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谷口 栄二, 陳 励志, 石崎 晴記, 前川 一之, 大島 康義
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Five new gmelinol-type lignans have been isolated from roots of Phryma leptostachya L.: leptostachyol acetate which is toxic, C_<26>H_<28>O_<12>, mp. 178°; epi-phrymarol, C_<23>H_<24>O_<10>, mp. 174°; iso-phrymarol acetate, amorph., C_<25>H_<26>O_<11>; phrymarolin-I, C_<24>H_<24>O_<11>, mp. 157°; phrymarolin-II, C_<23>H_<22>O_<10>, mp. 161°. This paper deals with evidence assigning the structures I-V for them. The tertiary monoalcohols (Ia, IIa, IIIa, lV, Va) have methylenedioxy(2) and aromatic methoxy(2,1,43,3), but no carbonyl. Hydrogenation of them with Pd-H_2 in EtOAc readily gave rise to dihydroglycols (If, IIc, IIIb, lVa, Vb) which consisted of a primary and tertiary hydroxy. The glycols gave 3-keto-tetrahydrofurans (Ig, IId, IIIc, lVb, Vc) together with HCHO, by NaIO_4 in wet MeOH-dioxane. These results strongly supported gmelinol-type structure of the alcohols. Ia and IIa were easily degradated by dil. HCl in MeOH to give 2-methoxysesamol and sesamol with two neutral compounds, C_<15>H_<18>O_7, mp.120°(Ic) and isomer, mp.150°(Id). By oxidation with KMnO_4 2-methoxypiperonylic acid was obtained from Ig, IId, lVb, Vc, and 2,6-dimethoxypiperonylic acid from IIIc, lVb and Vc. The chemical shift of methylene protons (H4, H8) showed equatorial configuration of the aryls. The stereochemistry of aroxyls in I and II was proposed to be axial by means of the low-field shift of the acetalic protons H2 by acetylating the hydroxyl on C1 (0.53 and 0.45ppm). In lV and V the position of two unequal aryls was effectively determined by mass spectrometry of lV, Va, lVb and Vc.
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宮内 哲子, 岡嶋 正枝
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The Pigment, spinochrome F, isolated from the spines of sea urchin HETEROCENTROTUS MAMILLATUS (Linne) (Paipu-uni in Japanese), was proved to be identical with spinochrome C (III), 2-acetyl-3,5,6,7,8-pentahydroxy-1,4-naphthoquinone, on the basis of the spectral data (IR, UV, NMR and Mass) and the results of elementary analyses. Besides spinochrome F, two kinds of pigments were obtained from the spines, and these were confirmed to be identical with spinochrome A (I), 2-acetyl-3,5,6,8-tetrahydroxy-1,4-naphthoquinone, and with spinochrome B, 2,3,5,7-tetrahydroxy-1,4-naphthoquinone, respectively by the spectral data and the analytical results.
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義平 邦利, 黒柳 正典, 手塚 美知子, 高橋 千加子, 名取 信策
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Thirteen naphthoquinone derivatives (1-13)(Table 2) have been isolated from the roots of Diospyros spp. and Maba buxifolia (Ebenaceae)(Table 3) and the structures of the compounds (1-4, 7-13) were determined. The linking positions of the two naphthoquinone units in isodiospyrin (11) was clarified by the determination of nuclear Overhauser effects. The structure of bisisodiospyrin (10), a novel tetrameric naphthoquinone, was elucidated from spectroscopic methods. The structure of shinanolone (3), a tetralone derivative, was established by the physical methods and the correlation with 7-methyljuglone (6). The absolute configurations of these compounds were also discussed.
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M. Tanabe, 瀬戸 治男, L. F. Johnson
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The use of ^<13>C-labeled substrates together with ^<13>C nmr spectroscopy simplifies biosynthetic studies of natural products since the ^<13>C isotopic excess incorporated at different sites can be located and identified by characteristic chemical shifts and an increased signal intensity over the natural abundance peaks. We report the application of the ^<13>C nmr method to the elucidation of the biosynthetic pathway of the microbial metabolite radicinin, which is produced by Stenphylium radicina. The ^<13>C nmr spectrum (Fig.1A) clearly indicates that six carbons of radicinin obtained from sodium acetate-2-^<13>C as precursor are derived from the methyl group of acetate, since only six peaks are evident and no peaks from carbon atoms at natural abundance are discernible. Spectrum (Fig.1B) also conclusively shows that the other six carbons of the labeled radicinin obatined from the sodium acetate-1-^<13>C are enriched at C_2, C_4, C_6, C_8, C_<10> and C_<13>, and must come from the carboxyl of acetate as indicated by the six peaks very evident from this ^<13>C enriched material. Our results confirm and fully support the polyacetate origin of radicinin with the expected alternating labeling of carbon atoms from either the methyl or carboxyl group of acetate. The polyacetate origin of fungal metabolites, sclerotiorin and citrinin was also confirmed with ^<13>C labeled precursors.
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五十嵐 喜九男, 本摩 恒利, 入沢 準二
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The same rather unstable product (III) was obtained when I or II was treated with silver perchlorate at 0° or -10℃ in an inert solvent such as anhydrous toluene, ether or liquid sulfur dioxide. Methanolysis of III gave a mixture of IV and V in good yield. The proportion of IV and V was varried with conditions used. Treatment of III with tetraethylammonium chloride gave a mixture of I and II in a ratio of 3.9 to 96.1 from which II was isolated in 75% yield. These results, the specific rotation value, and the nmr spectrum support that the structure of III is 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-α-D-glucopyranosyl perchlorate ester but not the corresponding ion. In analogy to the above results, the structure of VIII obtained from VI or VII and silver perchlorate is considered to be 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-α-D-mannopyranosyl perchlorate ester, methanolysis of which gave predominantly IX regardless the conditions used. Compound XII was obtained in the reaction of XI with silver perchlorate as expected. It is of interest to note the ratio of XV and XVI, obtained by the methanolysis of XII, was changed with solvent and conditions used. When liquid sulfur dioxide was used as the solvent, the anomerization of the product was so fast and XV was obtained in good yield. Treatment of XII with tetraethyl-ammonium chloride gave XVII in 59% yield. It is found that unstable β-D-glucopyranosyl chloride can be prepared from the corresponding α-D-glucopyranosyl halide via perchlorate ester in good yield.
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堀 哲雄, 前沢 功, 長浜 昇, 鈴木 真言
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An addition of 0.5% of sodium acetate to a basal medium (Table 1) retarded both the production of the antibiotics (Narbomycin and Picromycin complex) and the growth of Streptomyces venezuelae MCRL 0376 in the first stage (0〜2 days) of the cultivation, but the antibiotics biosynthesis was increased after 3 days up to 200% compared with the control with effecting the growth. These effects were observed only in the medium combined glucose and glycerol. A crystalline compound (mp 125-126°, C_<20>H_<32>O_5) named narbonolide (5) was isolated by the extraction with ethyl acetate from the fermentation beers in a basal medium added with 0.5% of sodium acetate, and determined to be the aglycone of narbomycin (1). The maximum accumulation of narbonolide (5) was observed at 2 days after the cultivation. The antibiotics biosynthesis was also stimulated by the addition of citric, succinic, α-ketoglutaric, fumalic, malic, pyruvic, malonic, and/or acetoacetic acid as was observed by that of acetic acid. Biosynthesis experiments were carried out using deuterium labeled compounds. Deuterioacetic acid (CD_3COOH, 99% D) was incorporated into narbonolide-d_n(n=0〜13, 17.5% of the protons are substituted by deuteriums, Table 2) when added to the fermentation medium of S. venezuelae MCRL 0376. When narbonolide-2d(7,95%) was added to the washed mycelium of S. narbonensis ISP 5016, it was converted to narbomycin-2d(8,25% D), and the latter(40% D) was also converted to picromycin-2d(9,13% D) when added to the washed mycelium of a picromycin-producing strain Streptomyces sp. MCRL 0405.
