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Drimane-type sesquiterpenoids from the liverwort Diplophyllum serrulatum
0031-9422(93) E0061-I
Pergamon
Phytochemistry,Vol. 35, No. 5, pp. 1263-1265, 1994 Copyright 9 1994 Elsevier Science Lid Printed in Great Britain. All tights reserved 0031 9422/94 $6.00+0.00
DRIMANE-TYPE SESQUITERPENOIDS FROM THE LIVERWORT D I P L O P H YLL UM SERR ULA TUM MASAO TOYOTA, YASUSHIOOISO, TATSUYAKUSUYAMAand YOSHINORIASAKAWA Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770, Japan
(Received4 August 1993)
Key Word |ndex--Diplophyllum serrulatum; Jungermanniales; Hepaticae; drimane-type sesquiterpenoids; (+)-albicanol; (-)-albicanic acid; (-)-albicanal; isoalbicanal; (+)-trans-?-monocyclofarnesol.
Abstract--The liverwort, Diplophyllum serrulatum afforded three new drimane-type sesquiterpenoids albicanic acid, albicanal and isoalbicanal, in addition to (+)-albicanol, (-)-drimenol, (+)-trans-7-monocyclofarnesol, ent-spathulenol and anastreptene. Their structures were established by chemical and spectral means. Albicanol and albicanal were major constituents of this species. This is the first report of the isolation of(-)-albicanic acid in nature and (+)-trans-?monocyclofarnesol from the liverworts.
INTRODUCTION
NMR data are described in the Experimental, as there is no report of these data in the literature. Compound 2, an oil, produced a yellow colouration when treated with 2,4-dinitrophenylhydrazine-sulphuric acid reagent on TLC plates. The E1 mass spectrum of 2 gave a molecular ion peak m/z 220. Its IR spectrum showed the presence of a carbonyl (1721 cm- ~) and an exomethylene (891 cm-1) group. Compound 2 gave the signals in its I H and 13C NMR spectra for the aldehyde (6n9.77 and fic203.4) and the exomethylene group (6n4.51, 4.79, t5c 109.2 and 145.3). The 1H NMR spectrum (see Experimental) showed the signals of three tertiary methyl groups. Lithium aluminum hydride reduction of 2 yielded an alcohol, the spectral and physical data of which were in agreement with those of (+)-albicanol (4) [3, I1, 12]. Accordingly, the above evidence established that 2 only differed from 4 by the replacement of a hydroxy methyl group by a formyl group. The structure of 3 was deduced by comparing its spectral data with those of 2 and chemical evidence. Compound 3 produced the same yellow colouration as 2 with 2,4-DNP on TLC plates, indicating the presence of a carbonyl group. The carbonyl band (1674 cm -~) was confirmed in the IR spectrum of 3 and its UV spectrum showed the presence of the conjugated carbonyl group (245 nm). The ~HNMR spectrum gave the signals for three tertiary methyls (6H0.79, 0.82 and 1.26), a vinyl methyl (6n 1.53) group and a formyl proton (6u 10.02). The pyridinium chlorochromate oxidation of 4 gave 2 and its isomer, ct,fl-unsaturated aldehyde. The GC-mass spectrum and Rt value of the latter compound were identical to those of 3. Thus, the structure of 3 was established as an isomer of 2. We propose a possible biosynthetic pathway for 1-6 (Scheme 1). The 13C
Classification of liverworts belonging to the Jungermanniaceae, a family rich in terpenoids [1], is very difficult and study of their chemical constituents is necessary. For this reason, we have been investigating the chemosystematics of liverworts [1]. In the genus of Diplophyllum, five epiphytic species Diplophyllum serrulatum, D. taxifolium, D. andrewsii, D. obtusifolium and D. albicans, which grow on trunks of deciduous plants, are known in Japan. Previous work on this genus resulted in the isolation of (+)-albicanol (4) and sesquiterpene lactones from D. albicans and D. taxifolium [2-6]. Here, we report on the isolation and structure elucidation of three new drimanetype sesquiterpenoids from D. serrulatum, a species which has not yet been investigated phytochemically. RESULTS A N D D I S C U S S I O N
The ether extract of D. serrulaturn was chromatographed on silica gel, Sephadex LH-20 and repurified by MPLC of silica gel to give three new drimane-type sesquiterpenoids 1-3, (+)-trans-?-monocyclofarnesol (6) [7, 8], ent-spathulenol (7), (-)-drimenol (5) [9, 10], (+)albicanol (4) [3, 11, 12] and a mixture of hydrocarbons containing anastreptene (8) [3, 13]. The E1 mass spectrum of 1 gave I-M] § at m/z 236. The IR spectrum showed the presence of a carboxyl group (3200-2800, 1710cm-1). The ~HNMR spectrum (see Experimental) showed the signals of three tertiary methyls and an exomethylene group. The above spectral data and specific optical rotation were identical to those of (-)-albicanic acid (1) [12]. This is the first isolation of (-)-albicanic acid in nature, although the synthesis and resolution to its enantiomers have been performed [12].
