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Volume 35, Issue 1
Displaying 1-50 of 66 articles from this issue
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MINORU TSUDA, SETSUKO OIKAWA, KIYOSHI NAGAYAMA1987 Volume 35 Issue 1 Pages 1-8
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSPotential energy hypersurfaces of the nitrogen elimination and the Wolff rearrangement were investigated for both cyclic and open-chain 2-diazoketones by means of semi-empirical MINDO/3 molecular orbital calculations with configuration interaction. In the case of 2-diazobenzen-1-one, the nitrogen elimination takes place simultaneously with the Wolff rearrangement in a concerted fashion and neither ketocarbene nor oxirene is produced. In contrast to the cyclic 2-diazoketone, 2-diazoethan-1-one produces oxirene through nitrogen elimination in a concerted fashion. The oxirene isomerizes to ketene via the Wolff rearrangement, passing over a second saddle point of low energy. No ketocarbene intermediate is produced in either case.View full abstractDownload PDF (989K) -
TAKEHIRO SANO, YOSHIE HORIGUCHI, YOSHISUKE TSUDA, KIMIO FURUHATA, HIRO ...1987 Volume 35 Issue 1 Pages 9-22
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe photocycloaddition of the dioxopyrroline 1 to olefins with electron donating substituents proceeded with regio-and stereo-selectivity to give the 7-substituted 2-azabicyclo [3.2.0] heptane-3, 4-diones 2 and 3, together with, in a few instances, the dihydropyridone 4. The stereochemistries of the [2 + 2] adducts were dependent on the nature of the olefins. Olefins carrying phenyl, vinyl, and alkyl substituents afforded the exo-adducts 2, while olefins carrying an O-substituent afforded the endo-adducts 3, predominantly. The structures of these cycloadducts were established by X-ray crystallographic analyses, chemical correlations, and spectroscopic means.View full abstractDownload PDF (2263K) -
TAKEHIRO SANO, YOSHIE HORIGUCHI, YOSHISUKE TSUDA1987 Volume 35 Issue 1 Pages 23-34
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe photocycloaddition of 4-ethoxycarbonyl-5-phenyl-2H-pyrrole-2, 3-dione 1 to (Z) -and (E) -d-styrenes proceeded in a stereoselective manner to give the compounds in which the styrene component added to 1 antarafacially as the major products. Including these results, the observed exo-or endo-stereoselectivity in the photocycloaddition of 1 to various acyclic olefins is well explained by assuming plural transition states, stepwise C-C bond formation, and a stereoselection rule which may be stated as follows : 1) the first C-C bond formation always occurs suprafacially; 2) the second C-C bond formation in a polar enone-olefin pair (an enone and an olefin with a weak electron donating substituent) occurs antara-selectively from the favored π-complex, while it occurs supra-selectively from the less favored transition state; and 3) in a very polar enone-olefin pair (an enone and an olefin with a strong electron donating group), the second C-C bond formation occurs supra-selectively from the favored π-complex and antara-selectively from the less-favored transition state. Many other stereochemical results hitherto reported can be rationalized in terms of this stereo-selection rule.View full abstractDownload PDF (1715K) -
HASHIME KANAZAWA, MISUZU ICHIBA, ZENZO TAMURA, KEITARO SENGA, KEN-ICHI ...1987 Volume 35 Issue 1 Pages 35-45