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坂上 良男, 植田 昭嘉
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An antibiotic, hondamycin (I), which showed the activity against the plant pathogenetic fungi including Piricularia oryzae in vitro, was produced from Streptomyces griseochromogenes var. albicus. The antibiotic was obtained as a hexagonal plate, mp.149-150(dec), from mycelia in culture. Hondamycin has C_<47>H_<78>O_<13> as the molecular formula. The maximums of the ultraviolet spectrum for (I) in methanol showed at 225mμ and 232.5mμ and, shoulders at 219mμ and 240mμ. Infra-red analysis indicated the presence of hydroxyl groups, lactone group and carbonyl group. Chemical studies showed that hondamycin have three carbon-carbon double bonds, three secondary hydroxyl groups, a conjugated lactone group, carbonyl groups, tirtiary hydroxyl groups and ten C-methyl groups as funitional groups, and the substance (I) consumed two moles of periodate to give about two moles of acetaldehyde and the acid (II). On oxidation of hondamycin (I) and the acid (II) with ozone there gave aldehyde (IV), C_<25>H_<50>O_7 and glyoxal. This aldehyde was changed to the polyol (VI), C_<25>H_<50>O_6. On oxidation of hondamycin with ozone there gave the polyol (V), C_<18>H_<38>O_8, too. Compound (V) and (VI) was oxidized with chromic acid and potassium permanganate. The antibiotic gave tiglicaldehyde on hydrolysis with methanolic sodium hydroxide. From the results of N.M.R. spectrums and chemical reactions for these partial structure of hondamycin it was understood the chemical structure of hondamycin as figure.
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田嶋 聖彦, 畑 辻明, 向山 光昭
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Attempts to prepare of oligonucleotides by means of Merrifield method have been investigated in several laboratories. But pure oligonucleotides have only been achieved by using of DEAE-cellulose column which is usual separating method in oligonucleotide synthesis. Because, the purity of oligonucleotides obtained by Merrifield method are depended on the yields of condensation reactions. Based on the above mentioned problem, a new method for the preparation of pure oligonucleotides was investigated in our laboratory. The principle of this method is shown in Fig 1. When a mixture of 2 and 3 was treated with TPS in dry pyridine, 5 was obtained along with 4. An ion exchange resin, having sulfonic acid group, was added to the mixture. Only a desired dinucleotide 5 was adsorbed in the resin. After washing the resin with water, 5 was eluted by means of aqueous solution of triethylamine and concentrated to dryness. The residue was treated with 80% of acetic acid for removal of N,N-dimethyl p-phenylenediamino group to affored 6. When the dinucleotide 6 was further allowed to react with 2 in the presence of TPS, 7 was obtained. After treatment with 80% of acetic acid, 8 was obtained as a pure sample. This method has two advantageous points, namely, (1) pure oligonucleotides can be prepared and confirmed in every separation step, (2) the oligonucleotides can be obtained on a relatively large scale without using of column chromatography.
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谷山 兵三, 沢田 洋介, 北川 常広
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Two antibiotics 476-A,B were isolated from filtered broth of Streptomyces No.476 strain. The 476-A was identified with emimycin (2-hydroxy pyr-azine 4-oxide). The 476-B was an antibiotic belongs to a basic, water-solble streptothricin group on its physico-chemical properties. Complete hydrolysis of 476-B gave streptolidine (V), N-methyl D-gulosamine (VI), sarcosine (VII), carbon dioxide, ammonia, and miner methylamine, and partial hydrolysis of it gave three inactive compounds of (II), (III) and (IV). A intresting fact was discovered that (II) was regenerated to (I) standing with DCC in pyridinium solution at room temperature for a week. N-guan.-streptolidyl, N-methyl- -D-gulosaminide (IV) was also isolated by D. B. Borders et al. from this group antibiotic LL-AC-541 and decided its structure. On hight resolution MASS spectra, streptolidine moiety and two formulas of C-10 units were decided. Therefore, the structure of new type streptothricin-like 476-B was presumed as (I) by us, and also identified with SF-701.
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野間 正名, 野口 正雄, 玉置 英之助
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During our studies of nitrogen metabolism in tobacco leaves, a new amino acid (1), C_<12>H_<23>N_3O_7, was isolated from green leaves of N. tabacum L. var. Hicks. In mass spectra of methyl and ethylesters, parent peaks were observed at m/e 345 and m/e 387 respectively, indicating that (1) has three carboxyl groups and exsists as a monohydrate. By deutero labeling method, it became clear that the methylester has three active hydrogen atoms. Neutral behaviours in column chromatography and paper eleatrophoresis suggested that the three nitrogen atoms in (1) are all basic. KMnO_4 oxidation of (1) afforded azetidine-2-carboxylic acid in addition to aspartic acid. In mass spectrum of the methylester, base peak, m/e 128(C_6H_<10>NO_2) and its fragmentation pattern confirmed the existence of azetidine-2-carboxylic acid in (1). In the U.V. spectrum of the DNP-derivative of (1), λ_<max> 360mμ and A_<390>mμ/A_<360>mμ=0.61 suggested that (1) has one NH_2 group. KMnO_4 oxidation of this compound yielded DNP-aspartic acid together with azetidine-2-carboxylic acid. In addition to these data, studies on n.m.d.r. and fragmentation pattern in the high resolution mass spectrum established the amino acid as (A).
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亀谷 哲治, 井原 正隆, 本多 利雄
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The structure of capaurimine, C_<20>H_<23>NO_5, mp 212°, [α]^<24>_D-287°(in chloroform), isolated from Corydalis species, was assigned as I from degradative evidence by Manske. Recently, one of the present authors, has synthesized I and XVII, but it has been found that natural capaurimine was different from our synthetic compounds (I) and (XVII). Therefore we undertook the reinvestigation of capaurimine, isolated from C. pallida var. tenuis Yatabe by us. From the i.r., n.m.r. and mass spectra of capaurimine and its deuterized compound, it was found that the most possible structure was II. This assignment was also confirmed by the reinvestigation of oxidation of O,O-diethylcapaurimine (XXI). Furthermore, on the basis of X-ray analyses of capaurimine mono-p-bromo-benzoate (XXXIII) and the hydrobromides of capaurine (IV) and XVII, it has been revealed clearly that capaurimine derivatives take a cis conformation preferably because of the non-bonded interaction between the oxygen at the 1-position and the hydrogens at 13-position.
