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Volume 24, Issue 6
Displaying 1-50 of 54 articles from this issue
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TOSHIMICHI TSUBOI, BUICHI FUJITANI, KAZUKO TAKENO, KOUICHI YOSHIDA, MA ...1976 Volume 24 Issue 6 Pages 1123-1127
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEffect of biotin on biochemical changes following isoproterenol-induced myocardial infarction in rats was investigated. Biotin inhibited an increase of myocardial water content, an elevation of plasma lactate dehydrogenase activity and a decrease of myocardial adenosine triphosphate (ATP) level in isoproterenol-treated rats. Prednisolone enhanced the inhibitory effects of biotin on myocardial water content and plasma lactate dehydrogenase activity, but did not influence on myocardial ATP level. A possible mechanism of the inhibition by biotin is discussed.View full abstractDownload PDF (607K) -
HARUNORI YASUO, NAOTO YONEDA1976 Volume 24 Issue 6 Pages 1128-1132
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAminomethylation of O-benzoylthiamine disulfide (VI) with chloromethyldialkylamine (VIII), methylenebisdialkylamine (IX) and ethyl piperidinomethyl ether (Xb) was carried out to afford the corresponding N-aminomethylated compounds (XI). The reaction of thiamine disulfide (VII) with VIII or Mannich reaction of VII by the use of 37% formalin and piperidine gave N-aminomethylated compound (XIIb) without formation of the N, O-substituted compound which was reacted with both NH2 and OH groups. Cyclobismethylenethiamine (II) was obtained by the treatment of XIIb with mercaptoethanol. The results supported that II would be formed through N-aminomethylthiamine (V).View full abstractDownload PDF (687K) -
KAYOKO FUKUDA, AKIRA HAMADA1976 Volume 24 Issue 6 Pages 1133-1136
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe results of periodate oxidation, Smith-type degradation and methylation studies showed that the purified neutral polysaccharide from Lampteromyces japonicus (the component sugars ; D-Man ; 46%, D-Glc ; 30%, D-Gal ; 24%) contained mainly 1, 6- and 1, 2-linked mannopyranosyl residues, 1, 3-linked glucopyranosyl residues and minorly 1, 6-linked galactopyranosyl residues, and this glycan was branching mainly at C-3, 6 position of glucose residues.View full abstractDownload PDF (600K) -
KAZUMI FUJIMOTO, SHUNICHI YOSHIDA, YUMIKO MORIYAMA, TAKASHI SAKAGUCHI1976 Volume 24 Issue 6 Pages 1137-1145
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe absorption, distribution, and urinary excretion of 1-(5-oxohexyl) theobromine (BL 191) after oral administration (400 mg/kg) or intravenous injection (25 mg/kg) were studied in rats, using thin-layer chromatography and colorimetry. At the same time, identification of the chemical structure on 4 metabolites of BL 191 in the urine was made. Plasma BL 191 levels reached a maximum within 10 min-1 hr after the oral administration and declined linearly thereafter. BL 191 was no longer detected in plasma 24 hr after the administration. After the intravenous administration, BL 191 was rapidly eliminated from plasma and could not be found 6 hr after the administration. The experiment in rats with the ligated pylorus revealed that a considerable amount of BL 191 administered was absorbed from the stomach as well as from the duodenum and the small intestine after the oral administration. In the organs like the brain, heart, liver, lung, and kidney and the skeletal muscle examined, BL 191 was found to approximately the same extent 10 min after the oral administration and showed the time-course similar to that of plasma levels. BL 191 and its metabolites were rapidly excreted largely in the urine. The total amount excreted in the urine was 1.3% and 68.3% of the dose administered as unchanged BL 191 and as the metabolites, respectively, and most of the excretion was carried out within 24 hr after the administration. 1-(4, 5-Dihydroxyhexyl) theobromine and 1-(3-carboxypropyl) theobromine were main urinary metabolites of BL 191.View full abstractDownload PDF (1021K) -
MASAKI OTAGIRI, TATSUAKI MIYAJI, KANETO UEKAMA, KEN IKEDA1976 Volume 24 Issue 6 Pages 1146-1154
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSInclusion complexation of various barbituric and thiobarbituric acid derivatives with β-cyclodextrin in aqueous solution was studied by ultraviolet (UV), circular dichroism (CD), and nuclear magnetic resonance (NMR) spectroscopies. It was found that the induced CD observed for barbituric acids were substantially different from those for thiobarbituric acids. Chemical Shifts changes in 1H-and 13C-NMR spectra suggested that not only 5-substituent but also heterocyclic moiety of barbiturate participated in inclusion formation. The stability constant of the inclusion complex was determined by UV method at various pH and temperatures from which the thermodynamic parameters were determined. Free barbituric acids were more favorable to form inclusion complex than ionized form. The relationship between the number of carbon atoms in 5-substituents and the formation constant were sigmoidal but barbituric acids bearing cyclic substituent at 5-C deviate from the correlation curves. Isoequilibrium relationship between ΔH and ΔS values were observed having a compensation temperature of 372°K.View full abstractDownload PDF (789K) -
TATSUAKI MIYAJI, YUKIHISA KURONO, KANETO UEKAMA, KEN IKEDA1976 Volume 24 Issue 6 Pages 1155-1159
