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T. Sano, J. Toda, N. Kashiwaba, Y. Tsuda
Article type: Article
Session ID: 45
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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An efficient synthesis of Erythrina alkaloid was described. 1. Synthesis of isoquinolinopyrrolinedione 5. The synthesis of 5 was achieved starting from arylethylamine 6 in yield of 60〜80% by following three steps: i) Condensation with ethyl or methyl malonyl chloride. ii) Intramolecularcyclization to isoquinoline. iii) Condensation with oxalyl chloride. 2. Diels-Alder Reaction of 5 with butadienes. Diels-Alder addition of 5 with butadienes, specially 1-methoxy-3-silyloxybutadiene or 1,3-disilyloxybutadiene, smoothly proceeded in a regio and stereospecific manner to give 1,4-adducts 12 and 13, respectively, having an erythrinan skelton. The structures were elucidated by the X-ray analysis of the diacetate 20 derived from 12c. 3. Syntheses of erysotramidine 2,3-epierysotramidine 28, 8-oxoerythraline 35 and 3-epi-8-oxoerythraline 34. The value of this approach to Erythrina alkaloid was demonstrated by the total synthesis of 2 and its epimer 28. Partial reduction of 12b or 13b with LiBH_4, followed by acidic treatment afforded a conjugated ketone 22. Decarboalkoxylation of 22 with MgCl_2 in DMSO gave a dienone 24. Reduction of this with NaBH_4 gave epimeric allyl alcohols 25 and 26, which on methylation with CH_3I furnished 3-epierysotramidine 28 and erysotramidine 2, respectively. 8-Oxoerythraline 35 and its 3-epimer 34 were also synthesized from the key intermediate 13c by similar procedure.
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T. Ibuka, H. Minakata, Y. Mitsui, T. Taga, Y. Inubushi
Article type: Article
Session ID: 46
Published: September 10, 1980
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Although synthetic studies on histrionicotoxins (HTX) which are toxic constituents of Neotropical arrow poison frogs of Dendrobates genus have been undertaken in many routes, we also have synthesized an important intermediate (35) of the toxin by a stereoselective manner outlined below. 1) Synthesis of the hydroxy-ester (17) A) Though treatment of the γ-acetoxy- orγ-t. butyldimethylsiloxy-α,β-unsat. esters (1a,1b,5) with ^nBu_2CuLi gave the reduced products (2,6), reaction with ^nBuCu-AlCl_3, a modified method of Yamamoto, yielded the α- and γ-substitution products. B) Although treatment of the ketones (9,13) with R_2CuLi provided the conjugate adducts in low yields, use of RCu-AlCl_3 yielded the 1,4-adducts in high yields (see Table). Hydrolysis of (10b) followed by acetylation gave the acetate (16), which was successively treated with NaOBr and CH_2N_2 to give (17). 2) Synthesis of a key intermediate (35) for perhydro-HTX. The THF-ester (18) derived from (17) was stereoselectively alkylated with allyl bromide to yield (21). The lactone (25), obtained by treatment of (21) with p. TsOH, was successively treated with OsO_4, (EtO)_2P(O)CHCO_2Et, and H_2/PtO_2 to afford the lactone-ester (27). The Dieckmann reaction of (27) with KH gave the keto-ester (28), which was decarboxylated to yield the ketone (29). Alternatively, the THF-ester (30), obtained from (21), was converted into the THF-ketone (33) by a similar procedure as above in a satisfactory yield. Oximation of (29) or (33) afforded the oxime (34), mp.56°. Beckmann rearrangement of (34) provided the lactam (35), mp. 164-165°, which is an intermediate for perhydro-HTX.
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Y. Nagao, S. Takao, K. Seno, T. Miyasaka, E. Fujita
Article type: Article
Session ID: 47
Published: September 10, 1980
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Total synthesis of codonocarpine (5), a 24-membered ring spermidine dilactam alkaloid isolated from Codonocarpus australis by Doskotch et al., has been accomplished. The key step is aminolysis of the compound (13) with spermidine (4). Codonocarpine (5) and its regio-isomer "iso-codonocarpine" (22) were effectively separated by droplet counter-current chromatography (DCCC). Codonocarpine and "iso-codonocarpine" were obtained as yellowish prisms of mp 183-187°and of mp 243-246°(decomp.), respectively. Although the direct comparison of our synthetic codonocarpine with an authentic sample was not possible because of no availability of the latter, the comparison of their melting points and their spectral data gave evidence for their identity. Furthermore, N,O-diacetate (23) was confirmed to be completely identical with the authentic sample supplied kindly by Prof. Doskotch. The second topic is concerned with an approach to the total synthesis of two 20-membered ring spermidine dilactam alkaloids, dl-lunarine (6) and dl-lunaridine (7), which have been isolated from the seeds of Lunaria biennis by Boit. After a model experiment (the synthesis of their racemic tetrahydro-derivatives), the synthesis of the racemates of the natural alkaloids was attempted. The key intermediate synthesized by Potier et al. was converted into diamide (40), which was treated with spermidine (4). The separation and characterization of the reaction products are in progress.
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T. Suga, T. Shishibori, T. Hirata, Y. Yoshioka, M. Okamura
Article type: Article
Session ID: 48
Published: September 10, 1980
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The malloprenols isolated from the leaves of Mallotus japonicus were elucidated to be (2z,6z,10z,14z,18z,22z,26E,30E,34E)-3,7,11,15, 19,23,27,31,35,39-decamethyl-2,6,10,14,18,22,26,30,34,38-tetraconta-decaen-1-ol and its C_<45>- and C_<55>-homologues, on the basis of observations of mass peaks due to succesive loss of an isoprene residue and ^1H NMR signal due to allylic methyls, methylenes, cis-and trans-olefinic protons, and an allylic primary hydroxyl group and demonstrations of the arrangement of the E- and z-isoprene units by comparing the incorporation of a homolog of all E-prenyl-1-^3H_2 pyrophosphates with that of the corresponding 2-z isomers. In the biosynthesis of isoprenoids, it is a tenet that the pro-4S hydrogen atom of mevalonic acid (MVA) is lost in the formation of an E-isoprene residue, while the pro-4R hydrogen atom is eliminated in the formation of a z-isoprene residue. However, the unusual elimination of the pro-4s hydrogen atom of mevalonic acid in the biological formation of z-isoprene residues of malloprenols by Mallotus japonicus was observed in feeding experiments of mevalonic acid-2-^<14>C,(4R)-4-^3H and its (4S)-4-^3H isomer. This is in contrast to the doctrinal isoprenoid pathway that the pro-4R hydrogen atom is eliminated in the formation of a z-isoprene residue.
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Shinichi Uesato, Shinichi Ueda, Koji Kobayashi, Satoko Matsuda, Hiroyu ...