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藤田 栄一, 佐伯 行一
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Seven new alkaloids, lythrancine-I〜IV and lythrancepine-I〜III, were isolated from Lythrum anceps Makino (Lythraceae). The i.r. and n.m.r. spectra of lythrancine-II, C_<29>H_<37>O_6N show the presence of a secondary acetoxy-, two aromatic methoxy- and two hydroxy-groups. Acetylation of lythrancine-II gave lythrancine-III, C_<31>H_<39>O_7N, and lythrancine-IV, C_<33>H_<41>O_8N, and alkaline hydrolysis of these three bases afforded lythrancine-I, C_<27>H_<35>O_5N. Both lythrancepine-II, C_<29>H_<37>O_5N, and lythrancepine-III, C_<31>H_<39>O_6N, on alkaline hydrolysis gave lythrancepine-I, C_<27>H_<35>O_4N. Lythrancine-III was converted into lythrancepine-I through its treatment with p-TsC1 in pyr. followed by LiAlH_4 reduction of the product. The foregoing chemical evidences show that these seven bases have the same skeleton. Treatment of lythrancine-II with phosgene readily gave 5-membered cyclic carbonate, which shows the presence of a cis-glycol in the molecule. One proton on each of two oxygenated carbons of the carbonate was recognized in the n.m.r. spectrum, thus, the original alcohols proved to be secondary. Lythrancine-II, on chromic acid oxidation, yielded 2,2'-dimethoxydipheny1-5,5'-dicarboxylic acid (IV), 4-methoxybenzene-1,3-dicarboxylic acid (V) and trans-6-carboxy-2-carboxymethylhexahydro-pyridine (VI), which were isolated as dimethyl esters. Jones' oxidation of lythrancine-III gave monoketone (XI), C_<31>H_<37>O_7N, and diketone (XII), C_<31>H_<35>O_8N. From the analysis of the n.m.r. spectrum of the latter (XII), structure (XIIa) was assigned to this compound. Then, the unique structures of seven natural bases were presented as shown in Chart 5.
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坂井 進一郎, 相見 則郎, 久保 陽徳, 北川 正之, 白鳥 雅子, 萩庭 丈寿
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Some time ago four kinds of new alkaloids were isolated from Gardneria nutans Sieb. et Zucc. (Loganiaceae) by us. The structures of three of them, i.e. gardnerine, gardnutine and hydroxygardnutine, were fully established and reported. The present paper deals with the structure elucidation of the last base gardneramine (I), C_<23>H_<28>N_2O_5, mp. 134-135, [α]_D=-287.7 (c=1.06, MeOH), to which the structural formula (I) has been deduced on the basis of the chemical and spectroscopic evidences. The iminoether ring of I can be cleaved by various reagents including HCOOH, AcOH, dil. HCl and CH_3I to give an oxindole derivative. (Chart 1). The revers reaction occurs when the oxindole with an adequate leaving group at C-22 (e.g. V or X) is treated with ethanolic KOH. Demethylgardneramine (XIII) derived from I was proved to be identical with Alkaloid G which had been isolated from G. multiflora Makino in our laboratory. Some efforts are under progress to determine the positions of the methoxyl groups on the benzene ring. Gardneramine is the first natural base with a masked oxindole system in its molecule.
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大橋 守, 森島 績, 岡田 耕治, 米沢 貞次郎, 西田 利昭
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Proton n.m.r. contact and pseudocontact shifts using nickel, cobalt, europium acetylacetonate have been applied to stereochemical problems of nicotine, tropanes, papaverine, cinchonine, cinchonidine and brucine. I) Chemical shifts and relative contact shifts for nicotine are shown in Fig. 1 and Table 1. A triplet signal at δ 3,11ppm shifted down and up-field on addition of Ni(AA)_2 and Co(AA)_2 respectively. This behavior is similar to that of the methyl's in β-picolins spectrum, thus the signal was assigned to C-2 hydrogen. Two structures, an envelop form (I) and a half chair form (II), are conceivable for the pyrrolidine ring of nicotine and the observed pseudo-contact shifts of triplet signal at δ 3.27 and the quartet signal at δ 2.34ppm made it possible to assign these signals to quasi-equatorial and -axial protons of I respectively. II) Scheme 1 summerizes the paramagnetic shifts for piperidines. The caluculated geometric factors, 3cos^2θ-1/r^3, of various conformers of piperidine are shown in scheme 2. The chemical shifts and the relative paramagnetic shifts for tropanes are summerized in Table 2. On the basis of these results the conformation of homatropine has been discussed. On addition of Co(AA)_2 the large downfield shifts of C-2 and C-4 equatorial protones and C-3 proton signals demonstrated that the conformation of the tropane ring must be in semi-planar form such as it is shown in Scheme 2(e). The paramagnetic shifts of proton n.m.r. of some quinoline, isoquinoline and indole alkaloids have been briefly discussed.
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大胡 惠明, 武内 征司, 吉村 寿次
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Catalytic asymmetric hydrogenation of benzil was examined by use of bis-dimethylglyoximato cobalt(II)-optically active amine complex. This system gave an extroadinarily high optical yield (50%) never seen before in the case of homogeneous metal complex-catalyzed asymmetric syntheses. The results were summarized as follows. a) Co(DMG)_2 complexes with optically active polyfunctional bases such as quinine, quinidine, cinchonidine, O-acetyl-quinine and brucine resulted in asymmetric hydrogenation, especially amino alcohols were highly effective. However, simple amine could not affect asymmetric induction. b) Increase in the molar ratio of substrate to cobalt or base does not bring about decrease in optical yield, but rather small increase. c) It is worthy to mention that molar equivalent of optically active base is enough to affect asymmetric induction. d) Asymmetric yield increased with increasing polarity of the solvent used. This asymmetric reaction is presumably due to an asymmetry induced on the bis-dimethylglyoxime ring by optically active axial base, provided that this reaction proceeds through the same mechanism as alkyl-Co(DMG)_2B formation from Co(DMG)_2B and olefines under hydrogen atmosphere.
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Th. Wieland, H. Faulstich, F. Fahrenholz, A. Fahrmeir
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The toxic mushroom Amanita phalloides contains 2 classes of lethal toxins, the phallotoxins and the amatoxins. Both of these are cyclic oligopeptides whose ring is divided into two moieties by a sulfur- or a sulfoxide bridge. In the phallotoxin series many chemical manipulations are possible at the periphery or in the centrum without loss of toxicity. A OH-group in γ-position of a side chain is not essential. Fission of only one of the 3 cross linkages, however, removes toxicity. There are some paralleles of ORD curves and toxicity demonstrating the strict dependence of biological action on molecular shape.-In the amatoxin series principally the same applies. Also here the intact shape of the rigid molecule is prerequisite of toxic effect but a OH group in γ-position of a side chain is essential. The amatoxins are strong inhibitory substances of a solubilized DNA dependent RNA polymerase of eukaryotic cells.