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe reaction of 2- (methoxycarbonyl) -4, 6-dimethylthiazolo [5, 4-d] pyrimidine-5, 7 (4H, 6H) -dione 1-oxide (1) with dimethyl acetylenedicarboxylate resulted in a new ring transformation of the thiazole nucleus to give 5- [2-methoxalyl-1, 2-bis (methoxycarbonyl) vinyl] imino-1, 3-dimethyl-6-thiobarbituric acid (4), 6, 7-bis (methoxycarbonyl) -1, 3-dimethylpyrimido [4, 5-b] [1, 4] thiazine-2, 4- (1H, 3H) -dione (8), 6, 7-bis (methoxycarbonyl) -1, 3-dimethylpyrrolo [3, 2-d] pyrimidine-2, 4 (1 H, 3H) -dione (9), and anhydro-2- [1-methoxalyl-1- (O-s-odiummethoxycarbonyl)] methyl-4, 6-dimethylthiazolo [5, 4-d] pyrimidine-5, 7 (4H, 6H) -dione hydroxide (11). Analogously, the reaction of 1 with ethyl phenylpropiolate gave 5 [2-benzoyl-2- (ethoxycarbonyl) -1- (methoxycarbonyl) vinyl] imino-1, 3-dimethy1-6-thiobarbituric acid (22), 5-benzoyl-7- (ethoxycarbonyl) -6- (methoxycarbonyl) -1, 3-dimethylpyrimido [4, 5-b] [1, 4] thiazine-2, 4 (1H, 3H) -dione (23), and 7- (ethoxycarbonyl) -6- (methoxycarbonyl) -1, 3-dimethylpyrrolo [3, 2-d] pyrimidine-2, 4 (1H, 3H) -dione (24). The structures of these products were supported by their spectral [infrared (IR), mass (MS), ultraviolet (UV), proton nuclear magnetic resonance (1H-NMR) or carbon-13 nuclear magnetic resonance (13C-NMR)] data or by single-crystal X-ray diffraction analysis as well as by chemical transformations. The ring transformation of the thiazole nucleus can be best explained by taking into account the initial involvement of a 1, 3-dipolar cycloaddition reaction.View full abstractDownload PDF (1562K) -
TAKAO KONOSHIMA, MUTSUO KOZUKA, TOKUNOSUKE SAWADA, TAKEATSU KIMURA1987 Volume 35 Issue 1 Pages 46-52
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA new triterpenoid saponin, gymnocladus saponin G (1), having a glycosyl monoterpene carboxyl moiety and a 2-methylbutyloyl group, was isolated from the fruits of Gymnocladus chinensis BAILLON. On the basis of chemical and physicochemical evidence, its structure was characterized as 2β, 23-dihydroxy-3-O- [β-D-xylopyranosyl- (1→2) -α-L-arabinopyranosyl- (1→6) -β-D-glucopyranosyl] -21-O- {(6S) -2-trans-2, 6-dimethyl-6- [3-O- (β-D-glucopyranosyl) -4-O- (2-methylbutyroyl) -α-L-arabinopyranosyloxy] -2, 7-octadienoyl} acacic acid 28-O-β-D-xylopyranosyl- (1→3) -β-D-xylopyranosyl- (1→4) -α-L-rhamnopyranosyl- (1→2) - [α-L-rhamnopyranosyl- (1→6)] -β-D-glucopyranoside.View full abstractDownload PDF (1030K) -
MASANORI KUROYANAGI, AKIRA UENO, KAORU UJIIE, SADAO SATO1987 Volume 35 Issue 1 Pages 53-59
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThree new sesquiterpenes, isozedoarondiol (8), methylzedoarondiol (9) and neocurdione (10), were isolated along with germacrone (1), curdione (2), (4S, 5S) -germacrone 4, 5-epoxide (3), dehydrocurdione (4), procurcumenol (5), zedoarondiol (6) and curcumenone (7) from Curcuma aromatica SALISB. The absolute configuration of 6 was determined by X-ray analysis and chemical correlation with 3. The structures of 8, 9 and 10 were also determined.View full abstractDownload PDF (1016K) -
KENSHI ANDO, KOUKI KITAGAWA, SHINYA KIYAMA, TATSUHIKO KAWAMOTO, TADASH ...1987 Volume 35 Issue 1 Pages 60-71
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe heptatriacontapeptide amide corresponding to the entire amino acid sequence of α-form of rat calcitonin gene-related peptide (α-rCGRP) was synthesized by the conventional solution method. All protecting groups employed were removed by treatment with 1 M trifluoromethanesulfonic acid-thioanisole-trifluoroacetic acid, and the deprotected peptide was subjected to airoxidation to form the intramolecular disulfide bond. After purification by gel-filtration on Sephadex G-50, followed by reversed-phase high performance liquid chromatography, a highly purified sample of synthetic α-rCGRP was obtained. In terms of suppression of bone 45Ca-release stimulated by synthetic human parathyroid hormone (1-34), synthetic α-rCGRP was as active as synthetic human CGRP.View full abstractDownload PDF (2121K) -