Article type: Article
Session ID: 49
Published: September 10, 1980
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Various combinations of ^<13>C-labeled and non-labeled acyclic monoterpenes including the following compounds were administered to the iridoid-producing cell suspension cultures of Gardenia jasminoides f. qrandiflora: 10-hydroxygeraniol (4), 9,10-dihydroxygeraniol (21), 10-hydroxycitronellol (19), 9,10-dihydroxycitronellol (22) or a pair of (10-^2H)-iridodial (13) and (11-^2H_2)-7,8-dehydroiridodial (17). The incorporation of ^<13>C or ^2H label of these substances into tarennoside (14), a major iridoid glucoside of the cultured cells, was traced by means of ^<13>C- or ^2H-NMR spectrometry. The results revealed that 10-hydroxygeraniol (4) and 7,8-dehydroiridodial (17) are the obligatory precursors of the iridoid glucosides of the Gardenia cells and that the ^2H label of (11-^2H_2)-17 was incorporated into 3 and 11 positions of tarennoside (14) with extensive randomization. Administration experiments of ^3H-labeled compounds including 10-hydroxygeraniol (4), 10-oxogeranial (11), 9,10-dihydroxygeraniol (21), 9-hydroxy-10-oxogeranial (24), 10-hydroxycitronellol (19), and iridodial (13) to Catharanthus roseus showed that incorporations of 10-hydroxygeraniol (4) and iridodial (13) into vindoline (23) are much greater than those of the other compounds. It is therefore highly probable that indole alkaloids, and therefore, secoiridoids are biosynthesized via iridodial (13) formed by way of the cyclization of 10-oxoneral (12). It has thus been clarified that all the iridoids are biosynthesized via the intermediate cation (16) formed through the cyclization of 10-oxogeranial (11) or 10-oxoneral (12).
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Trevor C. McMorris
Article type: Article
Session ID: 50
Published: September 10, 1980
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Recent work on the biosynthesis of the oogoniols, female-activating hormones of the aquatic fungus Achlya, is reviewed. Fucosterol, the major sterol with Achlya, is the precursor of the oogoniols and 29-hydroxy fucosterol may be an intermediate since the tritiated sterol is well incorporated into dehydrooogoniol-2. Progesterone is metabolized to 11α-hydroxy progesterone by Achlya.
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Tozo Fujii, Masashi Ohba
Article type: Article
Session ID: 51
Published: September 10, 1980
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The target molecule (±)-VIII was selected for synthesis with a view to establishing the structure of demethyltubulosine, one of the benzoquinolizidine alkaloids isolated from Alangium lamarckii Thw. (family Alangiaceae). Condensation of the tricyclic amino acid X, prepared from ethyl (±)-trans-5-ethyl-2-oxo-4-piperidineacetate in eight steps according to previously reported procedure, with 5-benzyloxytryptamine using the coupling reagent diethyl phosphorocyanidate gave the tryptamide XI (96% yield), which was then cyclized (POCl_3, boiling toluene) to XII in 59% yield. Catalytic hydrogenation of XII (Pt/H_2, dioxane) and chromatographic separation of the products afforded the base XIII (25% yield) and its 1'-epimer (XIV) (54% yield). The two bases were separately debenzylated (Pd-C/H_2, MeOH-AcOH) to produce the corresponding phenolic bases, VIII and XV, in good yields. The relative configuration at C-1' of XIII, XIV, VIII, and XV was confirmed by the method given in the literature. The UV, IR, PMR, and mass spectra and chromatographic behavior of the synthetic (±)-VIII thus obtained were found to be identical with those of natural demethyltubulosine, establishing the structure of this alkaloid as 10-demethyltubulosine.
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H. Takayama, S. Sakai, T. Okamoto
Article type: Article
Session ID: 52
Published: September 10, 1980
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Three new minor diterpene alkaloids, ezochasmanine 12, ezochasmaconitine 9 and anisoezochasmaconitine 10 together with major alkaloids pseudkobusine 2 and chasmanine 8 were isolated from Aconitum yesoense Nakai. (Chart 1). The structures of new bases 12, 9 and 10 have been established as 3-α-hydroxychasmanine, 14-acetyl-8-benzoylchasmanine and 14-acetyl-8-anisoylchasmanine respectively. The structure of ezochasmanine 12 was first postulated from it's ^<13>CNMR spectrum and ^1HNMR spectrum of the 3-acetyl derivative. To confirm the structure, transformation of ezochasmanine 12 to chasmanine 8 of known structure was carried out as shown in chart 3. Ezochasmaconitine 9 and anisoezochasmaconitine 10 were synthesized from chasmanine 8 by two steps via. acetylation, benzoylation or p-anisoylation. These two alkaloids are the first examples of the diterpene alkaloids possessing the aroyl groups at C8 and acetyl group at C14. All of the formerly known congeners have the aroyl groups at C14 and acetyl group at C8. Mild toxicity was observed for the two new bases, 9 and 10. Isodelphonine 33 which is an alkamine of isodelphinine 34, was stereoselectively synthesized from chasmanine 8 as described below. (Chart 4). Oxidation of diacetylchasmanine 27 with KMnO_4 in aqacetone gave the des-N-ethyl derivative 28, which was then formylated to give N-formyl compound 29. Pyrolysis of 29 gave the Δ^<8,15> olefinic derivative 30, which was converted into epoxy derivative 31 by m-CPBA oxidation. Ring opening reaction of 31 using formic acid gave rise to the trans diol derivative 32 which was reduced by LiAlH_4 to yield isodelphonine, mp 135-137°, 33.
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R. Nishida, W. S. Bowers
Article type: Article
Session ID: 53
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Two compounds with highly potent juvenile hormone activity were isolated from oil of sweet basil, Ocimum basilicum L., Labiatae. Each substance exhibited the activity in the milkweed bug juvenile hormone test in the picogram range. Structures of these compounds were determined to be I and II from their spectrometric analyses, and preparation of the skeletal compounds to III and IV, respectively. Since these compounds possess exceedingly high juvenile hormone activity and contain ocimene as a portion of their structure, we have named them juvocimene-I and II. In order to confirm the geometry of 2-methyl-1,3-butadienyl moiety, several analogs were studied, including trans and cis-dihydrojuvocimene (XV, XVI) which were prepared photochemically from a derivative of α-pinene (XIV). Synthesis of I was successfully achieved by a coupling reaction between a lithium salt of β-ocimene and p-methoxycinnamyl chloride. Epoxidation of I with m-chloroperbenzoic acid yielded II as a mixture of the diastereomers. These racemic I and II showed the same physical constants, and the same level of the biological activity as those of juvocimene-I and II isolated from oil of sweet basil. The unique structures and activity of the juvocimenes suggest that sweet basil may have developed such a chemical difense against insect predation through hormonal derangement of insect morphogenic development.