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B. Witkop, 徳山 孝, J. W. Daly, 清水 宏俊
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The batrachotoxins [see J. Am. Chem. Soc., 91, 3931 (1969)] are isolated not only from the Colombian arrow poison frog, Phyllobates aurotaenia, the kokoi of the Indians of the Choco Jungle of Western Colombia, but also from other Phyllobates species, such as P. vittatus and, presumably, P. lugubris. Roentgen-ray crystallo-graphic analysis by the symbolic addition procedure, J. and I. Karle, has not only furnished the stereo-structure of batrachotoxinin A O-p-bromobenzoate, but also the absolute configuration [Acta Crystallographica, B26, 440 (1970)]. The synthesis of 3-O-methyl-11,20-diacetyltetrahydrobatrachotoxinin A has been accomplished by H. Wehrli and W. Graf in the laboratory of O. Jeger, ETH, Zurich. A novel radioisotopic method for measuring the formation of cyclic AMP in brain slices [J. of Neurochemistry, 16, 1609 (1969)], has now shown batrachotoxin to be the most powerful stimulator known for the membrane-bound adenyl cyclase of brain [Proc. Nat. Acad. of Sciences, 65, 1033 (1970)], an effect which is potentiated by endogenous amines, such as norepinephrine and histamine. Species of the genus Dendrobates, such as pumilio and auratus from Panama, granuliferus from Costa Rica, leucomelus from Venezuela, minutus from Colombia, all contain Pumiliotoxin B, C_<19>H_<33>NO_3, LD_<50> 1.5mg/kg mouse in addition to other congeners, such as pumiliotoxin A, C, novel naturally occurring cis-decahydroquinoline derivative, as well as still unknown alkaloids. The Colombian frogs, Dendrobates histrionicus and truncatus contain novel C_<19>-bases, among them a ketone, while the active principles of D. parvulus from Ecuador represent still another group of amphibious venoms.
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山田 俊一, 大谷 元治
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The asymmetric synthesis of 4,4-disubstituted 2-cyclohexenone (V) by the alkylation of the aldehyde enamine (III), from disubstituted acetaldehyde (I) and L-proline pyrrolidide (II), with methyl vinyl ketone, was stutied. It was shown that every cyclohexenone (V) obtained was optically active and the absolute configuration could be determined. The method was successfully applied to the total synthesis of (+)-mesembrine. By this asymmetric synthesis with the aldehyde (Ih), was obtained (+)-cyclohexenone (VI), whose absolute configuration was clearly shown to structure (VI) by ORD. The transformation of the (+)-cyclohexenone (VI) to partially optically active (+)-mesembrine was proceeded easily with ethanolic hydrochloric acid in 70% yield. The repeated recrystallization of partially optically active (+)-mesembrine hydrochloride resulted to obtain the practically optically pure (+)-mesembrine hydrochloride. Thus obtained synthetic (+)-mesembrine has antipodal optical property compaired to the natural (-)-mesembrine. Since the absolute configuration of synthetic (+)-mesembrine is to be represented by the structure (VII), it leads to an assingment of the absolute configuration of natural mesembrine that is represented by the structure (VIII).
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尾中 忠正
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セッションID: 19
発行日: 1970/10/01
公開日: 2017/08/18
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It is curious that the question of "how to design the simplest synthesis of a given molecule" is hitherto much ignored in spite of its apparent gravity in organic synthetic chemistry. In this connection, the present authors have shown a simple methodology about the logic of synthesis which has been demonstrated by the two or three step synthesis of four different series of alkaloids having an interesting skeletal structure in these two years. This paper adds two more examples of the synthesis on these lines. (I) One step synthesis of halfordinol (2a) A comprehensive study of an imaginative bond disconnection of oxazole ring system aids the synthesis of halfordinol while a new one step synthesis of 2,5-disubstituted oxazole has also been developed through these consideration. Thus halfordinol (2a) is obtained in one step by the reaction of p-hydroxymandelonitril (3) with nicotinaldehyde in the presence of SOCl_2 and HCl. (II) Two step synthesis of dl-elaeocarpine (4) and dl-isoelaeocarpine (5) Upon the consideration of the hypothetical mechanism of reaction course, a new reductive condensation of dihydropyridines with salicylaldehydes is developed. Thus dihydroindolizinium salt 16 readily reacts with 6-methylsalicylaldehyde (17) in the presence of LiAlH_4 to give a reductive condensation product 18. Oxidation and cyclization of 18 by Jones' reagent completes the two step synthesis of dl-elaeocarpine (4) and dl-isoelaeocarpine (5).
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早川 芳宏, 中村 仁司, 青木 幸三, 鈴木 正昭, 山田 静之, 平田 義正
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セッションID: 20
発行日: 1970/10/01
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The result of synthetic studies on sesquiterpene alkaloids (dendrobine 1 and nobiline 2) obtained from Dendrobium nobile L. is presented. Starting from a tetralone 3, a conjugated cyclohexenone 12 was prepared, which was cyclized to give a tricyclic keto acid 13. A common intermediate for the synthesis of dendrobine 1 and nobiline 2, a bicyclic keto acid 18 was prepared by ozonization of the enol acetate 15 of the acid 13. In the carboxyl group of the compound 18 nitrogen function was introduced to afford derivatives such as 21, 24, and 26. Attempts were made to form the pyrrolidine ring (or pyrrolidone ring) of dendrobine 1 via tricyclic compounds (21, and 26) containing a piperidone ring.
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田中 雅, 飯島 郁夫, 宮崎 道彦
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セッションID: 21
発行日: 1970/10/01
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Total synthesis of dl-elaeocarpine (I) and dl-isoelaeocarpine (II), having the novel indolizidine skeleton, were accomplished. That is, reaction of the diazoketone (VIIIc) with pyrrole was found to afford the 2-pyrrolylmethyl ketone (IXc). Catalytic hydrogenation of IXc over platinum oxide in acetic acid gave the 2-pyrrolidylmethyl-ketone (XII), in which the carbonyl function was not reduced because of steric hindrance by the bulky ortho substituents. Addition of ethyl acrylate to XII furnished the aminoester (XIII), which was subjected to the Dieckmann condensation to give the diketoindolizidine (XIV). The compound (XIV) was derived to the chromone (XVII) via XV and XVI by the agency of boron tribromide, followed by treatment with boiling methanolic hydrogen chloride. Reduction of XVII with sodium borohydride gave two isomeric alcohol (XVIII) and (XIX). The former was oxidized with chromic trioxide to afford dl-isoelaeocargne, m.p. 75-76°, and the latter gave dl-elaeocarpine, m.p. 81-82°, by the same oxidation procedure. The infrared spectra (in chloroform) and Rf values on tlc of the synthetic products were identical with those of the natural products.
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入江 寛, 西谷 康宏, 杉田 稔, 上尾 庄次郎
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発行日: 1970/10/01
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The synthesis of dihydrolycorine, the sole hydrogenation product of lycorine, which is the main alkaloid of Lycoris radiata and a number of other species of the Amaryllidaceae, has been accomplished in the following way. Methanolysis of the anhydride (X) followed by the Friedel-Crafts cyclization with phosphorus pentachloride and stannic chloride gave the hydrofluorenone-ester (VIII) and the tetralone-ester (XIII). Reduction of the former (VIII) with lithium aluminum hydride gave the diol (XIV) which was re-oxidized with activated manganese dioxide to the keto-alcohol (XV). Schmidt reaction of (XV) with sodium azide in trichloroacetic acid and subsequent alkaline hydrolysis gave the hydroxy-lactam (XVI) along with a by-product of unknown structure. The hydroxy-lactam (XVI) was converted into the cyanolactam (XVIII) by tosylation followed by treatment with potassium cyanide. Acidic hydrolysis of (XVIII) gave the lactam-acid (IV), whose stereo-structure was comfirmed by its transformation into γ-lycorane (XIX). Treatment of (IV) with iodine and potassium iodide in aqueous sodium bicarbonate gave the iodo-lactone (XXII) which was easily converted into iodo-acetyl-imide (XXV) in acetic acid and acetic anhydride. Elimination of hydrogen iodide from (XXV) with lithium chloride in DMF yielded the olefine (XXVI) which was oxidized by m-chloroperbenzoic acid in chloroform to the epoxide (XXVII). Reduction of (XXVII) with a mixture of lithium aluminum hydride and zinc chloride in THF furnished (±)-dihydrolycorine which was identical with natural dihydrolycorine in the n.m.r. and mass spectra. Furthermore, the i.r. spectrum of the O-diacetyl derivative of this synthetic compound was superimposable on the spectrum of diacetyldihydrolycorine from natural sources.