HIROYUKI HAYAKAWA, KAZUHIRO HARAGUCHI, HIROMICHI TANAKA, TADASHI MIYAS ...1987 Volume 35 Issue 1 Pages 72-79
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe sugar moiety of adenosine, inosine, or guanosine was protected with a tert-butyldimethylsilyl group. The C-8 lithiation of these protected nucleosides was carried out with lithium diisopropylamide in tetrahydrofuran at below -70°C. The reactions of the C-8-lithiated species with MeI, HCO2Me, and ClCO2Me were examined. The resulting products having a carbon substituent at the C-8 position were converted to the corresponding 8-carbon-substituted purine nucleosides by treatment with tetrabutylammonium fluoride. The whole sequence constitutes a simple method for the preparation of 8-carbon-substituted purine nucleosides from intact purine nucleosides.View full abstractDownload PDF (1554K) -
SHIN-ICHI KODATO, HIROSHI WADA, SEIICHI SAITO, MIKIO TAKEDA, YOSHIHIKO ...1987 Volume 35 Issue 1 Pages 80-89
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSIn connection with the known antisecretory activity of the benzotriazepinone (1) and the pyridylurea (2), novel pyridotriazepinones (3 and 4) have been synthesized. They were prepared from aminopyridinecarboxylic acids via several steps, and their structures were confirmed by X-ray crystallographic analysis. Attempts to synthesize the positional isomer (24) resulted in formation of the pyridotriazine (25 or 26). Some of these compounds showed moderate antisecretory activity in rats.View full abstractDownload PDF (1597K) -
TOSHIO KINOSHITA, YASUJI UESHIMA, KOUJI SAITOH, YASUFUMI YOSHIDA, SUNA ...1987 Volume 35 Issue 1 Pages 90-96
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe reaction of 2-amino-2-thiazoline (1) with acetylene carboxylates (2) afforded 5-substituted 2, 3-dihydro-7H-thiazolo [3, 2-a] pyrimidin-7-ones (3). 7-Bromomethyl-2, 3-dihydro-5H-thiazolo [3, 2-a] pyrimidin-5-one (10) was obtained by the reaction of 1 with γ-bromoacetoacetyl bromide. Treatment of 10 with N-bromosuccinimide provided the 6-bromo compound (12). The 7-bromomethyl compounds (10 and 12) were converted to 7-morpholinomethyl derivatives by treatment with morpholine. When 3a (unsubstituted-), 3b (5-ethoxycarbonyl-), and 3c (5-hydroxymethyl-) were treated with 5% hydrochloric acid, covalent hydration occurred across the 5, 6-carbon-carbon bond, giving 5-hydroxy-2, 3, 5, 6-tetrahydro-7H-thiazolo [3, 2-a] pyrimidin-7-one derivatives (16a, 16b, and 16c). On the other hand, in the case of 11 (7-methyl-) and 17 (5-phenyl-), the dihydrothiazole ring was cleaved to give 3 (and 1) - (2-mercaptoethyl) -6-methyl (and phenyl) -2, 4 (1H, 3H) -pyrimidinedione (19 and 18).View full abstractDownload PDF (1198K) -
TAKATOSHI YOSHIDA, TAKASHI SAITO, SHIZUO KADOYA1987 Volume 35 Issue 1 Pages 97-107
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSSix flavonoids (1-6) were isolated from the leaves of Allium tuberosum ROTTLER (Liliaceae). Their structures were characterized as 3-Ο-β-sophorosyl-7-Ο-β-D- (2-Ο-feruloyl) glucosylkaempferol (1), 3, 4'-di-Ο-β-D-glucosyl-7-Ο-β-D- (2-Ο-feruloyl) glucosylkaempferol (2), 3-Ο-β-D- (2-Ο-feruloyl) -glucosyl-7, 4'-di-Ο-β-D-glucosylkaempferol (3), 3, 4'-di-Ο-β-D-glucosylkaempferol (4), 3, 4'-di-Ο-β-D-glucosylquercetin (5) and 3-Ο-β-sophorosylkaempferol (6) by examination of their physicochemical properties. On partial acid hydrolysis, 1 gave 7-Ο-β-D- (2-Ο-feruloyl) glucosylkaempferol (10), and on enzymatic hydrolysis, 1 and 3 afforded 3-Ο-β-D-glucosyl-7-Ο-β-D- (2-Ο-feruloyl) -glucosylkaempferol (11) and 3-Ο-β-D- (2-Ο-feruloyl) glucosylkaempferol (14), respectively. At pH 7.0 or at pH 11.0, or both, the 2-Ο-feruloyl group of 1, 2, 10 and 11 migrated to give the corresponding 6-Ο-feruloyl derivatives (15, 17, 16 and 18). Compounds 1-3 and their derivatives 10, 11, 14, 15, 16, 17 and 18 are new acylated flavonol glucosides.View full abstractDownload PDF (1753K) -