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Mitsumasa Haruna, Yoshihisa Sakakibara, Kazuo Ito
Article type: Article
Session ID: 54
Published: September 10, 1980
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Twenty new sesquiterpene lactones were isolated from four plants belonging to Japanese Eupatorium species (Japanese name: SAWAHIYODORI; HIYODORIBANA; YOTSUBAHIYODORI; and HAKONEHIYODORI). The structure of these new sesquiterpene lactones have been determined by the spectral methods and chemical transformations. Eupatorium lindleyanum DC. contains eupalinin-A (1), -B (2), -C (3), -D (4), and -E (5), which are closely related heliangolides. Among these compounds, eupalinin-A (1) showed significant inhibitory against KB cell culture. From Eupatorium chinense L. var. simplicifolium (Makino) Kitam., was isolated eupachifolin-A (10) which was cis-Δ^<4,5>, cis-Δ^<1,10>-germacranolide possessing α,β-unsaturated aldehyde group and eupachifolin-B (11), -C (12), -D (13), -E (14) belonging to mutually related guaianolides. Peroxysachalinin (19), sachalinin (20), and sachalin (21) were obtained from Eupatorium sachalinense (Fr. Schmidt) Makino, along with a known sesquiterpene lactone, eupatoriopicrin (18) which was a main component of this plant. The ingridients of Eupatorium chinense L. var. hakonense (Nakai) Kitam. consist of seven biogenetically related guaianolides; peroxyeupahakonin-A (25), -B (26), eupahakonin-A (27), -B (28), eupahakonenin-A (29), -B (30) and eupahakonesin (31). Peroxysachalinin (19) containing an allyl hydroperoxy group was a first isolated germacrane-type sesquiterpene lactone from Compositae. Finally, these three allyl hydroperoxy sesquiterpene lactones, peroxysachalinin(19), peroxyeupahakonin-A (25) and -B (26) seem to the important Key intermediates in the course of biosynthesis of germacranolides and guaianolides.
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A. Matsuo, N. Kubota, S. Uto, H. Nozaki, M. Nakayama, S. Hayashi
Article type: Article
Session ID: 55
Published: September 10, 1980
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Since, during the investigation on terpenoids of the liverworts, we had sometimes observed allelopathy between liverworts and some vascular plants in fields, the work was undertaken to isolate plant growth inhibitors from the liverworts. The present work was carried out on the methanol extract of the leafy liverwort Lepidozia vitrea Steph. because the extract showed a plant growth-inhibitory activity on the biological test using rice seedlings. Three sesquiterpene aldehydes naming (-)-isobicyclogermacrenal, (-)-lepidozenal, and (+)-vitrenal were isolated from the methanol extract by combination of column and preparative TLC together with ent-bicyclogermacrene and ent-aroma-dendrene. The structures including absolute configuration were determined, based on the chemical and spectroscopic examination and the X-ray analysis, to be ent-isobicyclogermacra-1(10)E,4E-dien-14-al (1), ent-lepidoza-1(10)E,4E-dien-14-al (2), and ent-vitr-4-en-14-al (3). These compounds inhibit almost perfectly the growth of leaves and roots of rice seedlings in concentrations of 50, 250, and 25ppm, respectively.
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H. Itokawa, K. Watanabe, S. Mihashi, Y. Iitaka
Article type: Article
Session ID: 56
Published: September 10, 1980
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The seeds of A. japonica (Zingiberaceae) have been used as an aromatic stomachic under the name, "Izu-shukusha", in Japan. From the fresh rhizomes of the plant, two new sesquiterpenes, 3α,4α-oxidoagarofuran(2) and hanalpinol(11) were isolated together with 4α-hydroxydihydroagarofuran(1), α-agarofuran(3), 10-epi-γ-eudesmol(4), β-eudesmol(5) and furopelargone B(15). The structure of (2) was elucidated by chemical correlation with (1). Hanalpinol(11) was obtained as a fairly stable oil. Chemical and physical evidences indicated that this compound is a novel sesquiterpene peroxide possessing the partial structure as shown in Fig. 1. Oxidation of (11) with pyridinium chlorochromate gave a crstalline α,β-unsaturated ketone(12), the structure of which was established by means of X-ray analysis. The IR spectrum of (11) revealed the presence of intramolecular hydrogen bond, and acid treatment of (11) resulted in the formation of furopelargone B(15). Therefore, the structure of hanalpinol can be illustrated as formula (11). It is noteworthy that some of the above sesquiterpenes have significantly antagonistic activities against histamine and barium chloride on excised guinea pig ileum.
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Tetsuro Fujita, Yoshio Takeda, Tetsuro Shingu
Article type: Article
Session ID: 57
Published: September 10, 1980
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In the course of the studies on biologically active substances from Labiatae plants, we examined the constituents of the aerial part of Rabdosia effusa (Maxim.) Hara and isolated eight diterpenoids. Five of those (named as effusanin A, B, C, D and E) are new compounds and their structures were elucidated as 1, 2, 3, 4 and 5, respectively, from spectral and chemical evidence. The other three compounds were identified as shikokianin (6), longikaurin E (7) and longikaurin F (8). The antibacterial activities of all the diterpenoids isolated here were also examined.
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T. Nohara, Y. Kashiwada, K. Murakami, T. Tomimatsu, M. Kido, I. Nishio ...
Article type: Article
Session ID: 58
Published: September 10, 1980
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Recently, Koda et al. have reported that the water extractives of Cinnamomi Cortex (the dried bark of Cinnamomum cassia Blume) exhibit potent anti-complement activity. For the purpose of identification of the substance(s) possessing this activity, we had isolated a series of diterpenes (compds. I-XIII) from the fraction exhibiting anti-complement activity of the water extractives and elucidated their structures. These diterpenes so far obtained from C. Cortex are classified into the three groups, namely those of ketal-, lactone- and diketone-type. In a continuation of this work, additional five kinds of diterpenes (compds. 1-5) have been characterized, which are closely related to each other in structure and belong to a new group different from the above three groups. They are novel pentacyclic diterpenes with a new skeleton consisting of two six-membered rings and three five-membered rings. As for pharmacological test of anti-complement activity for each diterpene (compds. I-XIII and 1-5) isolated from C. Cortex, it will be discussed in near future.
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H. Ohigashi, M. Hirota, A. Kobayashi, K. Koshimizu, H. Fujiki, M. Mori ...
Article type: Article
Session ID: 59
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Eight diterpene esters were isolated from two species of plants in the family Euphorbiaceae. There were two piscicidal and two related compounds from A. fordii and four piscicidal compounds from E. cotinifolia. On the basis of chemical and spectral evidences, the compounds from A. fordii were 16-hydroxy-phorbol- and related-esters as shown by 1, 2, 3 and 4, and those from E. cotinifolia were ingenol-esters shown to be 7, 8, 9 and 10. In addition to the piscicidal activity, inhibitory activity of the compounds on embryo cell division of sea urchin and ornithine decarboxylase inducing activity on mouse skin were examined. Common structural factors, required to show activity in all of the biological assays, were pointed out. Acyl moieties and 4β-hydroxy (or 4β-hydrogen) were essential to the activity of 16-hydroxyphorbol-esters. For the activity of ingenol-esters, the presence of an acyl group on the oxygen at C-3 and the free hydroxy group at C-5 are important. Furthermore active esters caused abnormal morphological change of unfertilized embryos of sea urchin. They stimulated the incorporation of ^3H-leucine into the protein fraction.