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe equilibrium constants of barbiturate-β-cyclodextrin complexations in aqueous media were determined by potentiometric titration method. The stability constants for complexes of unionized and ionized barbiturates with β-cyclodextrin and also the dissociation constants of complexed barbiturates can be determined simultaneously by simple procedure with good reproducibility. The results were fairly agreement with those obtained by ultraviolet, circular dichroism, and solubility method. This procedure is applicable even when the complexation accompanies no significant spectral change. The stoichiometric treatment presented was found to be pertinent also to other complexation and surfactant solubilization systems of weakly acidic or basic guest molecules.View full abstractDownload PDF (536K) -
YASUMITSU TAMURA, TOSHIKO SAKAGUCHI, TOMOMI KAWASAKI, YASUYUKI KITA1976 Volume 24 Issue 6 Pages 1160-1164
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA study has been made of the reaction of 3-aminocyclohex-2-enones and 6-amino-1, 3-dimethyluracil with diacylethylene. By the selection of reaction conditions either 4-oxotetrahydroindole or 5-oxotetrahydroquinoline derivatives from 3-aminocyclohex-2-enones and either pyrrolo- or pyrido [2, 3-d] pyrimidine derivatives from 6-amino-1, 3-dimethyluracil were obtained in fairly high yields, respectively.View full abstractDownload PDF (671K) -
KIKUKO HONMA, AKIRA HAMADA1976 Volume 24 Issue 6 Pages 1165-1168
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS1-O-Acyl-β-D-glucopyranose tetraacetates (I-IX) were obtained in high yields by the condensation of acetylated α-D-glucopyranose 1, 2-(t-butyl orthoacetate) with carboxylic acids in chlorobenzene under reflux. The similar reaction with some phenols and p-nitrothiophenol provided the corresponding aryl-β-D-glucoside derivatives (X-XII).View full abstractDownload PDF (500K) -
JUNKO MATSUNAGA, NAOKI NAMBU, TSUNEJI NAGAI1976 Volume 24 Issue 6 Pages 1169-1172
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe solid-solid transition of phenylbutazone polymorphs by heating was investigated by differential scanning calorimetry (DSC) and X-ray diffractometry, and also the difference in dissolution rate due to the polymorphism was confirmed. There were observed three polymorphs of phenylbutazone. Form I melted at 103°, Form II twice at 93° and at 103°, and Form III at 93°. Furthermore, the mutual transition phenomenon by heating among these three polymorphs was observed by DSC. Analyzing the dissolution curves of Forms I and II obtained by the stationary disk method and poltting the saturated concentration of the respective forms, the transition temperature estimated was 98° and the heat of transition 210 cal/mole. Form III was transformed to Form II through compression above a certain compressional pressure and to the intermediate form of Form II and Form III (designated here as "pseudo-Form III") under the compressional pressure 1 ton/cm2. Therefore, the intrinsic dissolution rate of Form III was not obtained. However, the dissolution rate of "pseudo-Form III" was faster than any of Form I and II. Accordingly, it was suggested that if the transition of Form III could be suppressed, more soluble preparations of phenylbutazone would be available.View full abstractDownload PDF (525K) -
MASAMI MORI, MASANOBU HAGA, SETSUZO TEJIMA1976 Volume 24 Issue 6 Pages 1173-1178
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSelective benzoylation of 1, 6-anhydro-4', 6'-O-benzylidene-β-maltose (1), using 2 molar equivalents of benzoyl chloride in pyridine at ca. -10°, yielded five benzoates which were designated 2 to 6 in order of decreasing Rf value on TLC. After column chromatography on silica gel, compounds 2 to 6 were separated as the 2, 2', 3, 3'-tetrabenzoate (2, 1.2%), 2, 2', 3'-tribenzoate (3, 2.8%), 2, 2'-dibenzoate (4, 9%), 2', 3'-dibenzoate (5, 7.3%), and 2'-benzoate (6, 48%), respectively. Thus, the order of reactivities of the secondary hydroxyl groups in 1 is 2'>2, 3'>3. Compound 3 to 6 have potential value in the chemical modification of maltose or the synthesis of maltose-containing oligosaccharides.View full abstractDownload PDF (843K) -
YASUTAKA NAGAI, AKIO MAKI, HISASHI KANDA, KAGAYAKI NATSUKA, SUSUMU UME ...1976 Volume 24 Issue 6 Pages 1179-1188
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of 3, 8-disubstituted-1-oxa-3, 8-diazaspiro [4, 5] decan-2, 4-diones (XI) were synthesized for pharmacological testing. 3-Substituted-8-benzyl compounds (IIIb-h), the intermediates of XI, were prepared by the following three methods : 1) condensation of methyl 1-benzyl-4-hydroxyisonipecotate (II) with urea, followed by alkylation, 2) treatment of II with isocyanates and 3) reaction of 1-benzyl-4-cyano-4-piperidinol (I) with isocyanates followed by hydrolysis. The last method was inferior to the other two methods. Reductive debenzylation of III followed by condensation with appropriate halides afforded XI. Among the compounds (XI) synthesized, 8-[3-(2-chlorophenothiazin-10-yl) propyl]-3-methyl compound (XIa) had excellent central nervous system depressing activities.View full abstractDownload PDF (906K) -
ISOO ITO, NORIICHI ODA, TETSUO KATO1976 Volume 24 Issue 6 Pages 1189-1196