Constituents of Wikstroemia sikokiana. II.Absolute Configurations of 1, 5-Diphenylpentane-1, 3-diolsMASATAKE NIWA, PEI-FENG JIANG, YOSHIMASA HIRATA1987 Volume 35 Issue 1 Pages 108-111
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSFurther examination of the chemical constituents of Wikstroemia sikokiana FRANCH. et SAV. (Thymelaeaceae) afforded (+) -chamaejasmenin B (C-3/C-3″-biflavanone) and (-) -erythro-1, 5-diphenylpentane-1, 3-diol. The unsettled absolute configuration of the 1, 3-diol was established as 1 (S) and 3 (S) on the basis of a synthesis using chiral styrene oxide as a starting material.View full abstractDownload PDF (670K) -
CHIKARA KANEKO, TAKESHI SUZUKI, MASAYUKI SATO, TOSHIHIKO NAITO1987 Volume 35 Issue 1 Pages 112-123
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSIrradiation of 4-allyloxy-2-quinolone and 4- (pent-4-enyloxy) -2-quinolone gave corresponding cross and parallel adducts specifically, whereas 4- (but-3-enyloxy) -2-quinolone led to a mixture of cross and parallel adducts. Regioselectivity in these photoreactions was not affected by the introduction of substituents into 4- (ω-alkenyloxy) -2-quinolones.
These cross adducts were transformed to 2-substituted 1, 2-dihydrocyclobuta [c] quinolin-3 (4H) -ones, whose synthesis could not be achieved by using so-far known intermolecular photocycloaddition of 4-alkoxy-2-quinolone to olefins (the Kaneko-Naito method). Preliminary experiments demonstrated that these 2-substituted derivatives could be used as synthons for 7, 8-disubstituted phenanthridin-6 (5H) -ones by an application of the benzocyclobutene method.View full abstractDownload PDF (1911K) -
ISAO KITAGAWA, ZHENG CUI, BYENG WHA SON, MOTOMASA KOBAYASHI, YOSHIMASA ...1987 Volume 35 Issue 1 Pages 124-135
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA new cytotoxic hydroperoxy-germacrane sesquiterpene named nephtheoxydiol (8) and several related sesquiterpenoids, ent-oplopanone (2), nephthenol (6), and nephthediol (9), were isolated from an Okinawan soft coral of Nephthea sp. (Nephtheidae), together with a new cadinanetype sesquiterpene named nephthene (17). Based on chemical reactions and physical data analyses, the absolute stereostructures of entt-oplopanone (2), nephthenol (6), nephtheoxydiol (8), nephthediol (9), and nephthene (17) have been determined as (+) -oplopanone (2), (4R, 7S)-germacra-1 (10) E, 5E-dien-4-ol (6), (1S, 4R, 7S)-1-hydroperoxygermacra-5E, 10 (15)-dien-4-ol (8), (1S, 4R, 7S) -germacra-5E, 10 (15) -diene-1, 4-diol (9), and (1S, 7R, 10S) -cadina-4 (14), 5-diene (17), respectively.View full abstractDownload PDF (2156K) -
MICHIO KIMURA, ICHIZO OKABAYASHI1987 Volume 35 Issue 1 Pages 136-141
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSDibenzo [c, h] xanthone and halogen-and methyl-substituted xanthones have been synthesized by the oxidation of novel spirolactones of dibenzo [c, h] xanthene and xanthene, which were prepared by a new condensation reaction of 1-naphthol or phenol derivatives with oxalic acid in the presence of sulfuric acid. The oxidation was carried out by using potassium permanganate in the presence of aqueous potassium hydroxide. The dibenzo [c, h] xanthone and xanthones were identical with samples obtained by another synthetic route.View full abstractDownload PDF (829K) -