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Munehiro Nakatani, Koji Nakanishi
Article type: Article
Session ID: 60
Published: September 10, 1980
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The root bark of the East African tree Trichilia roka has yielded a series of new limonoids, the trichilins, which exhibit a broad spectrum insect antifeedant and pesticidal activity against the Southern army-worm, Mexican bean beetle, Tobacco horn-worm and other pest insects. Except for azadirachtin, they are the only compounds which are active against the Southern army-worm. The isolation of various trichilins was only possible after very carefully controlled HPLC. Extensive NMR studies including two-dimentional J resolved techniques clarified assignments of all protons, carbons and the entire structures. Application of a recently found additivity rule in the amplitudes of coupled CD cotton effects was used in assignming the configurations at C-12 in trichilins A and B.
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M. Ochi, M. Watanabe, I. Miura, M. Kido, M. Taniguchi, T. Tokoroyama
Article type: Article
Session ID: 61
Published: September 10, 1980
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Constituents of four marine algae, Laurencia okamurai, Dictyota dichotoma, Dictyota linearis, and Dictyopteris undulata, which showed antimicrobial activity against yeast or mold, were examined. Six aromatic sesquiterpenes 1-6 were isolated from L. okamurai, three diterpenes 7-9 from D. dichotoma, five sesquiterpene-substituted phenols 10-14 from D. undulata, and five diterpenes 15-19 from D. linearis, respectively. Compounds 1-12 were previously known and identified by the comparison of spectral data. Structures of new compounds 13-19 were determined on the basis of spectral and chemical evidence. Compounds 13-18 have been found to have the dolastane skeleton and compound 19 to have a novel secodolastane structure. Antimicrobial activity of the respective compounds have been evaluated.
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Nobuyasu Enoki, Takeshi Matsumoto, Ryoichi Ishida, Shiro Urano
Article type: Article
Session ID: 62
Published: September 10, 1980
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Five new diterpenes, dictyofuran A(11), dictyofuran B(12) dictyofuran C(13) isoacetoxycrenulatin (14), dictyelemol (15) were isolated from the marine brown alga Dictyota dichotoma. The structures of these compounds were studied by spectroscopic means. Dictyofuran A, B and C are the new diterpenes with unusual C-skeleton and isoacetoxycrenulatin is an isomer of acetoxycrenlatin(19). Dictyelemol (15) has the same skeleton as that in elemene(25) but without the eight-carbon side chain.
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T. Komori, K. Sakamoto, Y. Itakura, H. Nanri, I. Maetani, T. Kawasaki
Article type: Article
Session ID: 63
Published: September 10, 1980
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As for the constituent steroid oligoglycosides of star fish, thornasteroside A, thornasterol B glycoside (from Acanthaster planci) and Asterosaponins A, B, glycosides B_1 and B_2 (from Asterias amurensis) have so far been isolated and characterized. Now, a new steroid hexaglycoside, mp250°, was isolated as pure crystals from the solvolysis products of a glycoside fraction of water extracts of Astropecten latespinosus M. (Astropectinidae) and assigned the structure 1. From the whole body of Acanthaster planci (Acanthasteridae), another new steroid pentaglycoside sodium sulfate, mp 208-210°, was also isolated in a pure crystals and a tentative structure (2) was proposed. Two constituents (3), mp199-201° and (4), mp209-212° of Luidia maculata M. et T. (Luididae), and one (5), mp214-215°, of Luidia quinaria von Martens (Luididae) were also obtained and their structures were investigated.
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T. Kikuchi, S. Kadota, H. Suehara, T. Namba
Article type: Article
Session ID: 64
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Two new triterpenes, named cyclonervilol and cyclohomonervilol, were isolated from I-tiam-hong (dried herbs of Nervilia purpurea and Nervilia aragoana), which is used as a folk medicine for contused wound and hypertension in Formosa. Structures of cyclohomonervilol and cyclonervilol were assigned to the formula (1b) and (8b), respectively, on the basis of chemical and spectroscopic evidence. Chemical transformation of cyclohomonervilol (1b) to cycloeucalenol (7) was also accomplished.
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K. Hayashi, K. Wada, H. Mitsuhashi, H. Bando, M. Takase, S. Terada, Y. ...
Article type: Article
Session ID: 65
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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The crude drug Condurango Cortex, the bark of Marsdenia cundurango Reich. has been used as an aromatic bitter stomachic and also used against cancer. We report herein that six new antitumor active glycosides: condurangoglycoside -A_0(8), -C_0(9), -B_0(10), -D_0(11), 20-O-methyl-condurangoglycoside-D_0(12) and 20-iso-O-methyl-condurangoglycoside-D_0(13), were isolated from this drug by effective use of HPLC systems. Mild acid hydrolysis and ^<13>C-NMR spectra suggested that the sugar moieties of those glycosides were identical. The sugar linkage was determined as β-D-glucosyl-(1→4)-6-deoxy-3-O-methyl-β-D-allosyl-(1→4)-β-D-oleandrosyl-β-D-cymarosyl-(1→3)-aglycone on the bases of ^<13>C-NMR technique and the analyses of the sugar fraction of the hydrolysate. Aglycones of 8 and 9 were identified as condurangogenin-A(14) and -C(22), respectively. Other four glycosides 10 to 13 were convertible to each other under proper conditions. Aglycone fractions from the hydrolysate of 10 to 13 afforded the same mixtures, which were hydrogenated to a compound 26. This compound was also obtained from 23, one of the aglycones by a catalytic hydrogenation. The structure of 26 was assigned by spectroscopy. These results lead to tentative structures of 10 to 13. Antitumor activities and LD_<50> of glycosides 8, 9, 10, and 12 were shown in the table V.
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Fumiko Abe, Tatsuo Yamauchi
Article type: Article
Session ID: 66
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Cardiac glycosides and sugar free cardenolides of Anodendron affine Druce (Apocynaceae) were isolated and the structure determined. As in affinoside B, of which the structure was already established by X-ray analysis, affinosides A, C, D, E, F and G, the glycosides in the stem (Group I) link 4,6-deoxy-3-O-methyl-D-xylo-2-hexosulose, forming dioxane ring between the 2α and 3β-hydroxyl group of the aglycones, and 2'-acetal and 1'-anomeric hydroxyls of the sugar, respectively. The aglycone of affinoside A, the main glycoside of the stem, was determined as 2α,3β,11α,14-tetrahydroxy-12-oxo-7,8β-epoxy-14β-carda-4,20(22)-dienolide. The glycosides in the leaves (Group II) were found to have 6-deoxy-3-O-methyl-hexosulose (L-1, L-2 and L-3) and 6-deoxy-hexosulose (L-4) as a component sugar. Free cardenolides (Group III) include 11-oxo-Δ^<16>-cardenolides with 2α,3β (D_g-1, aglycone of affinoside D), 2β,3β (D_g-2) and 2β,3α (D_g-3) glycol system, along with affinogenin C, 2α,3β,14-trihydroxy-11-oxo-5β,14β-cardenolide, the aglycone of affinosides C, L-2 and L-4. The cleavage of the oxide linkage between the aglycone and sugar moieties at C2 and C2' was conducted by NaBH_4 reduction. The product with usual glycoside linkage from L-2 was then hydrolyzed with 1%HCl in acetone to afford 2α,3β,11β,14-tetrahydroxy-cardenolide and 6-deoxy-3-O-methyl-hexose.
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Makoto Nishizawa, Takashi Yamagishi, Gen-ichiro Nonaka, Itsuo Nishioka ...