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山本 景祚, 川崎 一郎, 左右田 隆, 金子 武夫
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1. The molecular skelton (XIV) of Dendrobine, an alkaloid of Dendrobium nobile Lind1. was synthesized starting from carvotanaceton (I) as shown in Fig 1,3. Carvotanaceton (I) was treated with butadiene to afford the addition product (II), which was converted to unsaturated aldehyde (IV) via diol (III). The compound (XIV) was obtained via (IV)→(VI)→(XIII). Its structure was deduced from the results of n.m.r., mass and infra-red spectra. 2. The potential intermediates for the synthesis of Dendrobine were prepared from the compounds (VI) and (XVIII). (a) The aminoalcohol (XVII) was derived from the above obtained compound (VI) by way of several steps as shown in Fig 4. (b) Isopropyl group was introduced to cis-1-hydroxy-8-methyl-hydrindanone-5 (XVIII) synthesized according the method of C.B.C. Boyce to give the compound (XX) and αβ-unsaturated ketone (XXVII) was obtained by allylic oxidation of the keto olefine (XXV). The intermediate contains carboxyl function (XXXV) was obtained by the hydrocyanation of the αβ-unsaturated ketone and following hydrolysis. Investigations for conversion of the intermediates (XVII) and (XXXVI) to Dendrobine are now in progress.
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井深 俊郎, 田中 圭, 犬伏 康夫
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発行日: 1970/10/01
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The total synthesis of (±)-hasubanonine (56) has now been accomplished as follows. The compound (36), the synthesis of which had been reported in a previous paper, was chosen as a starting material in a present synthesis. Ketalization, demethylation, acetylation, and deketalization of the compound (36) gave the compound (44). Oxidation of (44) with Pb(OAc)_4, followed by bromination with pyridine-hydrobromide perbromide afforded the compound (46). Rearrangement reaction of the compound (46) with NaOAc-AcOH gave the compound (47), the partial hydrolysis of which afforded the compound (48). Bromination of (48), followed by methylation gave the compound (50). Treatment of (50) with 5% H_2SO_4-H_2O-dimethoxyethane in a sealed tube at 150-155° for 24hr afforded the compound (51) in a 30% yield. Methylation of (51) with diazomethane afforded the compound (52) together with its structural isomer (53). Separation of the compound (52) and (53) was effected by fractional crystallization. The desired product (52) was proved to be identical with 16-oxo-hasubanonine (35) which was transformed from natural hasubanonine by oxidation with KMnO_4. On the other hand, LiAlH_4 reduction of 16-oxo-hasubanonine, followed by MnO_2 oxidation regenerated hasubanonine.
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伊東 椒, 谷田貝 光克, 遠藤 勝也, 植田 泰次
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セッションID: 25
発行日: 1970/10/01
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Reaction of tricyclic sesquiterpene hydrocarbon, thujopsene, with proton acids, silica gel and palladium charcoal was investigated in order to see the behavior of cyclopropyl-carbinyl cation formed. Many new products having extensively rearranged structures were isolated and their structures determined by physical and chemical methods. Considering the structure of reaction products, the course of rearrangements in these reactions was illustrated. The reaction of (1) with silica gel is more vigorous compared with the homogeneous acid catalyzed reaction, giving more terminal therefore stable products. The difference of the stereoselectivity between homogeneous (acid-catalyzed reaction) and heterogeneous reaction (reaction with silica gel) was also described. The dehydrogenation of (1) gave daucalene (30) and 4 new compounds, (31), (27), (29) and (28) in addition to (2), (3), (4) and (6). The compounds, (31), (27), (29) and (28) were further dehydrogenated. The existence of two reaction paths was disclosed between (19) and (30). The essential difference of reaction path between general acid and palladium-charcoal was discussed.
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ヒキノ ヒロシ, 今野 長八, 竹本 常松
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セッションID: 26
発行日: 1970/10/01
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Germacradiene derivatives are thought to be precursors of a number of bicarbocyclic sesquiterpenoids. It is considered that the transformation from the former to the latter is initiated mainly by epoxidation of a double bond followed by cyclization of the resultant epoxide, during which the first epoxidation process must be stereospecific since it is conducted by an enzyme. Our interests on the stereospecificity of the reaction caused us to examine the enzymatic epoxidation using sesquiterpenoids of Curcuma zedoaria. Zederone (III), a constituent, is considered to be biosynthesized from furanodienone or isofuranodienone, the other constituents, each of which has been shown to be the 1: 1 mixture of the conformer I or II and its enantiomeric one, respectively. After the deduction of the conformation and absolute configuration of zederone as III A by spectral evidence, it is evident that the oxidation enzyme of the plant attacks stereospecifically on one (I) of the two enantiomeric conformers of furanodienone to afford zederone. On the other hand, fermentation of germacrone (V), another constituent of C. zedoaria, with the microbe Cunninghamella blakesleeana was carried out to yield two monoepoxides and a diepoxide whose conformations and absolute configurations have been deduced as VI, VII and VIII on the basis of the spectral evidence. Therefore, it is concluded that the oxidation enzyme induced by the microbe also has an affinity for one (V) of the two enantiomeric conformers, similar to I, selectively.
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加藤 紀元, 小杉 紘史, 吉越 昭
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セッションID: 27
発行日: 1970/10/01
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Solvolytic rearrangement of some cis-decalin derivatives (3a, 3b and 30b) was examined. In equilibrium between steroidal and non-steroidal conformations the α-methyl group of these cis-decalin derivatives at C_4 was anticipated to contribute to predominant distribution of the former conformation, which is favorable for the rearrangement of these cis-decalins into hydroazulenes. The α-methyl group was introduced at the C_4-position of the acetoxy-octalone (4), as shown in Scheme 1, in the over-all yield of 78%. While the methylation product (10a) was hydrogenated on Pd-SrCO_3 to a mixture of the trans- and cis-decalones (11a and 12), in the ratio of 3: 1, the acetoxy-octalone (10b) exclusively afforded the corresponding cis-decalone (11b). The tosylate (3a) was solvolyzed in hot HOAc containing KOAc yielding a mixture of the hydroazulenic products (13 and 15) and the octalone (14) in the yield of 38 and 46%, respectively. The preparation of the tosylate (3b) and the mesylate (30b) are given in Scheme 3 and 4, respectively. Solvolysis of the tosylate (3b) under similar condition afforded (±)-bulnesol (1) and its isomer (25) in the ratio of 1: 1, and, on the other hand, the mesylate (30b) did (±)-kessane (2) (30% yield) and the bridged bicyclic product (32) (50% yield).