KATSUHIDE MATOBA, YOSHIRO HIRAI, MINORU TOKIZAWA, YUKO WAKUI, MASANORI ...1987 Volume 35 Issue 1 Pages 142-148
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESStrans-2-Quinolizidinone (I) was treated with methyl 2-pyrrolidylacetate (III) to give a mixture of two isomers, 5, 14-diaza-1, 6-cyclo-1, 10-secogon-8-en-11-one (IV) and 5, 14-diazagon-8-en-11-one (Va) in 8.6 and 2.7% yields, respectively. 1, 2, 3, 3a, 4, 5, 6, 7, 8, 9-Decahydro-7-benzoylpyrrolo [1, 2-a]-[1, 6] -naphthyridin-5-one (VIb) [prepared from 1-benzoyl-4-piperidone (IIb) and III] was hydrolyzed and then allowed to react with methyl vinyl ketone to give a Michael adduct (VId). It was treated with mercuric acetate to afford regio-and stereoselectively 5, 14-diazagon-8-ene-2, 11-dione (Vb), whose angular protons at the C10 and C13 were anti to each other. The structure of Vb was determined by X-ray crystallographic analysis. Compound Vb was converted to Va via a thioketal (Vc).View full abstractDownload PDF (1045K) -
GEN-ICHIRO NONAKA, SATOSHI MORIMOTO, JUN-EI KINJO, TOSHIHIRO NOHARA, I ...1987 Volume 35 Issue 1 Pages 149-155
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe structures of proanthocyanidin A-1 (2) and two related proanthocyanidins, tentatively named A-4 (3) and A-5' (4), have been established unambiguously on the basis of spectroscopic evidence and chemical correlations with the structurally known proanthocyanidin A-2 (1). Chemical transformation of singly linked proanthocyanidin B-1 (6) into 2 also confirmed the stereostructure of 2.View full abstractDownload PDF (977K) -
AKIKAZU KAKEHI, SUKETAKA ITO, KENJI NAGATA, NAOSUMI KINOSHITA, NOBORU ...1987 Volume 35 Issue 1 Pages 156-169
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe formation of pyrazolo [1, 5-a] pyridine derivatives via the desulfurization and the rearrangement of pyrido [1, 2-d]-1, 3, 4-thiadiazine intermediates having various substituents at the 2-and 4-positions was investigated, and the wide applicability of this approach to the syntheses of pyrazolo [1, 5-a] pyridines was established. The substituent effect in these reactions was also clarified. The possibility of the extension of this reaction to other heterocyclic systems such as pyrido [1, 2-b]-pyridazine and pyrido [2, 1-f]-1, 2, 4-triazine was examined, but only pyridinium 1-aminide and 1, 2, 4-triazolo [1, 5-a] pyridine were obtained instead of the expected heterocyclic compounds.View full abstractDownload PDF (1615K) -
HIDEYUKI HARUYAMA, MICHIO KONDO1987 Volume 35 Issue 1 Pages 170-181
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA quantitative treatment of proton spin-lattice relaxation time (T1) and nuclear Overhauser effect (NOE) has been applied to the conformational analysis of two ML-236B (mevastatin) metabolites, 4β, 6α-dihydroxy ML-236B (1) and 3β-hydroxy ML-236B (2) in solution. The T1 values and NOE factors predicted for several candidate conformers were compared with the observed ones.
For 1, the best agreements between observed and calculated values were obtained when the A ring of its octalin moiety was assumed to adopt a chair conformation, and the B ring, a 7β-sofa conformation. In addition it was found that the δ-lactone side chain should be confined to some limited orientations to give calculated values consistent with the observed T1 values and NOEs. Based on the X-ray derived geometry, a similar analysis was done for 2, to check the validity of the method and to characterize the conformation of the δ-lactone side chain in solution. The δ-lactone side chain of 2 was concluded to have the same conformation as in the crystal state.