Article type: Article
Session ID: 67
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Gallotannins in six crude drugs (Galla Chinensis, Galla Halepensis, Paeoniae Radix, Moutan Cortex, Uvae Ursi Folium and Trapae Fructus) were isolated by a combination of Sephadex LH-20 column chromatography and high performance liquid chromatography(HPLC). The structures of gallotannins were determined mainly by ^1H-and ^<13>C-NMR spectroscopy as shown in Fig. 5. The gallotannins in Galla Chinensis, Paeoniae Radix and Moutan Cortex have a 1,2,3,4,6-pentagalloylglucose(6) core and those of Galla Halepensis have a 1,2,3,6-tetragalloylglucose(5) core. The depside galloyl group of hexagalloylglcuose in Paeoniae Radix and Moutan Cortex is attached to C-6 position of glucose, but that of Galla Chinensis is randomly distributed among C-2, C-3 and C-4 positions. The ^<13>C-NMR spectra indicated that the depside galloyl group in gallotannins is linked not only with m- but also p-hydroxyl group of another galloyl group. The presence of gallotannins in 154 crude drugs was tested by HPLC; seven crude drugs, Nupharis Rhizoma, Pylolae Herba, Rosa Multiflorae Fructus, Euclypti Folium, Guava (Psidium guajava L.) and Kayuptih (Melaleuca leucadendron), were found to contain gallotannins. The gallotannins in Paeoniae Radix decreased blood urea nitrogen concentration in rat serum in vivo. Moreover, gallotannins inhibited the growth of certain bacteria and the respiration of rat liver mitochondria in vitro.
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T. Okuda, T. Yoshida, R. Fujii
Article type: Article
Session ID: 68
Published: September 10, 1980
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The structure of terchebin to which Ib was assigned previously in a literature, has been revised to VII, based on the data as follows. The PMR signals which were previously regarded as due to the protons at C_2, and C_3,, in Ib, are now assigned to those at C_1, and C_3, in VII, based on the analogy of these signals to those in geraniin. The CMR spectrum shows that the structure of the ester residue at O-2 and O-4 of glucose is analogous to that in geraniin, and therefore that Ib is excluded. The evidences of the stereostructure have been obtained by the analogy of the shifts in the PMR spectrum of III to those of the corresponding derivative of geraniin, and also by the optical property of VIII which was derived from III. The structure of terchebin is accordingly represented by VII. The structures of chebulinic acid and chebulagic acid, which were previously regarded as dicarboxylic acids, XI and XII^2, have been revised to monocarboxylactones, XIII and XIX, respectively, based on the following data. The DIS measurement of chebulinic acid and chebulagic acid showed dual peak for only one carboxyl carbon. The absence of DIS in the phenolic carbon, C_6,, indicates formation of a lactone between C_6,, and a carboxyl group in both of these tannins. The results of structural investigations of the methylated derivatives are also in agreement with structure XIII. An additional ellagitannin has been isolated from myrobalans, and identified as punicalagin.
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T. Okuno, S. Oikawa, T. Goto, M. Toda, K. Sawai, K. Sawamura, T. Matsu ...
Article type: Article
Session ID: 69
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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The metabolites of a phytopathogenic fungus, Valsa ceratosperma, which causes Japanese apple canker, have been studied. From the filtrate of an artificial cultivation of the fungus five isocoumarin derivatives (1 5) were isolated. The structure of these compounds was determined by the spectroscopic data and chemical conversion. 2 5 are new compounds. All the compounds may be classified to phytotoxic substance from the result of a bioassay experiment using detached apple shoots and showed the antifungal activity against Valsa ceratosperma. The screening of fungi with the activity was also carried out. The few compounds with potent anti-Valsa ceratosperma activity were isolated from the metabolites of some fungi. These are 6, 7, 8, and 9.
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Y. Takahashi, N. Miyasaka, S. Tasaka, M. Wada, I. Miura, S. Urano, T. ...
Article type: Article
Session ID: 70
Published: September 10, 1980
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The 400MHz nmr and other spectroscopic data of carthamin, the main red pigment of safflower, suggest that its chemical constitution is expressed by formula 1. However, the stereochemistry at C^* is still obscure at present. Similar spectroscopic studies of the yellow pigment Sp_2 imply that this compound is a monomeric chalcone with formula 2, where the configuration at C^* is not yet clear. Treatment of Sp_2 with acid cleaves the C-glucosidic linkage to give compound 6.
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Y. Oshima, C. Konno, H. Hikino, K. Matsushita
Article type: Article
Session ID: 71
Published: September 10, 1980
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From the Oriental medicine "sohakuhi", the root bark of Morus plants (Moraceae), novel isoprenoid flavone derivatives, moracenin A, B, C and D, having hypotensive activity were isolated. Moracenin B, C_<40>H_<36>O_<11>, [α]_D-466°, was subjected to spectral analysis to reveal the presence of a 5,7,2',4'-tetrahydroxy-3,8-disubstituted flavone moiety, a 2,4-dihydroxyphenyl group, a 2,4-dihydroxybenzoyl group and a 1-methylcyclohexene ring. The observation of ^<13>C-^1H spin couplings deduced the gross structure of moracenin B to be I. Moracenin A, C_<45>H_<44>O_<11>, [α]_D-427°, moracenin C, C_<45>H_<44>O_<11>, [α]_D-445°, and moracenin D, C_<40>H_<38>O_<12>, [α]_-388°, were similar in spectral properties to moracenin B, which, along with the fact that moracenin A, C and D coexist with moracenin B, indicated that moracenin A, C and D are congeners of moracenin B. Analysis of the spectra led to the conclusion that the gross structures of moracenin A, C and D are represented by formulas II, III and IV (except for stereochemistry). The relative stereostructures of the moracenins were established by the ^1H NMR evidence and the absolute stereostructures deduced by the CD evidence. The moracenins having unique skeletons appear to be biosynthesized from two units of chalcone and two or three isoprene units.
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T. Nomura, T. Fukai, Y. Momose, T. Narita
Article type: Article
Session ID: 72
Published: September 10, 1980
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Two hypotensive compounds, kuwanon G (I) and kuwanon H (II), have been isolated from the root bark of the mulberry tree (Morus alba L.). Intravenous injection of both compounds (0.1-3mg/Kg) caused almost equally a transient dose-dependent decrease in arterial blood pressure in anesthetized rabbit. Kuwanon G (I), amorphous powder, C_<40>H_<36>O_<11>, [α]_D^<22>=-534°. Detailed spectroscopic analyses of I and its derivatives as well as degradation experiment have informed of the presence of a condensed structure of 2,4,2',4'-tetfahydroxydihydrochalcon and kuwanon C (III). The structure of kuwanon G was presumed to be I or I'. The structure I is suggested to be more favorable than the structure I' by the comparison of the pmr spectrum of kuwanon G octadeuteromethyl ether (Ig) and that of alcohol (Ih) obtained by sodium borohydride reduction of Ig. Kuwanon H (II), amorphous powder, C_<45>H_<44>O_<11>, [α]_D^<22>=-536°. Detailed comparative analyses of the spectroscopic data of II with those of I and its derivatives have suggested that kuwanon H is represented by structure II.