1263
1264
M. TOYOTAet al. COOH
1
CHO
2
CH20H
CHO
r/oPP
3
CH20H
~ 4
5
6
8
-OPP
HO...
.
7
OH
CH20H
....
8
9
CHO
Before the present work, two species. D. albicans and D. taxifolium of this genus had been investigated. Both species elaborate, among the hydrocarbons, mainly ent-~selinene and ent-selina-4,11-diene together with anastreptene and fl-elemene. The more polar constituent of each essential oil contained diplophyllin (9), a eudesmanetype sesquiterpene lactone, as the major component, in addition to 4 [2-4]. On the other hand, 9 and any other sesquiterpene lactones have not been found in D. serrulatum. On the basis of the present results, it is obvious that D. serrulatum is chemically quite different from D. albicans and D. taxifolium. Anastreptene (8) which occurs in the above three species, is quite common in liverworts.
5
2
3
COOH
Scheme 1. A possible biosynthetic pathway of 1-6.
EXPERIMENTAL
General. TLC was carried out on silica gel precoated glass plates with n-hexane-EtOAc (1:1 and 4: 1). Detection was with Godin reagent [14]. For normal phase CC, silica gel 60 (40-63#m) was used. The mixt. of CH2C12-MeOH (1 : 1) was used for CC on Sephadex LH20 as solvent. Spectral data. NMR spectra were recorded at 100 MHz for xsC and 400 MHz for tH. EI mass spectra were measured at 70 eV. GC-MS was carried out at 70 eV and on a fused-silica capillary column coated with DB-17 (30 m • 0.25 mm, df = 0.25 #m) using He as the carrier gas (1 ml min-1). The temp. programming was performed from 50~ isothermal for 3 min, then 50-250 ~ at 5~ rain- 1, and finally isothermal at.250 ~ for 15 min. Injection temp. "\ was 250~ ~ Plant material. Diplophyllum serrulatum (65.9 g) was collected in August 1992, at Tosa, Kochi prefecture in Japan. The voucher specimen (no. 92041) was deposited at the Institute of Pharmacognosy, Tokushima Bunri University. Extraction and isolation. The liverwort was dried for 1 week, and impurities removed under a stereo microscope
by tweezers. The ground material was then extracted with Et20 for 1 month. The Et20 extract (998 mg) was chromatographed on silica gel using n-hexane-EtOAc gradient, giving 7 frs (1-7). The GC-MS of the main compound of fr. 1 (44.2 mg; 4.4% of total extract) was identical to that of 8. Fr. 3 (73.6 mg) was chromatographed on Sephadex LH-20 and further purified by MPLC on silica gel using n-hexane-EtOAc (4: 1), affording 4 (30.1 mg; 3.0%) [3, 11, 12], 5 (6.9 mg; 0.7%) [9, 10] and 6 (5.5 mg; 0.6%) [7, 8], whose spectral data were identical to those