37.4 26.9 21.0 16.0
37.8 36.6 208. I 50.6 18.2 34.6 42.3 52. I 37.3 22. I 27.1 37.4 28.6 3s 5 34.2 142.0 134.1 32.2 28.4 40 I 76.2 15.4 16.1 17.2 14.3 24.7 31.5 2X.4
16.0 14.5 25.3 31.3 29.2
the z-effect of the 0x0 group in addition to the b-effect of the hydroxyl group, the C-4 signal was observed at 650.6 while the same carbon appeared at 47.2 in germanicone. All spectral data indicated 3-oxo-23_hydroxymethyleneolean-l&en for compound 4 (23-hydroxygermanicone). The 13C NMR signals and APT experiments confirmed the given structure for 4. EXPERIMENTAL
Plant material. The aerial parts of Saloia pomijera L. were collected from western Turkey (Kugadasi) in June 1982 and identified by Prof. Ertan Tuzlaci. A voucher specimen (ISTE 48942) is deposited in the Herbarium of the Faculty of Pharmacy, University of Istanbul. Isolation of compounds. Powdered aerial parts of the plant (700g) were extracted with Me&O. The Me&O soluble material (27 g) was fractionated by silica gel CC (5 x 70 cm); in the first study the following diterpenoids were obtained and purified: pomiferin A (14 mg), 1% hydroxy-8,11,13-abietatrien-7-one (7 mg), pomiferin B (8 mg), ferruginyl 12-methyl ether (10 mg), pomiferin C (11 mg), pomiferin D (25 mg). pomiferin E (7 mg). In this study, the remaining more polar frs were combined
G. TOPW et al. Table I. “C NMR (CDCI,) spectral data of germanicone (7) and 23-hydroxygermanicone (4)
R’
R*
R3
1
OH
OH
Me
la
OAc
OAc
Me
2
H
OH
Me
3
H
H
CH20Ac
R’
R*
R3
4
Me
0
CH20H
s
COOH
0
Me
6
CHzOH
B-0H.H
Me
7
Me
0
Me
shift was typical for olean-1%ene without an acid group at C-28 [6]. In case of the presence of a substituent other than a methyl group at C-28, the H-19 signal shifts ca 5.15-5.20 as we have observed for moronic acid (5) [2] and moradiol (6) [3,4], and as given in the literature [6] for similar triterpenes. Other ‘H NMR signals were at fi3.6l(lH,d.J=11 Hz,H-23)and4.17(1H,d,J=11Hz, H-23) which indicated the presence of an hydroxymethylene group at C-23. The chemical shifts of these two signals showed that they were dcshielded by the 0x0 group at C-3. The “C NMR spectrum of 4 was compared to that of germanicone (7) (Table 1) [7] and all signals were more or less similar except for the signals for C-4, C-23 and C24. Instead ofa methyl signal at 626.9, the appearance of a signal at 76.2 confirmed the presence of the hydroxymethylene group at C-23 and this was supported by the downfield shift of the C-24 methyl signal to 6 15.4. Due to
C
7
4
I 2 3 4 6 7 8 9 10 II 12 13 14 I6 17 18 19 20 21 22 23 24 2s 26 27 ‘8 29 30
39.9 34.0 217.8 47.2 19.7 34.0 40.7 50.6 37.0 21.7 26.3 38.6 27 6 37.7 34.4 142.6 130.4 32.4 33.4 37.4 26.9 21.0 16.0
37.8 36.6 208. I 50.6 18.2 34.6 42.3 52. I 37.3 22. I 27.1 37.4 28.6 3s 5 34.2 142.0 134.1 32.2 28.4 40 I 76.2 15.4 16.1 17.2 14.3 24.7 31.5 2X.4
16.0 14.5 25.3 31.3 29.2
the z-effect of the 0x0 group in addition to the b-effect of the hydroxyl group, the C-4 signal was observed at 650.6 while the same carbon appeared at 47.2 in germanicone. All spectral data indicated 3-oxo-23_hydroxymethyleneolean-l&en for compound 4 (23-hydroxygermanicone). The 13C NMR signals and APT experiments confirmed the given structure for 4. EXPERIMENTAL
Plant material. The aerial parts of Saloia pomijera L. were collected from western Turkey (Kugadasi) in June 1982 and identified by Prof. Ertan Tuzlaci. A voucher specimen (ISTE 48942) is deposited in the Herbarium of the Faculty of Pharmacy, University of Istanbul. Isolation of compounds. Powdered aerial parts of the plant (700g) were extracted with Me&O. The Me&O soluble material (27 g) was fractionated by silica gel CC (5 x 70 cm); in the first study the following diterpenoids were obtained and purified: pomiferin A (14 mg), 1% hydroxy-8,11,13-abietatrien-7-one (7 mg), pomiferin B (8 mg), ferruginyl 12-methyl ether (10 mg), pomiferin C (11 mg), pomiferin D (25 mg). pomiferin E (7 mg). In this study, the remaining more polar frs were combined