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M. Takasugi, S. Nagao, S. Ishikawa, T. Masamune, A. Shirata, K. Takaha ...
Article type: Article
Session ID: 73
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Phytoalexins are antimicrobial compounds produced newly by plants in response to microbial infection, and their production, coupled with the presence of antimicrobial principles in healthy plants, is believed to be an importance disease resistance mechanism in higher plants. We already reported on many antifungal metabolites produced by cortex and phloem tissues and xylem tissues of diseased mulberry and contained in epidermis tissues of healthy mulberry. We describe herein the structure elucidation of three related antifungal compounds, designated as chalcomoracin and albanins F and G. Chalcomoracin (1), mp 185℃ (dec), and [α]_D +194°, was isolated from leaves infected with Fusarium solani f. sp. mori., and qualified as a phytoalexin, and had a molecular formula of C_<39>H_<36>O_9. Albanins F (2) and G (3), each amorphous and [α]_D-458° and -404°, were isolated from healthy epidermis tissues and had molecular formulas of C_<40>H_<36>O_<11> and C_<45>H_<44>O_<11>, respectively. The structures of these metabolites were determined as shown in the formulas on the basis of the spectral and chemical data, especially of the synthesis of model compounds (21 and 22). It is to be noted that these metabolites possess structures (planar structure and relative configuration) regarded biogenetically as Diels-Alder adducts of two "natural" components.
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S. Omura, C. Kitao, N. Sadakane, H. Matsubara, A. Nakagawa
Article type: Article
Session ID: 74
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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We have obtained a mutant strain No. 261 by the treatment of the tylosin (1) producing strain, Streptomyces fradiae KA-427, with nitrosoguanidine. The structures of protylonolide (3) and mycarosyl protylonolide (4) isolated from the culture broth of the mutant were elucidated by mass and nmr spectrometry and X-ray crystallography. The absolute configuration of 1 was deduced from the evidence that 3 is bioconverted to 1 and spectral identity of 1, 3 and leucomycin A_3 in which the absolute configuration was already established. Cofermentation and bioconversion studies indicated that mutant No. 261 is an idiotroph of mycaminose. Hybrid biosynthesis of tylosin-related compound was attempted using an antibiotic producer and cerulenin, an inhibitor of polyketide biosynthesis. The feeding of 3 to the fermentation broth of Streptomyces sp. AM-4900 producing picromycin, a 14-membered macrolide antibiotic, gave a product designated as 5-O-desosaminyl protylonolide (9) (=M-4365 G_1, 6). Consequently, it was found that the absolute configuration of M-4365 G_<1-3> (6, 7, 8) are identical with that of 1. Furthermore, in order to clarify the biosynthetic pathway after the lactone ring formation of 1, we attempted the syntheses of many tylosin-related compounds and examined the ability for the bioconversion of these compounds to 1 by Sm. fradiae in the presence of cerulenin. As a result, the preferred pathway from 3 to 1 are as follows: 1) addition of mycaminose to C_5-OH of 3; 2) oxidation of C_<20>-methyl to aldehyde and C_<23>-methyl to alcohol in undetermined order; 3) addition of mycinose to C_<23>-OH; 4) addition of mycarose to C_4'-OH. The biosynthetic relation of 1 and relomycin (2) is also discussed.
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K. Kakinuma, N. Imamura, N. Ikekawa, H. Tanaka, S. Minami, S. Omura
Article type: Article
Session ID: 75
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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The Structure of an antibacterial and antitumor antibiotic Setomimycin produced by Streptomyces pseudovenezuelae AM-2947, was determined to be a unique substituted 9,9'-bianthryl (1), first to be reported from Antinomycetes, by means of the various new ^<13>C-nmr techniques including ^<13>C-{^1H}-selective decoupling, ^<13>C-{^1H}-selective population transfer and ^<13>C-{^1H}-NOE experiments. Biosynthetic studies of the antibiotic were also carried out by labeling either with [1-^<13>C]-or [1,2-^<13>C_2]-sodium acetates. The labeling pattern was determined by the ^<13>C-^<13>C coupling constants with the aid of ^<13>C-{^<13>C}-homonuclear decoupling experiments, which allowed to verify the assigned structure of setomimycin and to elucidate that the antibiotic is derived from two nonaketide metabolites via decarboxylation at the terminals.
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M. Kasai, M. Yoshida, N. Hirayama, F. Tomita, T. Tamaoki, K. Shirahata ...
Article type: Article
Session ID: 76
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Tetrocarcins are new antitumor antibiotics produced by Micromonospora chalcea KY11091, and show marked activity against experimental tumors such as mouse sarcoma 180 and mouse leukemia P388. Acid hydrolysis of tetrocarcin A and B gave a novel aglycone (tetronolide, C_<32>H_<40>O_8), a new nitrosugar (tetronitrose, C_9H_<16>N_2O_6), L-amicetose and L-digitoxose. The structures of tetronolide and tetronitrose were confirmed by spectroscopic and X-ray crystallographic analyses except the absolute configuration. The structures of tetrocarcin A (C_<67>H_<96>N_2O_<24>) and B (C_<61>H_<86>N_2O_<22>) have been determined as depicted in (22) and (23), respectively, on the basis of the conversion of tetrocarcin A into B by incubation with intact cells and methanolysis of permethylated tetrocarcin A and permethylated deacetyldihydrotetrocarcin A giving methyl 4-O-methyl-L-amicetoside and methyl 3-O-methyl and 4-O-methyl-L-digitoxosides.
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M. Hayashi, M. Ohno, S. Katsumata, S. Satoi, M. Suzuki, K. I. Harada
Article type: Article
Session ID: 77
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Mycinamicins, a new group of basic 16-membered macrolide antibiotics, have been obtained from Micromonospora griseorubida sp. nov., and named as mycinamicin in I, II, III, IV and V, respectively. They were characterized as in Table 1 and were composed of an amino sugar, desosamine, and a neutral sugar, mycinose or javose. When mycinamicin IV and V were heated in 0.2 N-HCl (pH 2.0) at 90℃ for 4 days, new products were formed and purification of this products by silica gel chromatography afforded IX, X, XI and XII, XIII, XIV, respectively. The isolated aglycone moieties (IX and XII) were different from those of well known similar macrolide antibiotics, namely, magnamycin, tylosin, chalcomycin and juvenimicin A_2 types. In order to investigate the structural relationships of mycinamicin I and II to IV and V, we studied their de-epoxidation (CrCl_2 in N-H_2SO_4). Reaction products from I and II were completely identical with natural mycinamicin IV and V, in all respects. The ^<13>C-NMR spectra of mycinamicins also supported the structures I, II, III, IV and V.
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M. Namikoshi, K. Sasaki, M. Amano, Y. Koiso, S Iwasaki, S. Okuda, S. N ...