of lit. values, respectively. Compound 6 [~t]22 + 18.2 (CHC13; c 0.3) {ref. [7] [~t]D+ 17.6 (EtOH)}. Fr. 5 (67.7 mg) was chromatographed on Sephadex LH20 to give a mixt. containing 1. The mixt. was repurified by MPLC on silica gel using n-hexane-EtOAc (4:1), affording 1; (1.4 mg; 0.14%). Compound 1; [~t]~1 -23.2 (CHCls; c0.07) {ref. [12] Ice]z5 -28.2 (CHC13;cl) }. lsC NMR (CDCls): 614.1, 18.9, 21.8, 23.2, 33.4, 33.5, 36.2, 39.1, 39.2, 42.0, 54.5, 62.5, 108.6, 143.2 and 175.2. Ft.2 (232.2 mg) was chromatographed on Sephadex LH-20, then purified by MPLC on silica gel using nhexane-EtOAc (9:1) to give 2 (61.6mg; 6.2%) and 3
Sesquiterpenoids from liverwort (6.4 mg; 0.6%). Compound 2, oil; [:t]22-69.8 (CHCI3; c3.1); IR Vmaxcm-l: 2730, 1721, 1644, 1460, 1387, 1368, 1113 and 891; IH NMR (C6D6)."60.71, 0.72 and 0.97 (each 3H, s), 2.30 (1H, d, J=4.4 Hz, H-9), 1.80 (1H, ddd, J= 14, 14, 2 Hz, H-7 axial), 2.16 (1H, ddd, J = 14, 4, 2 Hz, H-7 equatorial), 4.51 and 4.79 (each 1H, s), 9.77 (IH, d, J =4 Hz). 13CNMR (C6D6): 615.9, 21.9 and 33.5 (Me), 19.0, 23.3, 36.9, 39.7 and 42.0 (CH2), 53.8 and 67.8 (CH), 33.3 and 39.0 (C), 109.2 (=CH2), 145.3 (C=), 203.4 (CHO). EIMS m/z (rel. int.): 220 [M] § (23), 205 (21), 176 (19), 149 (25), 137 (49), 123 (54), 109 (100), 95 (56), 81 (60), 69 (56), 55 (42). Compound 3, IR Vma~ cm-i: 2760, 1674, 1611, 1460, 1373, 1258 and 1134. UV 2 Et~ nm (loge): 245 (3.96). 1HNMR (C6D6): 60.79, 0.82, 1.26 and 1.53 (each 3H, s), 2.86 (1H, br d, J = 13 Hz, H-1 equatorial), 10.02 (1H, s, H11). 13CNMR (C6D6)" 618.5, 18.6, 19.2, 20.3, 21.7, 33.3, 33.5, 36.2, 36.5, 38.4, 41.9, 51.6, 143.8, 151.7 and 191.3. ElMS m/z(rel, int.): 220 I'M] § (67), 205 (46), 191 (100), 135 (49), 121 (82), 109 (72), 95 (96), 91 (46), 81 (37), 69 (51), 55 (47). Oxidation of ( + )-albicanol (4) with pyridinium chlorochromate (PCC). To PCC (25 mg) in CH2C12 (4 ml) was added 4 (6.3 rag) in CH2C12 (0.2 ml) and then the mixt. was stirred for 2 hr at room temp. The resulting mixt. was filtered and the solvent removed to yield 2 aldehydes. The GC-MS and R t value of each product were identical to those of 2 and 3, respectively. Reduction of 2 with LiA1H 4. Compound 2 (22.7 rag) in dry Et20 was added dropwise to a suspension of LiA1H 4 (62 mg) in dry Et20 (2 ml) and stirred for 1 hr. An alcohol {19.8 mg; [:t] 22 + 10 (CHC13; c 1.0)} was obtained. The spectral and physical data were identical to those of 4 {purified albicanol, during the present work, [~t]~2+ 10 (CHCI3; c 1.5)} {ref. [11] [:t]D+6 (cnc13; c2.6)}.