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS2, 4-Diamino-5-hydroxy-6-methylpyrimidine (I) was reacted with acyl halides to give pyrimido [5, 4-b] [1, 4] oxazin-6 (8H)-ones (IIIa, b). Dialkyl acetylenedicarboxylate was made addition with I to afford alkoxycarbonylmethylene-pyrimido [5, 4-b] [1, 4] oxazines (VI, VII). The configuration of this compound was assumed to be cis from the evidence of building pyridazino or furano ring. Similarly, with maleimide, the adduct (XIV) was obtained and converted to pyrimido [5, 4-b] [1, 4] oxazines (XV, XXIa-f).View full abstractDownload PDF (831K) -
KATSUHIKO NAGAHARA, KANAME TAKAGI, TAKEO UEDA1976 Volume 24 Issue 6 Pages 1197-1201
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSous 1'action de hydrogenation catalytique, le cycle oxadiazolique des (amino-2 benzoyl)-5 phenyl-3 oxadiazoles 1 s' ouvre pour donner des oxo-4 quinazolines 3 en passant par des intermediaires du type N-(amino-2 benzoyl) benzamidines 4 qui ne peuvent etreisoles. Dans les memes conditions, les N-(amino-2 benzoyl) benzamidoximes 2 sedegradent en engendrant les anthranilate de benzamidinium qui se transforment aisement par chauffage a leur temperature de fusion en oxo-4 quinazolines 3. On envisage 1'intervention de la fonction hydroxyle du groupe oxime des molecules d'amidoximes du type 2 pour interpreter leur degradation.View full abstractDownload PDF (574K) -
MAMORU SUGIURA, MASAKAZU ISOBE, TSUTOMU OIKAWA, HIROYUKI OONO1976 Volume 24 Issue 6 Pages 1202-1208
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe activity of sterol ester hydrolase was found in the crude enzyme preparation of lipoprotein lipase from Pseudomonas fluorescence. The enzyme was purified by ammonium sulfate fractionation and chromatographies on diethylaminoethyl (DEAE)-cellulose, Sephadex G-75 and carboxymethyl (CM)-cellulose. The lipolytic activity and sterol ester hydrolytic activity at various stages in the purification were found in the same fraction and the ratio of both activities was constant. The purified enzyme was found to be homogeneous by disc electrophoresis and SDS-polyacrylamide gel electrophoresis. Furthermore, one single protein peak which contained lipolytic and sterol ester hydrolytic activities was observed by isoelectric focusing. Therefore, it was concluded that the actions of lipoprotein lipase and sterol ester hydrolase will belong to a same enzyme protein. The action of the purified enzyme for the cholesterol esters in human plasma was investigated. Cholesterol ester was hydrolyzed completely and the rate of hydrolysis of esters of long chain fatty acids was more rapid than that of short.View full abstractDownload PDF (819K) -
MASAYUKI SHIMAGAKI, AKIRA TAHARA1976 Volume 24 Issue 6 Pages 1209-1215
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSStereoselective conversion of l-abietic acid (1) to d-phyllocladene (16) was achieved by the use of two carbon units of the isopropyl group in 1 for the formation of its D-ring. Catalytic hydrogenation of methyl 13-methoxycarbonylmethyl-7-oxopodocarpa-8, 11, 13-trien-15-oate (2), derived from 1, over ruthenium oxide, followed by oxidation, gave stereoselectively methyl 13β-methoxycarbonylmethyl-7-oxopodocarpan-15-oate (4), without loss of the 7-oxygen function. Although attempts of cyclization reaction of methyl 7-hydroxy-13β-(2'-hydroxyethyl)-podocarpan-15-oate (6) to methyl 15-hydroxy-7-oxo-17-norphyllocladan-18-oate (7) were fruitless, the formation of the D-ring from methyl 13β-carboxymethyl-7-oxopodocarpan-15-oate (5) was accomplished by polyphosphoric acid-AcOH treatment to give methyl 7, 15-dioxo-17-norphyllocladan-18-oate (9) in high yield. Selective removal of the 7-oxygen function of 9, via monothioketalization, yielded methyl 15-oxo-17-norphyllocladan-18-oate (11), which was further converted to methyl 17-norphylloclad-15-en-18-oate (14). Hydroboration of 14, followed by oxidation, gave methyl 16-oxo-17-norphyllocladan-18-oate (15) accompanied with 11.View full abstractDownload PDF (889K) -
YOSHIO TAKEDA, HIROSHI NISHIMURA, HIROYUKI INOUYE1976 Volume 24 Issue 6 Pages 1216-1218
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom leaves and twigs of Tarenna kotoensis KAN. et SAS, var. gyokushinka, a new iridoid glucoside, tarennoside (1) has been isolated and its structure has been established. Simultaneously, the known geniposidic acid (2) and ixoside (3) have also been isolated.View full abstractDownload PDF (540K) -
HIDEO UTSUMI, KEIZO INOUE, SHOSHICHI NOJIMA, TAKAO KWAN1976 Volume 24 Issue 6 Pages 1219-1225
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSElectron spin resonance spectra of nitroxide-labeled stearates were investigated in the presence of dipalmitoyl or dimyristoyl lecithin-cholesterol liposomes. Beside the broad resonance lines, originated from the incorporated spin probes, the spectra were characterized with the sharp three resonance lines, which were attributed to the spin probes not incorporated in the liposomal membrane. The superposed spectra were analyzed in terms of the peak height ratio of the sharp and broad lines, and also of the "order parameter, " derived from hyperfine splittings of the broad lines. The two quantities changed depending on the cholesterol content in the liposomes, but appeared to behave entirely different from each other : in the dipalmitoyl lecithin-cholesterol system, the spin probes were more incorporated in the membrane of higher motional state, while, in the dimyristoyl lecithin-cholesterol, they were less incorporated. The relation was discussed and compared with permeability property of the liposomal membranes.View full abstractDownload PDF (854K) -