Article type: Article
Session ID: 78
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Azalomycin F-complex produced by Streptomyces hygroscopicus var. azalomyceticus exhibits a wide antibiotic activity and is efficacious against bacteria, yeast, fungi and protozoa. The structure of Azalomycin F4a, a main component of the F-complex, was studied. Azalomycin F4a (1) was obtained as microscopic needles from MeOH-H_2O, mp 131-132°(dec.), [α]_D +39°, UV λ^<EtOH>_<max>. nm ( log ε) ; 207 (4.11), 240 (4.58), 268 (4.36). Its molecular formula, C_<56>H_<95>O_<17>N_3 (M^+=1081), was determined from its spectroscopic and elemental analysis data. F4a (1) was subjected to a variety of chemical degradations to give a number of fragments. The chemical properties and spectroscopic data of 1 and the fragments allowed to elucidate the skeletal structure as shown in Fig. 1, particularly by the aid of extensive decoupling techniques on 400MHz ^1H- and 100MHz ^<13>C-NMR spectrometers and of field desorption mass spectrometry. Since ^<13>C-NMR spectrum of F4a showed no peak due to ketonic carbon but a hemiketal carbon peak, C(17) ketone group in 1 should be formed a hemiketal presumably with a hydroxy group at C(21). Azalomycin F4a was found to be a new 36-membered polyenic and polyhydroxy lactone which belongs biogenetically to a group of polyene macrolide antibiotics.
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K. Shirahata, M. Kono, I. Matsubara, M. Kasai
Article type: Article
Session ID: 79
Published: September 10, 1980
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Mitomycins (MM)(Fig. 1) were discovered first by Hata et al.in 1956 and by Wakaki et al.in 1958. MM-C has broad and highly potent antibacterial and anticancer activity but it also has strong toxicity as other anticancer agents have. Many chemical modification of MM have been tried to obtain their analogs with stronger activity or with less toxicity than the parent MM. As one of approaches to the goal, we have surveyed the broth of MM-C fermentation in detail and found that there are co-produced several minor components belonging to the family of MM. By a series of isolation procedure, nine natural MM were obtained. They were named as MM-D, E, F, G, I, J, K, L, and M in the order of isolation and their structures have been elucidated as shown in Fig. 2 and 4 by spectroscopic method and chemical transformation. MM-F is N-methyl MM-A. Six of them (MM-D, E, F, J, L, and M) were known compounds which had been already derived from the known MM although three of them (MM-E, J, and L) were believed to have the wrong structures depicted in Fig. 5. MM-G and K are new type of the class of mitomycins with exocyclic methylene. Their antibacterial and anticancer activity will be also discussed.
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N. Otake, T. Ogita, Y. Miyazaki, H. Yonehara, R. D. Macfarlane, C. J. ...
Article type: Article
Session ID: 80
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Structural elucidation of adenomycin(1), C_<25>H_<39>N_7O_<18>S, an antibiotic active against Mycobacteria, was undertaken by degradative (sheme 1) and spectroscopic studies. Spectral data of uv, ir and nmr revealed that 1 belongs to a new member of adenine nucleoside including two or three sugars and sulfate. Presence of a serine moiety in 1 was demonstrated by alkaline hydrolysis which afforded L-serine and deseryladenomycin(2). Identification of sugars in 1 was performed by acid hydrolysis or methanolysis of 2, which gave adenobiosamine(6)(isolated as its nonaacetate(5)), a disaccharide consisting of L-gulosamine and (-)-chiro-inositol, or methyl α and β adenotrioside(7a,7b), methylglycosides of trisaccharide consisting of 6 and D-ribose, respectively. Presence of ribose in 7a and 7b was elucidated by PRFT experiment of ^<13>C-nmr. Binding site of the ribose, sulfate and serine groups to the adenobiosamine moiety was established by the nmr analyses of NaBH_4 reduced products derived from 1 and 2, viz, adenotriitol (10), adenotriitol sulfate(8) and seryl adenotriitol sulfate(11) as well as periodate oxidation of 8.
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Takashi Tsuno, Masataka Konishi
Article type: Article
Session ID: 81
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Glysperin (Bu-2349) is a complex of basic, water-soluble antibiotics produced by a strain of Bacillus cereus. The antibiotic complex comprises three components, A (1a), B (1b) and C (1c). They showed potent antibacterial activity against gram-positive and gram-negative organisms, 1a being the major and most active component. The structures of 1a, 1b and 1c were determined on the basis of chemical degradation studies in conjugation with spectroscopic analyses. 1a (C_<44>H_<75>N_7O_<18>) was shown by acid hydrolysis to contain L-alanine, p-hydroxybenzoic acid, a C_<11>-alkyl tetramine and four sugar moieties. The structure of the C_<11>-amine was determined to be 1,13-diamino-4,9-diazatridecane (8), a new compound, whose structure was confirmed by synthesis. Three of the four sugar moieties were identified as D-ribose, D-galactose and 2,4-diamino-2,4,6-trideoxy-D-galactose. The fourth sugar moiety was a novel exoenohexose and its structure was established as 6-deoxy-D-xylo-hex-5-enose (9) based on the degradation studies performed after catalytic hydrogenation of 1a. The sequence of these structural units in 1a was elucidated by the spectroscopic studies on its partial degradation products. 1b (C_<40>H_<66>N_6O_<18>) was found to possess spermidine in place of 8 in 1a, while 1c (C_<44>H_<77>N_7O_<19>) contained D-glucose instead of 9 in 1a. Glysperins A, B and C are, in some respects, structurally related to the glycocinnamoylspermidine antibiotic LL-BM 123 which was produced by a strain of Nocardia species.
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K. Yokose, K. Ogawa, Y. Suzuki, Y. Suhara, P. Buchschacher
Article type: Article
Session ID: 82
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Trestatins A, B and C which were isolated from the culture filtrate of Streptomyces dimorphogenes NR-320-OM7HB are new amino-oligosaccharides possessing potent inhibitory activity against various α-amylases. Their structures have been determined by chemical degradation and spectral studies. Trestatins A (C_<56>H_<94>N_2O_<40>), B (C_<37>H_<63>NO_<28>) and C (C_<75>H_<125>N_3O_<52>) are water-soluble, basic substances of homologous nature. Upon acid hydrolysis, Trestatins A, B and C gave D-glucose and a tricyclic oxazolidine (1) derived from 3 in common. This finding coupled with titration, MW and PMR data revealed the components (Table 2) of each Trestatin. In order to determine the sequences, each Trestatin was subjected to mild acid hydrolysis which also gave D-glucose, trehalose, maltose, glucotriose (4) and glucotetraose (5) in common. The linkage between 3 and 5 was elucidated on the basis of T_1 data, which revealed the structure of Trestatin B. From the hydrolyzate of Trestatin A, basic fragments such as 13, 14, 15, 16, 17 and 18 were obtained. In case of Trestatin C, fragments 17 and 19 were obtained in addition to 13-16. Their structures were clarified mainly by PMR and CMR, which in turn led to revealing the structures of Trestatins A and C.