1265
Acknowledgement--We thank Dr M. Mizutani (Hattori Botanical Laboratory, Nichinan, Miyazaki, Japan) for the identification of the liverwort. REFERENCES
1. Asakawa, Y. (1982) Prog. Chem. Org. Nat. Prod. 42, 1. 2. Benegova, V., Samek, Z. and Vasickova, S. (1975) Coll. Czech. Chem. Commun. 40, 1966. 3. Ohta, Y., Andersen, N. H. and Liu, C.-B. (1977) Tetrahedron 33, 617. 4. Asakawa, Y., Toyota, M., Takemoto, T. and Suire, C. (1979) Phytochemistry 18, 1007. 5. Asakawa, Y., Tokunaga, N., Toyota, M., Takemoto, T., Hattori, S., Mizutani, M. and Shire, C. (1979) J. Hattori Bot. Lab. 46, 67. 6. Asakawa, Y., Tokunaga, N., Toyota, M., Takemoto, T. and Suire, C. (1979) J. Hattori Bot. Lab. 45, 395. 7. Suzuki, K. T., Suzuki, N. and Nozoe, S. (1971) Chem. Commun. 527. 8. Vig, O. P., Sharma, M. L., Trehan, N. and Verma, N. K. (1980) Ind. J. Chem. 19B, 450. 9. Appel, H. H., Brooks, C. J. W. and Overton, K. H. (1959) J. Chem. Soc. 3322. 10. Wada, K., Tanaka, S. and Marumo, S. (1983) Aoric. Biol. Chem. 47, 1075. 11. Toyota, M., Asakawa, Y. and Takemoto, T. (1981) Phytochemistry 20, 2359. 12. Ragoussis, V. and Liapis, M. (1987) J. Chem. Soc., Perkin Trans. I 987. 13. Andersen, N. H., Bissonette, P., Liu, C.-B., Schunk, B., Ohta, Y., Tseng, C. W., Moore, A. and Huneck, S. (1977) Phytochemistry 16, 1731. 14. Godin, P. (1954) Nature 174, 134.
Pergamon
Phytochemistry,Vol. 35, No. 5, pp. 1263-1265, 1994 Copyright 9 1994 Elsevier Science Lid Printed in Great Britain. All tights reserved 0031 9422/94 $6.00+0.00
DRIMANE-TYPE SESQUITERPENOIDS FROM THE LIVERWORT D I P L O P H YLL UM SERR ULA TUM MASAO TOYOTA, YASUSHIOOISO, TATSUYAKUSUYAMAand YOSHINORIASAKAWA Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770, Japan
(Received4 August 1993)
Key Word |ndex--Diplophyllum serrulatum; Jungermanniales; Hepaticae; drimane-type sesquiterpenoids; (+)-albicanol; (-)-albicanic acid; (-)-albicanal; isoalbicanal; (+)-trans-?-monocyclofarnesol.
Abstract--The liverwort, Diplophyllum serrulatum afforded three new drimane-type sesquiterpenoids albicanic acid, albicanal and isoalbicanal, in addition to (+)-albicanol, (-)-drimenol, (+)-trans-7-monocyclofarnesol, ent-spathulenol and anastreptene. Their structures were established by chemical and spectral means. Albicanol and albicanal were major constituents of this species. This is the first report of the isolation of(-)-albicanic acid in nature and (+)-trans-?monocyclofarnesol from the liverworts.