The applicability of the distance geometry method to calculate the coordinates of small organic molecules was confirmed.View full abstractDownload PDF (1636K) -
TAKUO OKUDA, TAKASHI YOSHIDA, XIN-MIN CHEN, JING-XI XIE, MAKOTO FUKUSH ...1987 Volume 35 Issue 1 Pages 182-187
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSPseudotutin previously isolated from Coriaria japonica A. GRAY was revealed to be a molecular compound consisting of equimolar tutin (2) and a new related sesquiterpene lactone, corianin (3). Corianin was also isolated together with coriamyrtin (1), tutin (2) and coriatin (4), from Loranthus parasiticus MERR., a parasitic plant that grows on the twigs of Coriaria sinica MAXIM. The structure of corianin was elucidated on the basis of nuclear magnetic resonance and chemical evidence. The previously proposed structure (4) for coriatin was also substantiated.View full abstractDownload PDF (971K) -
DAVID J. CRAIK, JON G. HALL, SHARON L. A. MUNRO1987 Volume 35 Issue 1 Pages 188-194
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSTwo-dimensional nuclear magnetic resonance (2D NMR) spectroscopy has been used to assign 13C spectra of the tricyclic antidepressants imipramine and chlorimipramine. The 2D-INADEQUATE method was used to unambiguously assign the aromatic spectral region for the former compound. Errors in previous literature assignments based on 1D methods were corrected. For chlorimipramine the pitfalls of classical substituent chemical shift arguments for 13C assignments and the difficulties of 1D selective 1H irradiation in overlapped systems are contrasted with the power and relative simplicity of the 2D-13C, 1H-correlated and 13C, 1H RELAY methods.View full abstractDownload PDF (1030K) -
MIYOJI HANAOKA, WON JEA CHO, MARI MARUTANI, CHISATO MUKAI1987 Volume 35 Issue 1 Pages 195-199
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESS2, 3, 9, 10-Tetraoxygenated protoberberin alkaloids, berberine (1a), palmatine (1b), and coptisine (1c), were efficiently converted into the corresponding 12-hydroxy-2, 3, 10, 11-tetraoxygenated protoberberines (6a, 6b, 6c) through an oxidative C8-C8a bond cleavage with m-chloroperbenzoic acid, followed by the enamide photo-cyclization. On successive treatment with diethyl chlorophosphate and sodium in liquid ammonia, the 12-hydroxy derivatives (6a, 6b, 6c) underwent reductive dehydroxylation to produce the corresponding 2, 3, 10, 11-tetraoxygenated protoberberines, tetrahydropseudoberberine (4a), (±) -xylopinine (4b), and tetrahydropseudocoptisine (4c), respectively.View full abstractDownload PDF (930K) -
SHIGETOSHI KADOTA, TAKEHIKO SHIMA, TOHRU KIKUCHI1987 Volume 35 Issue 1 Pages 200-210
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe C-24 stereochemistry of cyclohomonervilol, a non-conventional side chain triterpene isolated from Nervilia purpurea, was determined to be 24S by chemical transformation to 24S-dihydrocyclofuntumienol. Separation of a 24-epimeric mixture of chemically synthesized 24-isopropenylcholesterol was effectively achieved by reversed-phase high-performance liquid chromatography (HPLC), and the C-24 stereochemistry of each epimer was determined on the basis of chemical correlation with sitosterol or clionasterol. Then, 24ζ-isopropenylcholesterol, isolated from N. purpurea, was identified as 24S-isopropenylcholesterol by proton nuclear magnetic resonance and HPLC comparisons with the synthetic sample.View full abstractDownload PDF (1546K) -
SUGURU TAKATSUTO, NOBUO IKEKAWA, TADASHI MORISHITA, HIROSHI ABE1987 Volume 35 Issue 1 Pages 211-216
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSIn order to examine the biological role of the A/B-ring functional groups of plant-growth-promoting brassinosteroids, twenty-three brassinosteroids with some modifications at rings A and B (1-15 and 22-29) were bioassayed by means of the rice-lamina inclination test. The results showed that 1) removal of one or two hydroxyl groups from the A-ring reduced the biological activity of the steroids; 2) the 7-oxalactone brassinosteroids were almost as active as the corresponding 6-oxo steroids and they were much more active than their regioisomeric 6-oxalactone counterparts; 3) introduction of a double bond at the C-7 position and a hydroxyl group at the C-5 position of 6-oxo brassinosteroids significantly decreased the biological activity of the hormonal steroids. These data suggest that the presence of a 2α, 3α-diol, 7-oxalactone or 6-oxo group, and the A/B-trans ring junction are important for high biological activity.View full abstractDownload PDF (822K) -