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山村 庄亮, 井口 正信, 西山 敦子, 丹羽 正武, 加藤 国基, 小山 英世, 平田 義正
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セッションID: 28
発行日: 1970/10/01
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We here describe the structures of four monocyclic sesquiterpenes [Shyobunone (I), Epishyobunine (II), Isoshyobunone (III) and Preisocalamendiol (XII)] as well as two cadinane-type compounds [Calameone (XX) and Isocalamendiol (XXI)], all of which have been isolated from Acorus calamus L. Especially, shyobunone (I), which has been synthesized from 1-santonin, has been converted into other sesquiterpenes [(II), (III), (XII), (XX) and (XXI)]. Finally, the biogenesis of these sesquiterpenes and some biogenetic model reactions have been discussed.
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林 耀堂, 鄭 玉瑕, 郭 悦雄
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セッションID: 29
発行日: 1970/10/01
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The wood constituents of Taiwania cryptomerioides Hayata, indigenous to Taiwan, was found to be rich in sesquiterpene alcohols by K. Kafuku and R. Kato. We reinvestigated the neutral portion of the steam volatile from acetone extract of the wood and were able to isolate eight sesquiterpenes and fifteen sesquiterpene alcohols. These sesquiterpenes were identified as α-cedrene, β-cedrene, γ-cadinene, calamenene, α-cadacorene, cadaleme, α-muurolene, and γ-munrolene. Eleven of the fifteen sesquiterpene alcohols have been identified as α-cadinol, δ-cadinol, T-cadinol, T-muurolol, cedrol, epi-cubenol, cadinan-3-en-9α-ol-2-one, muurolan-3-en-9β-ol-2-one, muurolan-2α-, 9β-diol-3-ene, muurolan-2β, 9β-diol-3-ene, and cadinan-3α, 4α 9α-triol. Two additional saturated sesquiterpene diols, one (XVII) from n-hexane extractive and the other (XVIII) from acetone extractive of the woods were obtainted more recently. The structure of these two diols (XVII, XVIII) as well as the newly revised structure of ζ-cadinol (VII) have been elucidated by conventional chemical and spectroscopic methods.
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沖川 正善, 河野 信助
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セッションID: 30
発行日: 1970/10/01
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The structure (III) including absolute configuration was proposed for pseudoanisatin, C_<15>H_<22>O_6, a sesquiterpene lactone component obtained from the fruits of Illicium anisatum Linn. (Magnoliaceae) on the basis of the following evidences. a) Pseudoanisatin gave a triacetate (IV) and a ketone (V) on periodate oxidation. V was reduced to XI by sodium borohydride reduction. b) A translactonization product (VII) was obtaind by treating with sodium methoxide in methanol solution. VII gave IX on Jones oxidation. X was obtained from VII with thionyl chloride. c) The IR, MS and NMR (including NMDR and NOE) spectra of these compounds were all compatible with these structures. d) The molecular rotation difference between V and its 3-monobenzoate was estimated as +85°, showing S-configuration at C-3.
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William G. Dauben, Edward I. Aoyagi
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セッションID: 31
発行日: 1970/10/01
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Treatment of the tricyclic sequiterpene thujopsene (1) with mild acid (0.02M HClO_4 in refluxing 80% aqueous dioxane) gives widdrol (2) as the initial product. Similar treatment of the trans-thujopsene (4) yields epi-widdrol (5) as the initial product. The prolonged heating of the reaction mixture results in the formation of the diene 3 from thujopsene and the diene 6 from the trans-thujopsene. These results indicate that under the mildly acidic conditions, stereochemical integrity of the cyclopropylcarbinyl system is preserved. However, under the strongly acidic conditions, namely 0.02M HClO_4 in refluxing acetic acid, both cis thujopsene and the diene 6 yield a mixture of three hydrocarbons 9, 10 and 11. The structure of the major hydrocarbon 9 was reported previously. The structures of the two minor compounds 10 and 11 are reported here.
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坂田 完三, 河津 一儀, 三井 哲夫
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セッションID: 32
発行日: 1970/10/01
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A piscicidal constituent was isolated from the milky sap of Hura crepitans, and named huratoxin. Huratoxin (I), resinous matter, [α]^<28°>_D+55.1°, TLm (24h.) to Oryzias laptipes 0.0014ppm, absorbed three molar equivalents of hydrogen to give hexa-hydrohuratoxin (II). Diacetates (III) and (IV) were obtained from I and II, respectively. From the spectral analysis of I, II, III and IV it is suggested that I contains an isopropenyl, a secondary methyl, a primary hydroxyl, a secondary hydroxyl, a tertiary hydroxyl and partial structure (c). The spectral data of triacetate (VI) of the octahydro-derivative (V) and lithium-ammonia reduction product (VII) of IV indicated partial structure (d) in I. Periodic acid oxidation of V afforded an α-methyl-α,β-unsaturated aldehyde ketone (VIII). This suggests that partial structure (d) can be expanded to (e). Formation of bromohydrins (IX) and (X) suggests partial structure (f). Ozonolysis of III with two molar equivalents of ozone gave formaldehyde, n-decanal and a keto-enal (XI). The M^+ peak in the high resolution mass spectrum of XI assigned C_<27>H_<30>O_<12> to XI, accordingly C_<34>H_<48>O_8 to I. Hydrolysis of IV afforded myristic acid. This expands partial structure (c) to (g), and shows that the C_<14>-straight chain is bonded through oxygen to the C_<20>-moiety. Thus partial structures shown in Fig.3 were derived.
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佐藤 藹也, 倉林 正明, 永堀 均, 小木曽 彰, 三島 洋
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セッションID: 33
発行日: 1970/10/01
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'Chettaphangkhi' is an indigenous drug applied for stmachics in Thailand and is obtained from the roots of Adenochlaena siamensis Ridl. From a methylene chloride extract, we have isolated three crystalline furanoditerpenoids, chettaphanin-I (1), chettaphanin-II (2) and anhydrochettaphanin-I (3) by column chromatography. The structures of these natural products were determined by spectroscopic analyses and chemical reactions. These compounds are members of rearranged labdane, and 2 is the novel furanoditerpene having a hydroacenaphthene skeleton. The structural relationship between 1 and 3 was provided by means of an acid catalyzed dehydration of 1. The structure of 2 was suggested by the fact that treatment of 1 with Zn-AcOH afforded 2, which was also derived from 3 by aldol condensation and hydrogenation, Intermediate (11) obtained in the alternate course for conversion of 1 to 2, was derived to a ketone (16) supporting the hydroacenaphthene skeleton of chettaphanin-II. The stereochemistry of these compounds is under investigation by X-ray analysis.