HIROSHI KISHIMOTO, KUNIHARU SUMIDA1976 Volume 24 Issue 6 Pages 1226-1235
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to elucidate the behavior of ionic portion as well as hydrophobic one of surfactant at solution and micelle formation with the view-point of enthalpy and heat capacity changes, the molar standard enthalpies of solution and micelle formation of lithium, sodium and potassium dodecyl sulfates (generically abr. as DMS), ΔsolH^-<M^^oDS> and ΔmH^-<M^^oDS>, were determined by calorimetry at various temperatures from 20° to 50°, and also their critical micelle concentrations, CMC's by electric conductivity measurement. The molar standard Gibbs free energy and entropy of micelle formation as well as the degree of counter-ion dissociation in micelle were calculated using thermodynamic relations from the values of CMC at various temperatures and ΔmH^-<M^^oDS>. On the basis of Born's theory, ΔsolH^-<M^^oDS> was expressed in the terms, explicitly containing the ionic radii of both dodecylsulfate anion and counter-cation, Li+, Na+, and K+, in MDS crystal and in water, and the terms, representing the hydrophobic contributions of MDS to lattice and hydration energies. The substitution of experimental and literary values into the above-mentioned expression gives, e.g. 2.2 A and 2.0 A as ionic radii of dodecylsulfate ion in crystal and in water, respectively. Also, ΔmH^-<M^^oDS> and its corresponding heat capacity, ΔmC^-<p^^o.MDS>, were analyzed with respect to the hydrophobic and ionic contributions to micelle formation.View full abstractDownload PDF (1020K) -
YUTAKA YAMAMOTO, HITOSHI KIMURA1976 Volume 24 Issue 6 Pages 1236-1241
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSInsertion of diketene into the N-Si bond of silylated secondary amides (Ia-d) followed by hydrolysis afforded N-acetoacetyl derivatives (IVa-d) of the corresponding amides in good yields, respectively. In the reaction with silylated primary amides (Va-c), insertion of diketene into the N-Si bond with subsequent reaction of another mole of diketene resulted in the formation of the corresponding 4-pyrone derivatives (VIa-c), respectively.View full abstractDownload PDF (722K) -
TAMOTSU SAITOH, TAKESHI KINOSHITA, SHOJI SHIBATA1976 Volume 24 Issue 6 Pages 1242-1245
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structure of a new flavonol licoflavonol (II), isolated from Seihoku Kanzo (Glycyrrhiza spp., Leguminosae) along with already known compounds kumatakenin (I), glycyrol (VI) and licoricone (VII), has been determined as 6-γ, γ-dimethylallyl-kaempferol by spectroscopic analysis.View full abstractDownload PDF (510K) -
TETSUJI KAMETANI, KAZUO KIGASAWA, MINEHARU HIIRAGI, KIKUO WAKISAKA, TS ...1976 Volume 24 Issue 6 Pages 1246-1253
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSN-(4-Hydroxybenzyl)-3-benzazocine (II) and its similar compounds (I, III, and IV) were prepared by two routes, and selective N-debenzylation of the quaternary salts (II and III) of the benzazocines (VIII and IX) was achieved under a Hofmann degradation condition to give pentazocine (V). A normal Hofmann degradation is also described.View full abstractDownload PDF (956K) -
TADAO SAKAI, ITSUKO HARA, MASAHIRO TSUBOUCHI1976 Volume 24 Issue 6 Pages 1254-1259
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA singly charged tetrabromophenolphthalein ethyl ester (TBPE) anion was found to be extracted with alkaloids as 1 : 1 complexes in 1, 2-dichloroethane. Of various solvents, TBPE-1, 2-dichloroethane system gave a red color for alkaloids, while in the absence of alkaloids, an organic phase shows a pale yellow color. In this way, the spectrophotometric methods were investigated for the determination of a small amount of the alkaloids, such as quinine, emethine and ephedrine, by solvent extraction. Quinine is determined by measuring the absorbance of the extracts over a range from 0.5-5×10-6M (0.20-1.98 μg/ml) at 555 nm. Emethine is determined from 2×10-6M to 1×10-5M (1.1-5.5 μg/ml) at 570 nm and ephedrine, from 1×10-6M to 1×10-5M (0.20-2.0 μg/ml) at 555 nm. From the conductivity measurements, it is concluded that red species in the extract is considered to be a kind of charge transfer complexes.View full abstractDownload PDF (676K) -
ISAO KITAGAWA, KWANGSIK IM, ITIRO YOSIOKA1976 Volume 24 Issue 6 Pages 1260-1267
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA piscicidal saponin mixture (named boninsaponin) isolated from the bark of Schima mertensiana KOIDZ. (syn. S. boninensis NAKAI, Theaceae) was treated with alkali and the major desacylated product of boninsaponin was isolated and designated as desacyl-bonin-saponin A. On the basis of chemical (including the photolytic cleavage of the glucuronopyranoside linkage) and physicochemical evidence, the structure of desacyl-boninsaponin A has been determined as A1-barrigenol (3)-[β-D-glucopyranosyl (1glu→2glr)] [α-L-rhamnopyranosyl-(1rham→2gal)-β-D-galactopyranosyl (1gal→4glr)]-β-D-glucuronopyranoside (9a), in which the structure of oligosaccharide portion is identical with that of desacyl-jegosaponin obtained from the pericarps of Styrax japonica SIEB. et ZUCC. (Styracaceae).View full abstractDownload PDF (1073K) -
YOSHIHISA KURASAWA, ATSUSHI TAKADA, TAKEO UEDA1976 Volume 24 Issue 6 Pages 1268-1272