INTRODUCTION
NMR data are described in the Experimental, as there is no report of these data in the literature. Compound 2, an oil, produced a yellow colouration when treated with 2,4-dinitrophenylhydrazine-sulphuric acid reagent on TLC plates. The E1 mass spectrum of 2 gave a molecular ion peak m/z 220. Its IR spectrum showed the presence of a carbonyl (1721 cm- ~) and an exomethylene (891 cm-1) group. Compound 2 gave the signals in its I H and 13C NMR spectra for the aldehyde (6n9.77 and fic203.4) and the exomethylene group (6n4.51, 4.79, t5c 109.2 and 145.3). The 1H NMR spectrum (see Experimental) showed the signals of three tertiary methyl groups. Lithium aluminum hydride reduction of 2 yielded an alcohol, the spectral and physical data of which were in agreement with those of (+)-albicanol (4) [3, I1, 12]. Accordingly, the above evidence established that 2 only differed from 4 by the replacement of a hydroxy methyl group by a formyl group. The structure of 3 was deduced by comparing its spectral data with those of 2 and chemical evidence. Compound 3 produced the same yellow colouration as 2 with 2,4-DNP on TLC plates, indicating the presence of a carbonyl group. The carbonyl band (1674 cm -~) was confirmed in the IR spectrum of 3 and its UV spectrum showed the presence of the conjugated carbonyl group (245 nm). The ~HNMR spectrum gave the signals for three tertiary methyls (6H0.79, 0.82 and 1.26), a vinyl methyl (6n 1.53) group and a formyl proton (6u 10.02). The pyridinium chlorochromate oxidation of 4 gave 2 and its isomer, ct,fl-unsaturated aldehyde. The GC-mass spectrum and Rt value of the latter compound were identical to those of 3. Thus, the structure of 3 was established as an isomer of 2. We propose a possible biosynthetic pathway for 1-6 (Scheme 1). The 13C
Classification of liverworts belonging to the Jungermanniaceae, a family rich in terpenoids [1], is very difficult and study of their chemical constituents is necessary. For this reason, we have been investigating the chemosystematics of liverworts [1]. In the genus of Diplophyllum, five epiphytic species Diplophyllum serrulatum, D. taxifolium, D. andrewsii, D. obtusifolium and D. albicans, which grow on trunks of deciduous plants, are known in Japan. Previous work on this genus resulted in the isolation of (+)-albicanol (4) and sesquiterpene lactones from D. albicans and D. taxifolium [2-6]. Here, we report on the isolation and structure elucidation of three new drimanetype sesquiterpenoids from D. serrulatum, a species which has not yet been investigated phytochemically. RESULTS A N D D I S C U S S I O N
The ether extract of D. serrulaturn was chromatographed on silica gel, Sephadex LH-20 and repurified by MPLC of silica gel to give three new drimane-type sesquiterpenoids 1-3, (+)-trans-?-monocyclofarnesol (6) [7, 8], ent-spathulenol (7), (-)-drimenol (5) [9, 10], (+)albicanol (4) [3, 11, 12] and a mixture of hydrocarbons containing anastreptene (8) [3, 13]. The E1 mass spectrum of 1 gave I-M] § at m/z 236. The IR spectrum showed the presence of a carboxyl group (3200-2800, 1710cm-1). The ~HNMR spectrum (see Experimental) showed the signals of three tertiary methyls and an exomethylene group. The above spectral data and specific optical rotation were identical to those of (-)-albicanic acid (1) [12]. This is the first isolation of (-)-albicanic acid in nature, although the synthesis and resolution to its enantiomers have been performed [12].
1263
1264
M. TOYOTAet al. COOH
1
CHO
2
CH20H
CHO
r/oPP
3
CH20H
~ 4
5
6
8
-OPP
HO...
.
7
OH
CH20H
....
8
9
CHO
Before the present work, two species. D. albicans and D. taxifolium of this genus had been investigated. Both species elaborate, among the hydrocarbons, mainly ent-~selinene and ent-selina-4,11-diene together with anastreptene and fl-elemene. The more polar constituent of each essential oil contained diplophyllin (9), a eudesmanetype sesquiterpene lactone, as the major component, in addition to 4 [2-4]. On the other hand, 9 and any other sesquiterpene lactones have not been found in D. serrulatum. On the basis of the present results, it is obvious that D. serrulatum is chemically quite different from D. albicans and D. taxifolium. Anastreptene (8) which occurs in the above three species, is quite common in liverworts.
5
2
3
COOH
Scheme 1. A possible biosynthetic pathway of 1-6.