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安江 政一, 榊原 仁作, 加藤 武, 高部 誠一
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Lyoniol-A (I) contains one acetoxyl group, four hydroxyl groups and an ethereal oxygen atom. Alkaline hydrolysis of lyoniol-A afforded deacetyl derivative, lyoniol-B (II). Lyonibl-B consumed one mole of sodium periodate, but lyoniol-A did not. Thus, the acetoxyl group must be located vicinal to a hydroxyl group. Oxidation of lyoniol-A with chromic acid gave a monoketone (V). Reduction of lyoniol-A with LiAlH_4 yielded dihydrolyoniol-B, a hexahydric alcohol (VII). This result suggested that the ethereal oxygen atom converted into a hydroxyl group and the cyclic ether must be an epoxide. Dihydrolyoniol-B was treated with p-tolu-enesulfonic acid in acetone to yield a monoacetonide (IX) and two monoanhydromonoacetonide (X) and (XI). The compound (X) gave a cyclopentanone derivative (XII) with chromic acid oxidation. Thus, the epoxide ring must be situated in the cyclopentane ring. The structure of lyoniol-A was suggested to be (I) from above results and by the analogy of grayanotoxin-I and rhodojaponin-II. The A,B-ring juncture was proved as trans by ORD measurement of 10-ketocompound derived from lyoniol-A. The cis and trans configuration of 3-ketocompound show a small difference in their octant frameworks (fig. 3). But 10-ketocompounds show a remarkable difference between their cis and trans configuration (fig. 4). The cis form is predicted to have slightly positive Cotton effect and the trans form negative. The observed ORD curve of 10-keto-compound derived from lyoniol-A (fig. 5) and grayanotoxin-II (fig. 6) have typical negative Cotton effects. Thus, the A,B-ring juncture of lyoniol-A and grayanotoxin-II must be trans.
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村江 達士, 池田 徹, 露木 孝彦, 西浜 忠明, 高橋 武美
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セッションID: 35
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In addition to the previously reported nigakilactone A(I), B(II), C(III) and D(IV, quassin), eight bitter principles (nigaki-lactones E(V), F(VI), G(VII), H(VIII), I(XI) and nigakihemiacetals A(IX), B(X), C(XII)) have been isolated from Picrasma ailanthoides Planchon (=P. quassioides Bennett). Recently, isolation of picrasin A and B from the same plant has been recorded by Takamoto et al. Nigakilactone F(VI) was obtained by the alkaline hydrolysis of nigakilactone E(V). On oxidation with Na_2Cr_2O_7, VI yielded a ketone(XIII), which was then converted to quassin(IV). On oxidation with Na_2Cr_2O_7 nigakilactone H(VIII) afforded a ketone(XIV). Oxidation of nigakihemiacetals A(IX), B(X) and C(XII) with Ag_2O yielded VI, IV and I, respectively. From these facts, along with their spectral data, the structures V, VI, VIII, IX, X and XII are given for nigakilactones E, F, H and nigakihemiacetals A, B and C, respectively. Nigakilactone G(VII) was shown to be identical with picrasin A. Spectral data of nigakilactone I(XI) suggest that this substance would be identical with picrasin B.
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加藤 忠弘, 種村 満, 菅野 亟, クマニレン A. S., 北原 喜男
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セッションID: 36
発行日: 1970/10/01
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1. Synthesis of Levantenolides Levantenolides(1,2), isolated from Turkish tobacco, are closely related to labdanolic acid having tetracyclic ring system. Based on an assumption that a biogenesis of 1, 2 would involve cyclization of hypothetical keto-acid(5), presumed to arise in nature by oxidation at C-1 and 4 positions of geranylgeraniol(4), biogenetic type reaction involving the cyclization of its equivalents (6, 7) were carried out. 1) Synthesis and Cyclization of 6 Monocyclofarnesol(8) was converted to bromo-derivative(9), which was treated with 2,2'-di-3-methylfurylmercury to afford the addition product(10). Photooxidation of 10 and subsequent treatment of a mixture of the oxidized products (6, 11, 11) with CrO_3・Pr afforded the intermediate 6 in 60% yield. Cyclizations of 6 were carried out by treatment with SnCl_4 to give 1(30%), 2(12%) and 13(25 %), respectively. ii) Synthesis and Cyclization of 7 The intermediate 7 was synthesized from 14 by the similar sequence of reactions described in section i. 7 gave 1(16%) and 2(6%) by treatment with SnCl_4. iii) Synthetic Approach to the minor Component 3 18, obtained by LAH reduction of 1, gave 3(not isolated) and 19(20%) by contact upon SnCl_4. 2. Syntheses of Cinnamolide and Polygodial Syntheses of 27 and 33 were tried based on the sequence of reactions described in scheme-1.
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田中 治, 三橋 進, 柳沢 勲, 二階堂 保
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セッションID: 37
発行日: 1970/10/01
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Isolation and structural determination of the diterpenes (I, II, IV, V, VI, VII, VIII and IX) of Aralia cordata and A. racemosa have been reported. During the course of the study, we have encountered that some of the axial aldehyde at C-4(IX, XIII and XVI) were quite unstable especially in solution and were rapidly autoxidized on standing at room temperature by neither irradiation nor addition of radical initiators. The structure of the degradation products(IX→I and X; XIII→II, XIV and XV; XVI→XVII, XVIII, XIX, XX and XXI) and the reaction sequence in each case were elucidated. The structural dependence and the mechanism of this reaction were discussed. (c.f. Chart 1) The present finding would be significant in relation to the studies on biosynthesis and chemical synthesis of the 4-hydroxy-18(or 19)-norditerpenes such as XXXVIII, XXXIX, XL, XLI, XLII and XLIII which have been recently found in plants.
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染井 正徳, 岡本 敏彦
原稿種別: 本文
セッションID: 38
発行日: 1970/10/01
公開日: 2017/08/18
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We have attempted the synthesis of Aconit-Alkaloids and Gibberellins from Enmein (1). The most important point is how to functionalize the non-activated C_<19>-methyl group of Enmein. We have many methods for attacking non-activated C-H bond, our trials by these methods did not success, for example, the photolysis of acylazide(2), etc. On our hypothesis that the C_<19>-methyl shoud be attacked by the photolysis of some nitrone, we finally irradiated the nitrone (18), which had been derived from Enmein. The nitrone(18) afforded the expected product (20), formed by attack on the C_<19>-methyl, and another compound (21). Yields of (20) and (21) under various conditions were examined and the results were explained by some possible mechanisms, a) and b). We propose the photolysis of nitrone as a novel method for attacking non-activated C-H bond. The compound (20) was isomerized to imine (27). The ring system of (27) was converted to Gibbane-skeleton treated with HNO_2. Immediate oxidation of the products mixture afforded the compounds (29) and (30). The compounds (29) and (30) were reduced, mesylated and demesylated to give the products (35) and (36), which were refluxed with KOH in abs. D.E.G to afford iso-GA_<15> (38) and GA_<15> (39). The compound (39) was identical with natural Gibberellin A_<15> in every respects.
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永田 亘, 若林 利生, 成定 昌幸, 早瀬 善男, 鎌田 進
原稿種別: 本文
セッションID: 39
発行日: 1970/10/01
公開日: 2017/08/18
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Starting from the tetracyclic enone 1, the key intermediate for our total synthesis of diterpene alkaloids, we have succeeded in the first stereo-controlled total synthesis of dl-gibberellin A_<15> (dl-GA_<15>). A general synthetic plan which we envisaged for the total synthesis of dl-GA_<15> is presented. Difficulties and conspicuous features encountered in carrying out this plan are discussed in terms of the following; (1) B-ring contraction, (2) hydrocyanation, (3) two-carbon homologation, (4) selective ozonization, (5) a new cyclization, (6) selective alkylation, and (7) demethylation.