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe color reaction of estrone with the antimony trichloride reagent was investigated in order to clarify the reaction mechanism. Two reaction products, 3'-methyl-7-acetoxy-1, 2-cyclopenteno-3, 4-dihydrophenanthrene (I) and estrone acetate (II), were isolated from the colored reaction mixture. It was found that acetyl chloride is indispensable for the color reaction, and that the respective steroids are colored by the formation of the cation-radicals. It was assumed that the cation-radical of the substance I should be responsible for the coloration. The reaction mechanism for the formation of the substance I was inferred, and the relationship between the absorption maxima observed in the absorption spectra and the cation-radicals was discussed.View full abstractDownload PDF (585K) -
TAKANORI SONE, SHIRO TERASHIMA, SHUNICHI YAMADA1976 Volume 24 Issue 6 Pages 1273-1287
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSExploitation of the synthetic route to optically active (R) (-)-4a-methyl-4, 4a, 9, 10-tetrahydro-2 (3H)-phenanthrone ((R) (-)-6a) and its 7-methoxy derivative ((R) (-)-6b) from optically active (R)-2-cyclohexenones ((R) (+)-1) or (S) (+)-δ-ketoaldehydes ((S) (+)-2) were attempted. (R) (+)-1 and (S) (+)-2 could be obtained by the asymmetric synthesis via the enamines prepared from L-proline-derived pyrrolidines ((S)-5) and dl-2-arylpropionaldehydes (dl-4). Base-catalysed cyclization of (S) (+)-2, followed by ketalization and Jones oxidation, gave (S) (-)-cyclohexanone ((S) (-)-7). The same compounds could be also prepared from (R) (+)-1 by successive epoxidation, ketalization, reduction, and Jones oxidation. Addition of N, N-dimethyl lithioacetamide 1, 4-diazabicyclo [2, 2, 2] octane complex to (S) (-)-7, followed by reduction with Vitride and cyclization with polyphosphoric acid, afforded (R) (-)-6a, 85% optically pure, and (R) (-)-6b, [α]20D-223° (ethanol). Detailed studies on reaction products and conditions, and preliminary experiments with racemic compounds were also carried out.View full abstractDownload PDF (1719K) -
TAKANORI SONE, SHIRO TERASHIMA, SHUNICHI YAMADA1976 Volume 24 Issue 6 Pages 1288-1292
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOptically active methyl deoxypodocarpate ((S) (+)-5b), 92% optically pure, was synthesized from (R) (+)-δ-ketoaldehyde ((R) (-)-3a) which was obtainable by the asymmetric synthesis using D-proline-derived pyrrolidine ((R)-4 (R2=CH2NC4H3)) as a chiral additive. The chemical scheme which was previously developed, was used for the conversion of (R) (-)-3a to (S) (+)-phenanthrone derivative ((S) (+)-1a), and a combination of reductive carbomethoxylation and reductive alkylation was adopted for preparing (S) (+)-5b from (S) (+)-1a. Since (S) (+)-5b had already been converted to naturally occurring podocarpic acid ((S) (+)-5a), the asymmetric synthesis of (S) (+)-5a was accomplished.View full abstractDownload PDF (680K) -
TAKANORI SONE, SHIRO TERASHIMA, SHUNICHI YAMADA1976 Volume 24 Issue 6 Pages 1293-1298
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn connection with our studies on asymmetric synthesis of optically active diterpenes and steroids, introduction of a two carbon unit into the carbonyl group of 5, 5-ethylenedioxy-2-methyl-2-phenylcyclohexanone (1) was examined using several kinds of organometallic reagents as nucleophiles. Although N, N-dimethyl lithioacetamide (4f) could afford the desired 1, 2-addition product (8e), other organometallic reagents (4a-e) simply behaved as bases which cleaved the ketal ring of 1, giving the enol ether (5). Use of 4f-1, 4-diazabicyclo [2, 2, 2] octane complex could further improve the yield of 8e from 26% to 84%.View full abstractDownload PDF (765K) -
KAZUMICHI MIZUYAMA, YOKO MATSUO, YOSHINORI TOMINAGA, YOSHIRO MATSUDA, ...1976 Volume 24 Issue 6 Pages 1299-1304
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction of 3-ethoxycarbonyl-2-methylthiothiazolo [2, 3-a] isoquinolinium sulfate (II) with various active methyl and methylene compounds in the presence of a base afforded mesoionic compound (V, VI) substituted by methylthio group with active methylene and pyrrolo [2, 1-a] isoquinoline (=benzoindolizine) derivatives (III, IV, VII, VIII, IX, Xa, b, XI) with opening of the thiazole ring and formation of a pyrrole ring. 1, 3-Diethoxycarbonyl-2-methylthiopyrrolo [2, 1-a] isoquinoline (Xb) was converted to 1-ethoxycarbonyl-2-methylthiopyrrolo [2, 1-a] isoquinoline (XII) by the treatment with polyphosphoric acid (PPA).View full abstractDownload PDF (727K) -
YOSHIAKI TANAKA, MITSUJI SANO1976 Volume 24 Issue 6 Pages 1305-1309
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMass fragmentographic determination of mepirizole in human serum was carried out with the aid of its deuterium labeled compound as the internal standard. Maximal serum level was observed at 60 minutes after oral administration. Simultaneous observation of isotope effect on metabolic rate revealed that serum level of mepirizole deuterated at the methyl group of the pyrazole ring was slightly higher than that of mepirizole, but the isotope effect was observed on the formation of the metabolites.View full abstractDownload PDF (577K) -
KATSUHIKO NAGAHARA, KANAME TAKAGI, TAKEO UEDA1976 Volume 24 Issue 6 Pages 1310-1313
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new synthetic method of o-aminobenzamide derivatives with ethyl ethoxymethylenecyanoacetate or ethoxymethylenemalononitrile gave high yield of 3, 4-dihydro-4-oxoquinazoline and 3-aryl-3, 4-dihydro-4-oxoquinazoline derivatives, and the mechanism of this synthetic reaction was discussed.View full abstractDownload PDF (507K) -