EXPERIMENTAL
General. TLC was carried out on silica gel precoated glass plates with n-hexane-EtOAc (1:1 and 4: 1). Detection was with Godin reagent [14]. For normal phase CC, silica gel 60 (40-63#m) was used. The mixt. of CH2C12-MeOH (1 : 1) was used for CC on Sephadex LH20 as solvent. Spectral data. NMR spectra were recorded at 100 MHz for xsC and 400 MHz for tH. EI mass spectra were measured at 70 eV. GC-MS was carried out at 70 eV and on a fused-silica capillary column coated with DB-17 (30 m • 0.25 mm, df = 0.25 #m) using He as the carrier gas (1 ml min-1). The temp. programming was performed from 50~ isothermal for 3 min, then 50-250 ~ at 5~ rain- 1, and finally isothermal at.250 ~ for 15 min. Injection temp. "\ was 250~ ~ Plant material. Diplophyllum serrulatum (65.9 g) was collected in August 1992, at Tosa, Kochi prefecture in Japan. The voucher specimen (no. 92041) was deposited at the Institute of Pharmacognosy, Tokushima Bunri University. Extraction and isolation. The liverwort was dried for 1 week, and impurities removed under a stereo microscope
by tweezers. The ground material was then extracted with Et20 for 1 month. The Et20 extract (998 mg) was chromatographed on silica gel using n-hexane-EtOAc gradient, giving 7 frs (1-7). The GC-MS of the main compound of fr. 1 (44.2 mg; 4.4% of total extract) was identical to that of 8. Fr. 3 (73.6 mg) was chromatographed on Sephadex LH-20 and further purified by MPLC on silica gel using n-hexane-EtOAc (4: 1), affording 4 (30.1 mg; 3.0%) [3, 11, 12], 5 (6.9 mg; 0.7%) [9, 10] and 6 (5.5 mg; 0.6%) [7, 8], whose spectral data were identical to those of lit. values, respectively. Compound 6 [~t]22 + 18.2 (CHC13; c 0.3) {ref. [7] [~t]D+ 17.6 (EtOH)}. Fr. 5 (67.7 mg) was chromatographed on Sephadex LH20 to give a mixt. containing 1. The mixt. was repurified by MPLC on silica gel using n-hexane-EtOAc (4:1), affording 1; (1.4 mg; 0.14%). Compound 1; [~t]~1 -23.2 (CHCls; c0.07) {ref. [12] Ice]z5 -28.2 (CHC13;cl) }. lsC NMR (CDCls): 614.1, 18.9, 21.8, 23.2, 33.4, 33.5, 36.2, 39.1, 39.2, 42.0, 54.5, 62.5, 108.6, 143.2 and 175.2. Ft.2 (232.2 mg) was chromatographed on Sephadex LH-20, then purified by MPLC on silica gel using nhexane-EtOAc (9:1) to give 2 (61.6mg; 6.2%) and 3
Sesquiterpenoids from liverwort (6.4 mg; 0.6%). Compound 2, oil; [:t]22-69.8 (CHCI3; c3.1); IR Vmaxcm-l: 2730, 1721, 1644, 1460, 1387, 1368, 1113 and 891; IH NMR (C6D6)."60.71, 0.72 and 0.97 (each 3H, s), 2.30 (1H, d, J=4.4 Hz, H-9), 1.80 (1H, ddd, J= 14, 14, 2 Hz, H-7 axial), 2.16 (1H, ddd, J = 14, 4, 2 Hz, H-7 equatorial), 4.51 and 4.79 (each 1H, s), 9.77 (IH, d, J =4 Hz). 