- 著者
- 古森 徹哉 瀬戸口 信郎 川崎 敏男
- 出版者
- 天然有機化合物討論会実行委員会
- 雑誌
- 天然有機化合物討論会講演要旨集 10 (ISSN:24331856)
- 巻号頁・発行日
- pp.216-223, 1966-09-15 (Released:2017-08-18)
The unknown, nonsteroidal, nonglycosidal and N-free substance, which had been obtained as crystals from the root tubers of Dioscorea bulbifera L. forma spontanea Makino et Nemoto, was found to be a mixture of at least three compounds. One of them, named bulbiferin C, m.p.255°, (α)_D +17.3°, was isolated only in trace and the structures of major component, bulbiferin B, m.p. 285°, (α)_D+103.0° and minor, bulbiferin A, m.p. 283°, (α)_D +16.2°, were investigated. Bulbiferin B, C_<19>H_<20>O_6, m.w. 344 (mass) has γ-lactone, β-substituted furane and no hydroxyl groups (positive Ehrlich reaction, I.R., U.V. and mass spectra). B is converted to A by hydrolysis with NaOH in pyridine followed by neutralisation and methylation with diazometane. Bulbiferin A,C_<20>H_<24>O_7, m.w. 376 (mass), has hydroxyl, ester, γ-lactone and β-substituted furane functions (Ehrlich reaction, I.R., U.V. and mass spectra). On treatment with NaBH_4 B is unchanged but by catalytic hydrogenation over PtO_2 it gives a hexahydro-compound having tertiary hydroxyl group indicating B (and also A) has an ether oxygen. The hydrogenated B is reduced with LiAlH_4 and the product is subjected to the Se-dehydrogenation to give 1,2,5-trimethyl naphthalene. The N.M.R. spectra of tetrahydro-B and -A indicate the presence of one tertiary methyl group. From these and other experimental data B and A are respectively assigned the partial formulae (a) and (b) of furano-norditerpene type. The results of a further investigation on the location of the functional groups which lead to the tentative structures of B and A are presented.
- 著者
- 古森 徹哉 瀬戸口 信郎 川崎 敏男
- 出版者
- 天然有機化合物討論会実行委員会
- 雑誌
- 天然有機化合物討論会講演要旨集
- 巻号頁・発行日
- vol.10, pp.216-223, 1966
The unknown, nonsteroidal, nonglycosidal and N-free substance, which had been obtained as crystals from the root tubers of Dioscorea bulbifera L. forma spontanea Makino et Nemoto, was found to be a mixture of at least three compounds. One of them, named bulbiferin C, m.p.255°, (α)_D +17.3°, was isolated only in trace and the structures of major component, bulbiferin B, m.p. 285°, (α)_D+103.0° and minor, bulbiferin A, m.p. 283°, (α)_D +16.2°, were investigated. Bulbiferin B, C_<19>H_<20>O_6, m.w. 344 (mass) has γ-lactone, β-substituted furane and no hydroxyl groups (positive Ehrlich reaction, I.R., U.V. and mass spectra). B is converted to A by hydrolysis with NaOH in pyridine followed by neutralisation and methylation with diazometane. Bulbiferin A,C_<20>H_<24>O_7, m.w. 376 (mass), has hydroxyl, ester, γ-lactone and β-substituted furane functions (Ehrlich reaction, I.R., U.V. and mass spectra). On treatment with NaBH_4 B is unchanged but by catalytic hydrogenation over PtO_2 it gives a hexahydro-compound having tertiary hydroxyl group indicating B (and also A) has an ether oxygen. The hydrogenated B is reduced with LiAlH_4 and the product is subjected to the Se-dehydrogenation to give 1,2,5-trimethyl naphthalene. The N.M.R. spectra of tetrahydro-B and -A indicate the presence of one tertiary methyl group. From these and other experimental data B and A are respectively assigned the partial formulae (a) and (b) of furano-norditerpene type. The results of a further investigation on the location of the functional groups which lead to the tentative structures of B and A are presented.
- 著者
- 杉山 重夫 本田 昌徳 古森 徹哉
- 出版者
- 天然有機化合物討論会実行委員会
- 雑誌
- 天然有機化合物討論会講演要旨集
- 巻号頁・発行日
- vol.31, pp.22-29, 1989
In our study on the isolation and structure elucidation of biologically active compounds from marine invertebrates, we synthesized the four diastereomers of C_<16>-phytosphingosine (10, 12, 25, and 26), acanthacerebroside A (1), and D-galactosylceramide (3b) as described below. (2S, 3S)-Allylic alcohol, which was prepared from the L-serine derivative and the (E)-vinylalane compound, was converted into (2S, 3S, 4R)- and (2S, 3S, 4S)-phytosphingosines by epoxidation, DIBAH reduction, and debenzylation. The same treatment of (2S, 3R)-allylic alcohol gave (2S, 3R, 4R)- and (2S, 3R, 4S)-phytosphingosines. (2R)-Acetoxytetracosanoic acid was prepared and coupled to (2S, 3S, 4R)-phytosphingosine to give the ceramide (34). Glycosylation of 34 gave the desired monoglycoside (36) and the bisglycoside (37). 36 was converted into 1 by deacetylation. New D-galactosylceramides were isolated from Chondropsis sp., but the absolute stereochemistry has not been determined. Therefore, (2S, 3S, 4R, 6E)- and (2R, 3R, 4R, 6E)-phytosphingosines were prepared via asymmetric epoxidation. The former was transformed to (2S, 3S, 4R, 6E, 2'R)-D-galactosylceramide and its heptaacetate. The spectral data of them were in excellent agreement with those of the natural specimens.