RYUICHI HIGUCHI, TOSHIO KAWASAKI1976 Volume 24 Issue 6 Pages 1314-1323
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structures of two free triterpenoids, Y and Z, and two saponins, PH and PJ1, isolated from the fresh pericarps of Akebia quinata DECNE. (Lardizabalaceae) were investigated. Y, mp 317-320°, [α]D+62°, was identified with arjunolic acid (I), while Z, mp 303-305°, [α]D+75°, was assigned the structure 20 (29)-dehydro-30-norarjunolic acid (XII) and conventionally named norarjunolic acid. PH, mp 207-210°(decomp.), [α]D+3°, was defined as 28-O-α-L-rha·pyr-(1→4)-β-D-glc·pyr-(1→6)-β-D-glucopyranside (XIX) of XII, and PJ1 was characterized as 28-O-β-D-xyl·pyr-(1→3)-α-L-rha·pyr-(1→4)-β-D-glc·pyr-(1→6)-β-D-glucopyranoside (XXIV') of I. XXIV' is the first arjunolic acid oligoglycoside, and XII and XIX are second to eupteleogenin and eupteleoside, respectively, as a naturally occurring noroleanane derivative and its glycoside.View full abstractDownload PDF (1110K) -
TSUNEHIRO KITAGAWA, TAKAKO MIURA, CHIEKO TAKAISHI, HYOZO TANIYAMA1976 Volume 24 Issue 6 Pages 1324-1330
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe limited acylations of I on the two amino functions of β-lysine residue with protected amino acid active esters followed by de-protection by catalytic hydrogenolyses resulted N1-amino acid acylated viomycins. While, the limited carbobenzoxylation followed by the reaction with dicarbobenzoxylysine active ester and the decarbobenzoxylation gave N6-acylated product VI. Antimicrobial assay of the above obtained derivatives result that neutral amino acid derivatives of I have reduced potencies while, basic amino acid derivatives possess almost the similar potencies with I in vitro and in vivo tests. Thus, one of the provable reason for the importance of the two free amino functions of β-lysine residue for the exhibition of the potency of I is concluded to be due to their basicity.View full abstractDownload PDF (758K) -
MINORU SEKIYA, JIRO SUZUKI, YOSHIYASU TERAO1976 Volume 24 Issue 6 Pages 1331-1335
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFacile one step purine syntheses from phenylazomalonic acid derivatives are described. Adenine, xanthine and guanine were synthesized directly from phenylazomalononitrile, N-(2-cyano-2-phenylazoacetyl) urea and 2-cyano-2-phenylazoacetylguanidine, respectively, by catalytic hydrogenation in formamide in the presence of ammonia (in the latter two the presence of ammonia was not indispensable) in excellent or good yields. Course of the reaction was revealed to involve the initial pyrimidine ring-closure followed by the imidazole ring-closure.View full abstractDownload PDF (654K) -
SEIJU KUBOTA, MASAYUKI UDA1976 Volume 24 Issue 6 Pages 1336-1342
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe product distributions resulting from methylation of 3-phenyl-1, 2, 4-triazolin-5-one (1a) and 3-phenyl-1, 2, 4-triazoline-5-thione (1b) and their monomethylated derivatives (2a, b-5a, b) with methyl iodide and diazomethane in various solvents were studied by nuclear magnetic resonance spectroscopy. The methylations of 1-methyl-3-phenyl-1, 2, 4-triazolin-5-one (3a), 5-hydroxy-2-methyl-3-phenyl-1, 2, 4-triazole (4a), and 4-methyl-3-phenyl-1, 2, 4-triazolin-5-one (5a), with methyl iodide in alkaline solution occurred preferentially at the N-atoms and afforded mainly 1, 4-dimethyl-3-phenyl-1, 2, 4-triazolin-5-one (9a), mesoionic anhydro-2, 4-dimethyl-5-hydroxy-3-phenyl-1, 2, 4-triazolium hydroxide (11a), and 9a, respectively. The product ratios on methylations of 3a, 4a, and 5a with diazomethane were affected variously by the type of solvent, the nucleophilicities of the four reaction sites, and the steric factor. Dimethyl sulfoxide (DMSO) increased O-methylation in all cases and especially with 4a, which exists in the OH form, methylation occurred almost exclusively at the oxygen atom in DMSO. The methylations of 1b and its N-methylated derivatives (3b-5b) with either methyl iodide or diazomethane gave S-methylated products predominantly in all the solvents used.View full abstractDownload PDF (670K) -
MOTOKO KUNISHIMA, YUKIO SUGIURA, MAYUMI TAKIMOTO, HISASHI TANAKA1976 Volume 24 Issue 6 Pages 1343-1348
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe additional coordination of inorganic sulfur or selenium to ditiothreitol (DTT)-iron complex induced a dramatic change of iron spin state from g=4.4 (high) to g=2.0 (low). The average g-values of DTT-Fe-S (1.99) and DTT-Fe-Se (2.02) complexes were larger than those of native S-adrenodoxin (1.97) and Se-adrenodoxin (2.00). The ability of O2-uptake and activity of aniline hydroxylation increased in the order, DTT-Fe-Se>DTT-Fe-S>DTT-Fe complexes. In addition, the optimum pH regions for O3-uptake and aniline hydroxylation by the model complexes were approximately parallel with those for complex formation in these DTT-iron systems. On the other hand, the hydroxylation activity of reduced S-adrenodoxin (yield of p-aminophenol : 10.90% per 90 min.) was clearly larger than that of reduced Se-adrenodoxin (7.64%). The effect of DTT-Fe-S and DTT-Fe-Se complexes on the activity of aniline hydroxylation, was compared with that of adrenodoxin and its selenium derivative.View full abstractDownload PDF (718K) -
ATSUSHI SUGII, NAOTAKE OGAWA1976 Volume 24 Issue 6 Pages 1349-1353