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Y. Fujimoto, H. Tsunoda, J. Uzawa, T. Tatsuno
Article type: Article
Session ID: 83
Published: September 10, 1980
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Two typical mycotoxins, luteoskyrin and cyclochlorotine have so far been isolated from the culture broth of Penicillium islandicum Sopp known as an infectant of yellowed rice. In this report, we describe the isolation and the structural elucidation of the new metabolites(named islandic acid-I and -II) which are the inhibitors of DNA synthesis on the transfection assay using Bacillus phage M_2, Bacillus subtilus 222 strain. The ^1H-nmr decoupling studies and the ^<13>C-nmr spectral analysis of islandic acid-I methyl ester[m/e 364, C_<18>H_<20>O_8] revealed the presence of the partial structures [A], [B], [C], [D], [E] and [F]. The order of the arrangement of the partial structures were determined by the application of long range selective proton decoupling and the structures of islandic acid-I and -II were confirmed as 1 and 2.
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K. Yakushijin, R. Suzuki, T. Tohshima, H. Murata, H. Furukawa, T. Naka ...
Article type: Article
Session ID: 84
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Phytoquinoids are known only few examples occurring in higher plants, and are of interest in exhibiting both antitumor and cytotoxic activities. We here report the isolation and structure elucidations of novel phytoquinoids and their analogues from leaves of Illicium tashiroi Maxim. (Japanese name, Yaeyama-shikimi, Illieiaceae) collected on Iriomote island. The structure of illicinone-A (13) have been determined on the basis of the results of spectral and chemical analyses. And the structures of illicinone-B, -C, and -D were assigned with formulae 14, 15, and 16, respectively, by the comparisons of PMR and CMR spectra with those of illicinone-A (13) and by the chemical correlations with illicinone-A. The absolute configurations of illicinones were elucidated by CD spectra of 20 and 21 derived from illicinone-A (13) by the treatments of NaBH_4, H^+, and Pd-C/H_2, successively. The structures of illifunone-A (22), -B (23), -C (24), and -D (25) were also proposed by spectral evidences. Furthermore, some biological activities of illicinones were discussed.
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T. Ando, M. H. Vu, K. Arai, N. Takahashi
Article type: Article
Session ID: 85
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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The application of the electroantennogram (EAG) technique suggested that the sex pheromone of the pine moth, Dendrolimus spectabilis Butler ( Lasiocampidae), one of the most harmful defoliators of the pine tree, is 5,7-dodecadien-1-ol. All the geometrical isomers of this compound were synthesized stereoselectively via acetylenic compounds. Analyses of the virgin female abdominal tip extracts with GC and GC-MS using above isomers as standard compounds showed the presence of (Z)-5,(E)-7-isomer and (E)-5,(E)-7-isomer in a ratio of ca. 5: 1. After the field tests it was concluded that (Z)-5,(E)-7-dodecadien-1-ol was the main component of the female pheromone. The experiments to clarify the role of the (E)-5,(E)-7-isomer are in progress. Similar experiments showed (E)-11,(Z)-13-hexadecadienal to be the sex pheromone of the cabbage webworm, Oebia nudalis Fabricius (Pyralidae), one of the pest insects of cruciferous crops. The successful determination of the diene sex pheromones of the two lepidopterous insects indicated usefullness of the EAG method especially for the study of diene sex pheromones. Namely, it is possible not only to monitor the activity of natural pheromones by EAG tests but also to determine double bond positions of diene pheromones by the measurement of EAG activities of seriated monoene isomers after examinations of functional group and carbon number of the pheromones. Then, double bond geometries of diene pheromones can be rather easily determined by chemical analyses of pheromone extracts and field trials with synthetic pure isomers, each of which can be prepared stereoselectively via acetylenic compouds.
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T. Okaichi, T. Tokumura
Article type: Article
Session ID: 86
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Recently the presences of the cyclo hexene compounds with strong absorption at 310-360nm in various marine organisms have been reported by Hirata et al., Tsujino et al. and others. The present authors also found the compounds in cell extracts of marine phytoflagellates including Noctiluca miliaris Suriray. The isolation of the compounds were achieved with gel filtration (Sephadex G 10) and ion exchange chromatography (DEAE Sephadex A 25, Hitachi custom 2616 and 2612) (Fig.1 and 2). Five compounds with absorption maxima at 298nm(compd. B), 310nm (A), 334 nm(C) and 337nm(D and E) were obtained. Compound C was confirmed to be identical with mytilin B or shinorine (II) by the Data of CMR, PMR and amino acid analysis. D and E (III and IV) were found to be new compounds of cis- and trans-isomers at carbon position 14. These compounds seem to be the intermediates on the biogenetic interrelationship between palythene and mytilin B or shinorine. We designate these compounds as cis-palythenic acid and trans-palythenic acid.
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Y. Hashimoto, K. Shudo, T. Okamoto
Article type: Article
Session ID: 87
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Mitomycin C, a potent antibiotic and clinically useful antitumor agent, was reductively activated and reacted with 5'-guanylic acid. The structure of the adduct was determined as cis-2,7-diamino-1-(5'-guanylyl) mitosene (4). Two potent mutagens, 3-amino-1-methyl-5H-pyrido[4,3-b]-indole (Trp-P-2), isolated from a tryptophan pyrolysate, and 2-amino-6-methyldipyrido[1,2-a: 3',2'-d]imidazole (Glu-P-1), isolated from a glutamic acid pyrolysate, modified DNA in the presence of rat liver microsomes. The major base modified with Trp-P-2 was identified with 3-(C^8-guanyl)amino-1-methyl-SH-pyrido[4,3-b]indole (9). The major base modified by Glu-P-1 was identified with 2-(C^8-guanyl)amino-6-methyldipyrido-[1,2-a: 3',2'-d]imidazole (14).
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H. Kasai, Z. Yamaizumi, K. Wakabayashi, M. Nagao, T. Sugimura, S. Yoko ...
Article type: Article
Session ID: 88
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Two potent mutagens (compound 1 and 2) on Salmonella typhimurium TA98 were isolated from a methanol extract of sardines broiled under normal domestic cooking conditions. The methanol extract of broiled sardines (10kg) was fractionated by acid-base partitioning, column chromatographies of Diaion HP-20,Sephadex LH-20 and silica-gel and the two pure mutagens (200μg each) were finally isolated by high pressure liquid chromatography using reverse phase column. The structures of compound 1 and 2 were determined as 2-amino-3-methyl-imidazo[4,5-f]quinoline (IQ) and 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (Me-IQ), respectively, based on 270MHz ^1H-NMR, mass and FTIR spectra, UV absorption, pK_a values, and chemical synthesis. IQ and Me-IQ were synthesized from 5,6-diamino-quinoline and 5,6-diamino-7-methylquinoline, respectively, by two step reactions. Synthetic IQ and Me-IQ showed strong mutagenic activities towards S. typhimurium TA98. These mutagens require metabolic activation by microsomal enzymes (S-9). Specific activities of these compounds towards TA98 and TA100 were determined to be 433,000 and 7,000 revertants/μg for IQ and 661,000 and 30,000 revertants/μg for Me-IQ. The mutagen IQ was also isolated from heated beef extract and hamburger, suggesting that these mutagens are commonly present in ordinary cooked foods. Carcinogenic tests are in progress for evaluation of these mutagens on humans.
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Article type: Index
Pages
687-692
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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Article type: Appendix
Pages
App4-
Published: September 10, 1980
Released on J-STAGE: August 18, 2017
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