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森 謙治, 中原 義昭, 松井 正直, 住木 諭介
原稿種別: 本文
セッションID: 40
発行日: 1970/10/01
公開日: 2017/08/18
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A New method was developed for the construction of a bioyolo [3.2.1] octane ring system with a bridgehead hydroxyl group (10→11→12). This reductive rearrangement (13→14 ; 41→43) was employed in the key step in the total synthesis of (±)-epiallogibberie acid (1) as well as in that of (±)-steviol (2). The conversion of steviol (2) into erythroxydiol A (3) was accomplished by using another interesting skeletal rearrangement (44→45) in the key step.
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野副 重男, 鈴木 和夫, 鈴木 伸幸
原稿種別: 本文
セッションID: 41
発行日: 1970/10/01
公開日: 2017/08/18
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Trans-γ-monocyclofarnesol (VI) was found to be formed by the incubation of mevalonio acid lactone with the soluble enzyme preparations from the mycelia of Helminthosporium siccans, which was known to produce an antibiotic, siccanin (I). 4,8,14-^<14>C-farnesyl pyrophospahte (XI) was also shown to convert to VI by the same incubation condition. In the presence of the joint substrate, orsellinic acid, the product of the enzymic reaction was found to be siccanochromene-A (III). Divaricatinic acid, oroinol, resorcinol, and resorcylic acid did not act as a substrate of this enzymic reaction. Tritium labelled siccanochromenic acid (III), siccanochromea-A (IV), and siccanochromene-B (V) were effectively incorporated into siccanin (I) by the incubation with the intact growing cell systems of H. siccans.
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井上 博之, 上田 伸一, 井上 謙一郎, 武田 美雄
原稿種別: 本文
セッションID: 42
発行日: 1970/10/01
公開日: 2017/08/18
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The oxidative sequences shown in Scheme 1 were established by the incorporation of [10-^3H]-10-deoxygeniposidic acid (12) and [10-^3H]-geniposide (6) into asperuloside (8) in Daphniphyllum macropodum, [10^3H]-scandoside (9) into gardenoside (7) in Gardenia jasminoides and [10-^3H]-(6) into theviridoside (13) in Cerbera manghas. The results of the last experiment biosynthetically established the structure (13) of the glucoside proposed by Schmid. The incorporation of [10-^3H]-(9) into aucubin (10) in Aucuba japonica and [10-^3H]-(10) into catalposide (17) in Catalpa ovata was also established. Two mechanisms have been proposed for the cyclopentane ring cleavage of loganin (1) into the secoiridoid glucoside. One is the pathway via 10-oxyloganin (28) and the other is that through the Baeyer-Villiger type oxidation of 7-ketologanin (23) into 8-epikingiside (24). [7-^3H]-(1) was incorporated into morroniside (20) in Gentiana Thunbergii. [10-^3H]-7-Deoxyloganic acid (4), [10-^3H]-(1), [8-^3H]-(24), and [8-^3H]-kingiside (19) were all incorporated into jasminin (22) in Jasminum primulinum while [10-^<14>C]-sweroside (2) was not incorporated into the glucoside (22).
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井口 和男, 柿沢 寛
原稿種別: 本文
セッションID: 43
発行日: 1970/10/01
公開日: 2017/08/18
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For the synthesis of fernane-type triterpenes, a ketoacetate (VIIIa), prepared from α-onocerin diacetate, was treated with hydriodic acid-acetic acid. The reaction accompanied with epimerization at asymmetric center C_<18> and afforded an αβ-unsaturated ketone(XVI). The reaction seemed to proceed with two steps and the intermediate (XXI) should be epimerized to (XV). A diene (XXIIa), which also derived from α-onocerin acetate, was refluxed with activated Fuller's earth in xylene to afford fernadiene (XXIII). The diene was converted into 8-fernene by reduction with lithium-ethylamine. Thus the total synthesis of ferna-7,9(11)-diene and 8-fernene has been accomplished.
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菊池 徹, 高山 雅治, 小山 峰雄, 有本 昌弘
原稿種別: 本文
セッションID: 44
発行日: 1970/10/01
公開日: 2017/08/18
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Pachysandiol-B (IIa) and pachysonol (IIIa) are new triterpenes isolated from Pachysandra terminalis SIEB. et ZUCC. and their interrelationship was indicated by the partial acetylation of IIa followed by CrO_3 oxidation, yielding pachysonol acetate (IIIb). The ORD curve and the bromination experiments of IIIb suggested that the compounds (IIa, IIIa) are the members of friedelin series. This was proved by the reaction of IIIa with mesyl chloride, which gave mainly a rearranged product (tentatively assigned to XI) and a small amount of anhydro compound (XII). The latter, on hydrogenation, afforded a saturated ketone whose IR spectrum (KBr) was almost superimposable upon that of friedelin. Additional evidence was provided by the acid induced rearrangement of an unsaturated ketone (X) derived from IIa (IIa→VI→VIIIa→X). The major product was found to be XIV on the basis of chemical and spectral evidences. Therefore the structure of pachysandiol-B and pachysonol are assigned to IIa and IIIa, respectively. The configuration of the 16-hydroxyl group is now under investigation. The triol (XVIa) is a minor triterpene which was characterized as its triacetate (XVIb) and diacetate (XVIc). The CrO_3 oxidation of XVIc gave a keto-diacetate (XVII), which on alkali treatment afforded a diosphenol (XVIII) and on alumina chromatography isomerized easily to give XIX. The Wolff-Kishner reduction of both XVII and XIX followed by acetylation gave rise to a saturated acetate (IXb) which was identified with IXb obtained from IIIb. Thus the structure of the triol is assigned to XVIa.
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津田 喜典, 礒部 公明, 佐野 武弘, 藤本 琢憲, 遠藤 雅子
原稿種別: 本文
セッションID: 45
発行日: 1970/10/01
公開日: 2017/08/18
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In addition to 16 known triterpenoids, eight new compounds were isolated from various Lycopodium plants, and their structures were established by spectroscopic evidence and by chemical correlation with the known specimens. For the latter purpose, two new methods-acetonide formation under forced condition and degradation of monosulphonate-played important role (see text). Thus, lycoplanatol (isolated from L. complanatum, L. annatinum, and L. alpinum(?)), epilycoplanatol (isolated from L. clavatum), and lycocryptol (isolated from L. cryptomerium) were shown to be serrat-14-en-3β,21β,24,30-tetraol(1), serrat-14-en-3α,21β,24,30-tetraol(2), and serrat-14-en-3β,21α,24,30-tetraol(3), respectively. New triterpenoid-acids, lycernuic acid-A and -B (both isolated from L. cernuum) were settled to be 3β,21β-dihydroxyserrat-14-en-24-oic acid(4) and 3β,21β,30-trihydroxyserrat-14-en-24-oic acid(5) respectively. Minor triterpenoids of L. clavatum, lyclaninol and lyclanitin (isolated also from L. complanatum) were proved to be serrat-14-en-3α,20β,21β,24-tetraol(6) and serrat-14-en-3α,20β,21β,24,30-pentaol(7) respectively. The most highly oxygenated specimen, 16-oxolyclanitin (isolated from L. clavatum) was shown to be 16-oxoserrat-14-en-3α,20β,21β,24, 30-pentaol(8) (hydroxy lycoclavanin).
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