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new macroreticular polystyrene resin containing thiohydantoinyl groups was prepared by the cyclization of thioureido resin derived from DL-alanine and isothiocyanate resin. Hg (II) showed the highest adsorption on the resin at the range above pH 1, while the adsorption of Cd (II), Co (II), Cu (II), Ni (II) and Zn (II) depend on the pH values. This resin was stable in the solutions below pH 10. Adsorption and elution behavior of Hg (II) was also investigated by a column experiment.View full abstractDownload PDF (575K) -
TETSUJI KAMETANI, HIDEO NEMOTO, MIE TAKEUCHI, SATOSHI HIBINO, KEIICHIR ...1976 Volume 24 Issue 6 Pages 1354-1361
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS3-(1', 4'-Dioxopentyl)-3-methylcyclohexanone (V) was transformed to the compounds (VIa, VIb, and VII) under acidic conditions. 2-Isopropyl-4, 9-dimethyl-Δ2(3)-1, 5-octadione 5-ethylenethioketal (XIII) was synthesized from compounds (VIa and VIb). 6-Isopropyl-3-methyl-3-(5'-methylfuryl-2') cyclohexanone (XVIII) was obtained from compound (III).View full abstractDownload PDF (1020K) -
SADAO OHKI, NAGANORI OZAWA, YUICHIRO YABE, HIDEAKI MATSUDA1976 Volume 24 Issue 6 Pages 1362-1370
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn connection with 1, 1-diethyl-2-methyl-3-diphenylmethylenepyrrolidinium bromide (1) (anticholinergic agent), 1, 1, 4-trimethyl-(2) and 1, 1, 5-trimethyl-3-diphenylmethylene-pyrrolidinium iodide (3) were synthesized. In the pharmacological examination of anticholinergic activity, the relative potencies of 2 and 3 were 0.01 and 0.27 respectively, in contrast to atropine which was defined as 1.00.View full abstractDownload PDF (1149K) -
NAGANORI OZAWA, HIDEAKI MATSUDA, YUICHIRO YABE, SADAO OHKI1976 Volume 24 Issue 6 Pages 1371-1375
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to examine the structure-activity relationship, trans- and cis-4-diphenylmethylene-1, 1, 2, 3-tetramethylpyrrolidinium iodides (1a, b) were synthesized via trans-(8a) and cis-α, α-diphenyl-1, 2, 3-trimethyl-4-pyrrolidinemethanol (8b). These two intermediates were found to be derived readily from ethyl α-cyano-β-methyllevulinate. Although dehydration of 8a by refluxing with sodium acetate in acetic anhydride resulted in the ring-opening to form N-methyl-N-(4, 4-diphenyl-1, 2-dimethyl-3-butenyl) acetamide, the treatment of 8a and 8b with 20% sulfuric acid in acetic acid gave smoothly trans- and cis-1, 2, 3-trimethyl-4-diphenylmethylenepyrrolidine (10a, b), respectively. Anticholinergic activity of the methiodides (la, b) were tested.View full abstractDownload PDF (656K) -
TSUYOSHI GOROMARU, ATSUKO NODA, KENJI MATSUYAMA, SADAO IGUCHI1976 Volume 24 Issue 6 Pages 1376-1383
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe metabolism and urinary excretion of aminopyrine in man were examined after an oral administration of drug solution. The metabolites were identified and measured quantitatively by gas chromatography and gas chromatography-mass spectrometry. For the microanalysis of metabolite, mass fragmentography was applied. It was clarified that a new metabolite, 4-formylaminoantipyrine, was detected in all cases and it must be noticed as an important metabolite. It was also meaningful that the individual difference among subjects in their urinary excretion behavior of aminopyrine was remarkable beyond our expectations.View full abstractDownload PDF (855K) -
SHORYO HAYASHI, TAKASHI SAKAGUCHI, HIKARU OZAWA1976 Volume 24 Issue 6 Pages 1384-1386
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS3, 7-Dimethyl-1-(5-oxo-hexyl)-xanthine (BL 191) and its major urinary metabolites were examined for the inhibitory effect on the cyclic 3', 5'-nucleotide phosphodiesterase (PDE) activity and for the stimulating effect on lipolysis in rat epididymal fat pads in vitro. In addition, the relationship between these effects of BL 191 and plasma level of free fatty acid (FFA) was investigated in rats. The addition of BL 191 at 2 mM to the incubation mixture inhibited the activity of PDE about 50% and evoked a lipolytic activity 1.5-fold, and BL 191 and theophylline exerted approximately the same effects on PDE and lipolysis. Furthermore, the PDE inhibition and lipolytic response evoked by metabolites I and II possessing an oxohexyl group at the side chain were slightly less than those by BL 191, and metabolites III and IV having a carboxyl group at the side chain had no effects on PDE activity and lipolysis. When BL 191 was given orally, plasma FFA level was elevated in the blood taken 30 min after the administration, increased linearly until 1 hr after the administration when the level was nearly 1.6 times higher than the basal level, and remained at this level till 2 hr after the administration. The above-described results suggested that BL 191 along with its metabolites I and II by the oral administration of BL 191 inhibited the PDE activity and secondarily stimulated the lipolytic activity within the living body.View full abstractDownload PDF (480K) -
YUKIO MORI, KAZUMI TOYOSHI, SHIGEO BABA1976 Volume 24 Issue 6 Pages 1387-1390