GEN-ICHIRO NONAKA, KANJI ISHIMARU, MICHIYO WATANABE, ITSUO NISHIOKA, T ...1987 Volume 35 Issue 1 Pages 217-220
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe chirality of the nonahydroxytriphenoyl group in castalagin (1) and vescalagin (2) was determined to be in the S, S-series on the basis of circular dichroism analysis. In addition, a new ellagitannin (4) has been isolated from the leaves of Eugenia grandis (Myrtaceae), and the structure was established to be 1-Ο-galloyl castalagin on the basis of chemical and spectroscopic evidence.View full abstractDownload PDF (597K) -
MASAHIDE NOJI, KENJIRO SUZUKI, TAZUKO TASHIRO, MAKOTO SUZUKI, KEN-ICHI ...1987 Volume 35 Issue 1 Pages 221-228
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSNew 1R, 2R-cyclohexanediamine (=1R, 2R-dach) Pt (II) complexes containing dicarboxylate ions, i.e., ketomalonate, malate, saccharate, glutarate, diphenate, and α, β-diphenylsuccinate were synthesized and tested against leukemia L1210 in vivo. All of the dicarboxylato Pt (II) complexes showed relatively high antitumor activities with T/C% values of more than 200 at optimal doses. In particular, mucato and α, β-diphenylsuccinato Pt (II) complexes exhibited excellent antitumor activities with T/C% values of 348 and 369, respectively, with 3 cured mice out of six.
The dicarboxylato Pt (II) complexes were determined by elemental analyses to contain dicarboxylates : Pt : 1R, 2R-dach in a ratio of 1 : 1 : 1. The molecular secondary ion mass spectra of saccharato and glutarato Pt (II) complexes indicate that these complexes exist in a binuclear form together with a mononuclear form in aqueous solution.View full abstractDownload PDF (1115K) -
TAICHI OHMOTO, KEEKO KANATANI (née INAGAKI), KYOKO YAMAGUCHI1987 Volume 35 Issue 1 Pages 229-234
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSFrom the pollen grains of Cedrus deodara LOUD., five known compounds, dehydroabietic acid (I), 15-hydroxydehydroabietic acid (II), 7α, 18-dihydroxydehydroabietanol (IV), naringenin (VI) and β-sitosteryl β-D-glucoside (VII), and two new compounds, 7β, 15-dihydroxydehydroabietic acid (III) and hexadecane-1, 16-diol 7-caffeoyl ester (V), were isolated. The structures of III and V were elucidated on the basis of spectroscopic studies and chemical evidence.View full abstractDownload PDF (979K) -
MYUNGKOO LEE, HITOSHI NOHTA, KENJI OHTSUBO, BEONGTAE YOO, YOSUKE OHKUR ...1987 Volume 35 Issue 1 Pages 235-240
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA simple and highly sensitive method for the determination of L-3, 4-dihydroxyphenylalanine (L-DOPA) in human plasma and urine is described which employs high-performance liquid chromatography with fluorescence detection. After cation-exchange chromatography on a Toyo-pak IC-SP S cartridge, L-DOPA and α-methyldopa (an internal standard) in 300μl of plasma or 10 μl of urine are converted into the corresponding fluorescent compounds by reaction with 1, 2-diphenylethylenediamine. These compounds are separated by reversed-phase chromatography on a TSK gel ODS-120T column with isocratic elution. The detection limit for L-DOPA is 10 fmol in a 100-μl injection volume.View full abstractDownload PDF (820K) -
SUSUMU HIAI, YUICHI SASAYAMA, CHITARU OGURO1987 Volume 35 Issue 1 Pages 241-248
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe effects of chronic treatment with ginseng saponin, saikosaponin, glycyrrhizin and flavin adenine dinucleotide (FAD) on the adrenal and thymus weight, and the size of the adrenal cortex and medulla were determined in intact or hypophysectomized rats. A high dose of ginseng saponin significantly decreased the thymus weight, although ginseng saponin and a low dose of adrenocorticotropin (ACTH) induced insignificant hypertrophy of the adrenals. Ginseng saponin evoked a significant increase in the relative thickness of the adrenal cortex. Saikosaponin d increased the area of the adrenal cortex, but not that of the medulla, and induced adrenal hypertrophy and thymus atrophy, whereas saikosaponin c did not affect the weight of either. A high dose of glycyrrhetinic acid, like ginseng saponin, induced thymus atrophy, but not adrenal hypertrophy. FAD evoked adrenal hypertrophy in dexamethasone-treated rats but not in control rats. In hypophysectomized rats these effects of ginseng saponin, saikosaponin d and FAD disappeared, while a low dose of dexamethasone or ACTH induced thymus atrophy or adrenal hypertrophy, respectively.View full abstractDownload PDF (1271K) -