- 著者
- 本田 昌徳 上田 義隆 杉山 重夫 古森 徹哉
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.39, no.6, pp.1385-1391, 1991-06-25 (Released:2008-03-31)
- 参考文献数
- 24
- 被引用文献数
- 12 20
A cerebroside, 1-O-(β-D-galactopyranosyloxy)-(2S, 3S, 4R, 6E)-2-[(R)-2-hydroxytetracosanoylamino]-17-methyl-6-octadecene-3, 4-diol (2), was asymmetrically synthesized from isobutyraldehyde. On the basis of a comparison of the physical data, the absolute structure of a new cerebroside 1b from a Chondropsis sp. sponge is thought to be the same at that of 2.
- 著者
- 樋口 隆一 時光 義徳 古森 徹哉
- 出版者
- 天然有機化合物討論会実行委員会
- 雑誌
- 天然有機化合物討論会講演要旨集
- 巻号頁・発行日
- vol.28, pp.224-231, 1986
Mechanisum of the diazomethane degradation for the sugar-aglycone linkage of the gypsogenin 3-O-glycoside(1) was studied and the useful degradative reaction was applied to the structure determination of quillayasaponin. Since three kinds of functional groups of 1, the 4α-CHO group in the aglycone, COOH and 4-OH group in the glucuronic acid were presumed to contribute to the degradative reaction, the necessarity of the each functional group was examined using a model compound 7, and only the 4α-CHO group was showed to be essential. By taking the above evidence and the usual reaction products of aldehyde with diazomethane into account, the reaction must be proceeded through such a oxide intermediate as shown in the scheme 6. QS-III(25), a major acylated genuine bisdesmoside of the so-called quillayasaponin, afforded a 28-O-glycosidal triterpenoid(29) still possessing acyl moiety by this diazometane degradation. On the basis of chemical and spectral evidence, especially, comparison of the ^<13>C NMR spectra of 29 and its desacyl compound(30)(Table 1), the site of linkage of acyl moiety of 29 was determined. The structure of 25, therefore, was complex acylated oligosaccharide as shown in scheme 8.
1 0 0 0 有棘目動物の生産する細胞毒性活性成分の化学的研究
沖縄県那覇近海で採集した有棘目動物オニヒトデの棘の凍結乾燥粉末について、魚毒活性を指標に溶媒分画、従来法による各種クロマトグラフィ-並びに購入設備を駆使して毒成分の精製を行い、メタノ-ルエキスより1種のステロイドオリゴ配糖体サルフェ-ト(20S-thorasterosideA)及び、2種のアルキルグリセロリン脂質(sn-1-0-hexadecylglycerol-3-phosphorylcholine,sn-1-0-octadecylglycerol-3-phosphoryl-choline)の単離同定に成功した。これら3種の化合物はいずれも強い溶血作用を有し、従来不明であったオニヒトデ棘の溶血毒はこれら3種の成分に起因することが判明した。次に、上述棘粉末の水エキスについて購入設備を駆使したゲル濾過によるクロマトグラフィ-を繰り返し、in vitroで細胞毒性を示す2種の蛋白質(Protein I 並びに Protein II)を得た。Protein Iは最終的にμBondasphereを使用したHPLCで精製した結果、分子量は約14650であり、アミノ酸分析により、Asp_<17>・Thr_<11>・Ser_8・Glu_<15>・Pro_5・Gly_<18>・Ala_9・Val_<12>・Met_2・Ile_7・Leu_6・Tyr_2・Phe_7・Lys_<14>・His_1・Arg_2の16種のアミノ酸組成を明らかにすることができた。また、N末端配列分析の結果、末端より25種のシ-クエンスが判明した。この結果をもとにGENASを用い、既知蛋白質との比較を行ったが、類似シ-クエンスを示す酢蛋白質は検索されず、新規蛋白質と考えられた。Protein Iはin vitroで選択的細胞毒性を示す結果を得ており、現在1次構造解析が進行中である。Protein IIについては、まだ、単離には至っていないが、SDS-PAGEで分子量約8万と推定され、マウスに対しては未精製ながらも強い致死作用を示すことから、Protein IIがオニヒトデ棘毒成分のマウスに対する致死毒の本体であることが推察された。