13CNMR (C6D6): 615.9, 21.9 and 33.5 (Me), 19.0, 23.3, 36.9, 39.7 and 42.0 (CH2), 53.8 and 67.8 (CH), 33.3 and 39.0 (C), 109.2 (=CH2), 145.3 (C=), 203.4 (CHO). EIMS m/z (rel. int.): 220 [M] § (23), 205 (21), 176 (19), 149 (25), 137 (49), 123 (54), 109 (100), 95 (56), 81 (60), 69 (56), 55 (42). Compound 3, IR Vma~ cm-i: 2760, 1674, 1611, 1460, 1373, 1258 and 1134. UV 2 Et~ nm (loge): 245 (3.96). 1HNMR (C6D6): 60.79, 0.82, 1.26 and 1.53 (each 3H, s), 2.86 (1H, br d, J = 13 Hz, H-1 equatorial), 10.02 (1H, s, H11). 13CNMR (C6D6)" 618.5, 18.6, 19.2, 20.3, 21.7, 33.3, 33.5, 36.2, 36.5, 38.4, 41.9, 51.6, 143.8, 151.7 and 191.3. ElMS m/z(rel, int.): 220 I'M] § (67), 205 (46), 191 (100), 135 (49), 121 (82), 109 (72), 95 (96), 91 (46), 81 (37), 69 (51), 55 (47). Oxidation of ( + )-albicanol (4) with pyridinium chlorochromate (PCC). To PCC (25 mg) in CH2C12 (4 ml) was added 4 (6.3 rag) in CH2C12 (0.2 ml) and then the mixt. was stirred for 2 hr at room temp. The resulting mixt. was filtered and the solvent removed to yield 2 aldehydes. The GC-MS and R t value of each product were identical to those of 2 and 3, respectively. Reduction of 2 with LiA1H 4. Compound 2 (22.7 rag) in dry Et20 was added dropwise to a suspension of LiA1H 4 (62 mg) in dry Et20 (2 ml) and stirred for 1 hr. An alcohol {19.8 mg; [:t] 22 + 10 (CHC13; c 1.0)} was obtained. The spectral and physical data were identical to those of 4 {purified albicanol, during the present work, [~t]~2+ 10 (CHCI3; c 1.5)} {ref. [11] [:t]D+6 (cnc13; c2.6)}.
1265
Acknowledgement--We thank Dr M. Mizutani (Hattori Botanical Laboratory, Nichinan, Miyazaki, Japan) for the identification of the liverwort. REFERENCES
1. Asakawa, Y. (1982) Prog. Chem. Org. Nat. Prod. 42, 1. 2. Benegova, V., Samek, Z. and Vasickova, S. (1975) Coll. Czech. Chem. Commun. 40, 1966. 3. Ohta, Y., Andersen, N. H. and Liu, C.-B. (1977) Tetrahedron 33, 617. 4. Asakawa, Y., Toyota, M., Takemoto, T. and Suire, C. (1979) Phytochemistry 18, 1007. 5. Asakawa, Y., Tokunaga, N., Toyota, M., Takemoto, T., Hattori, S., Mizutani, M. and Shire, C. (1979) J. Hattori Bot. Lab. 46, 67. 6. Asakawa, Y., Tokunaga, N., Toyota, M., Takemoto, T. and Suire, C. (1979) J. Hattori Bot. Lab. 45, 395. 7. Suzuki, K. T., Suzuki, N. and Nozoe, S. (1971) Chem. Commun. 527. 8. Vig, O. P., Sharma, M. L., Trehan, N. and Verma, N. K. (1980) Ind. J. Chem. 19B, 450. 9. Appel, H. H., Brooks, C. J. W. and Overton, K. H. (1959) J. Chem. Soc. 3322. 10. Wada, K., Tanaka, S. and Marumo, S. (1983) Aoric. Biol. Chem. 47, 1075. 11. Toyota, M., Asakawa, Y. and Takemoto, T. (1981) Phytochemistry 20, 2359. 12. Ragoussis, V. and Liapis, M. (1987) J. Chem. Soc., Perkin Trans. I 987. 13. Andersen, N. H., Bissonette, P., Liu, C.-B., Schunk, B., Ohta, Y., Tseng, C. W., Moore, A. and Huneck, S. (1977) Phytochemistry 16, 1731. 14. Godin, P. (1954) Nature 174, 134.