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of tritiated or deuterated 3-methylacetanilide with photolysis of pyridine-N-oxide, m-chloroperbenzoic acid, photolysis of hydrogen peroxide and the Fenton or Udenfriend system has been investigated. The retention of tritium (21%) obtained on the 4-hydroxylation of 3-methylacetanilide-4-3H with pyridine-N-oxide photolysis is corresponding to the tritium retention in the enzymic hydroxylation by rat in vivo and in vitro metabolisms, and the retention value (12%) observed in the reaction with m-chloroperbenzoic acid to the results obtained in the metabolism by rat pretreated with 3, 4-benzpyrene or 3-methylcholanthrene. Isotopic hydrogen in the 3-methyl-4-hydroxyacetanilide produced from 3-methylacetanilide-4-2(3)H by Fenton or Udenfriend system was also retained. The reactions with these systems under a few conditions are presented.View full abstractDownload PDF (590K) -
TSUNEO ITOH, MIEKO HONMA, HARUO OGURA1976 Volume 24 Issue 6 Pages 1390-1393
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAttempts to prepare 5-oxothiopyrano [2, 3-d] pyrimidine derivatives by the reaction of 6-mercapto-1, 3-dimethyluracil (I) with various acetylenecarboxylates and ethyl ethoxymethylenecyanomalonate have led instead to the synthesis of substituted thiopyrimidine-2, 4-dione. the condensation of (I) with diethyl ethoxymethylenemalonate yielded readily the corresponding 5-oxothiopyrano [2, 3-d] pyrimidine-2, 4-dione. Elimination of ethoxycarbonyl group in V obtained 1, 3-dimethyl-5-oxothiopyrano [2, 3-d] pyrimidine-2, 4-dione.View full abstractDownload PDF (546K) -
MASAHIKO SETO, TAKESHI OISHI, HIROSHI MITSUHASHI, YOSHIO BAN1976 Volume 24 Issue 6 Pages 1393-1397
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe condensation of 2-hydroxytryptamine hydrochloride (IX) with the hemiacetals such as tetrahydropyran-2-ol (X) and morroniside (III), a member of the iridoids, was investigated. A condensation of IX with X was carried out by standing a solution of IX, X, and sodium acetate in the molar ratio of 1 : 1 : 2 in an aqueous ethanol at room temperature or at reflux for 42 hr to give the amino-alcohol (XI) in 85% yield, which was further characterized as two isomeric diacetyl derivatives (XIIa, XIIb). A condensation of IX with morroniside (III) was conducted under a similar condition only by heating a solution of the components at reflux for 42 hr to give the lactams (XIVa, b), which seemed to have been generated through the processes of the Mannich type of condensation like the preliminary work, followed by elimination of methanol. Attempts to prevent the lactam formation and to isolate the Mannich base were unsuccessful in the latter case, but the condensations of 2-hydroxytryptamine with hemiacetals were proved to have smoothly proceeded to afford the mannich bases in high yields.View full abstractDownload PDF (670K) -
MINORU MAEDA, HIROSHI KOMATSU, MASAHARU KOJIMA, HIROSHI OGAWA1976 Volume 24 Issue 6 Pages 1398-1400
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe title compounds were synthesized by homoallylic rearrangement of 19-bromo- and 19-chlorocholest-5-en-3β-ol, respectively.View full abstractDownload PDF (493K) -
MASAZUMI IKEDA, SAEKO MATSUGASHITA, YASUMITSU TAMURA1976 Volume 24 Issue 6 Pages 1400-1402
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIrradiation of ethyl 2-ethoxy-1, 2-dihydroquinoline-1-carboxylate (1) in ether and ethanol resulted in the formation of a trans head-to-head dimer 2 and an ethanol adduct 5 in 66 and 45% yields, respectively.View full abstractDownload PDF (453K) -
KENSUKE SAKURAI, HIROSHI ISHII, SHINOBU KOBAYASHI, TORU IWAO1976 Volume 24 Issue 6 Pages 1403-1405
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom the leaves of Physalis peruviana L. (Solanaceae), a new withanolide, 4β-hydroxywithanolide E (I) has been isolated together with the known withanolide E (II). Chemical conversion of I into II confirmed the structure of I.View full abstractDownload PDF (510K) -
HIROYUKI INOUYE, SHUSAKU TOBITA, MAKOTO MORIGUCHI1976 Volume 24 Issue 6 Pages 1406-1407
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSChemical conversion of secologanin (3) into bakankosin established the absolute structure of the latter to be represented as 1.View full abstractDownload PDF (377K) -
TETSUZO KATO, MASAKI NODA1976 Volume 24 Issue 6 Pages 1408-1410
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of β-aminocrotonamide (I) with α, β-unsaturated ketones is described. Benzylideneacetophenone (IIa) reacts with β-aminocrotonamide (I) to give 2-methyl-4, 6-diphenylpyridine-3-carboxamide (IIIa), 3-acetimidoyl-4, 6-diphenyl-3, 4-dihydro-2 (1H)-pyridone (IV) and 6-carbamoyl-3, 5-diphenyl-2-cyclohexenonimine (V). Similar reaction of β-aminocrotonamide (I) with 3-buten-2-one (IIb) and 4-phenyl-3-buten-2-one (IIc) affords 2, 6-dimethylpyridine-3-carboxamide (IIIb) and 2, 6-dimethyl-4-phenylpyridine-3-carboxamide (IIIc), respectively.View full abstractDownload PDF (458K) -
KAZUICHI HAYAKAWA, CHINGTAN CHEN, TOSHIO IMANARI, ZENZO TAMURA1976 Volume 24 Issue 6 Pages 1411-1413
Published: June 25, 1976
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSGlucuronide (CF-G) and sulfate (CF-S) of 5-chloro-7-iodo-8-quinolinol were hydrolyzed in water in the presence of metal ions at pH 7. In this condition, CF-G was hydrolyzed more easily than CF-S. The rate of the hydrolysis, pseudo-first order reaction, was in parallel with the stability constants of 8-quinolinol-metal complexes. The rate of hydrolysis increased with reduction of concentration of H+ and tris buffer suppressed the hydrolysis of CF-G. These results suggest that metal catalyzed hydrolysis of CF-G and CF-S was derived from the formation of complexes between the conjugates and metal ions.View full abstractDownload PDF (365K)