MACHIKO MATSUBARA, HISATORA KURODA1987 Volume 35 Issue 1 Pages 249-255
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe chemical structure of a glycoprotein secreted from conidia of Mycosphaerella pinodes into the medium during germination was investigated, and its elicitor activity to induce pisatin synthesis in peas was examined. The glycoprotein showed a higher elicitor activity than the intra-conidial polysaccharide. The glycoprotein, whose molecular weight is about 130×104, has ap partial structure in which a reducing terminal mannosyl residue of a trisaccharide 1Man6-α←1Man6β←1Glu is Ο-glycosidically attached to serine in the protein portion.View full abstractDownload PDF (1014K) -
KUNIO OKUMURA, YASUMARU HATANAKA, HITOSHI NAKAYAMA, YUICHI KANAOKA1987 Volume 35 Issue 1 Pages 256-261
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA new leucine-enkephalin analog containing p-azidophenylalanine was synthesized. It binds to the δ-opioid receptors of NG 108-15 cells with high affinity. Iodination of the compound decreased the affinity by 5 times, but the iodinated derivative still retains significant binding activity to the cells. Photochemical reactions revealed that the derivative predominantly labeled a 58 kilodaltons (kDa) polypeptide in the cells (possibly a δ-receptor component)View full abstractDownload PDF (811K) -
KYOKO ADACHI, HIROAKI NANBA, HISATORA KURODA1987 Volume 35 Issue 1 Pages 262-270
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSA polysaccharide (3-branched β-1, 6-glucan MT-2) extracted from fruit bodies of Grifola frondosa (maitake) showed an antitumor effect against mouse syngeneic tumors (MM-46 carcinoma and IMC-carcinoma). It is not only directly activates various effector cells (macrophages, natural killer cells, killer T cells, etc.) to attack tumor cells, but also potentiates the activities of various mediators including lymphokines and interleukin-1. Thus, it acts to potentiate cellular functions and at the same time to prevent a decrease of immune functions of the tumor-bearing host.View full abstractDownload PDF (1343K) -
ATSUKO HINATA, MICHIKO IIJIMA, YASUKO NAKANO, TERUFUMI SAKAMOTO, MOTOW ...1987 Volume 35 Issue 1 Pages 271-276
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSRabbit α2-macroglobulin was isolated from rabbit plasma by polyethylene glycol precipitation, diethyl aminoethyl-Sephacel chromatography and gel chromatography. The protein subunit migrated as a single band with a molecular weight of 190000 on sodium dodecyl sulfate-gel electrophoresis under reducing conditions. Its amino-terminal amino acid sequence was determined for the first 13 residues. The amino terminus corresponded to the third residue of human α2-macroglobulin, and eleven of the 13 residues determined were identical with those of human α2-macroglobulin. These results, together with the amino acid compositions, indicate that rabbit and human α2-macroglobulins have a very similar structure. However, rabbit α2-macroglobulin was much more sensitive to methylamine inactivation than human α2-macroglobulin, and rat antisera against rabbit α2-macroglobulin did not react with human α2-macroglobulin.View full abstractDownload PDF (890K) -
HIROSHI NODA, SEIJI ETO, MASAO MINEMOTO, ATSUKO NODA, KOHJI OHNO1987 Volume 35 Issue 1 Pages 277-281
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe inhibitory effects of isoniazid, its metabolites and related compounds on phenytoin biotransformation were studied in an isolated rat hepatocyte system. Oxidation of phenytoin was inhibited strongly by isoniazid, acetylhydrazine, benzoylhydrazine and phenylhydrazine, and weakly (but significantly) by acetylisoniazid and hydrazine. Isonicotinic acid and diacetylhydrazine showed no effect. These observations may indicate that active hydrazine compounds are ones which can give a relatively significant rise to reactive intermediates such as radicals, diazene compounds or their reratives during the oxidation metabolism. On the other hand, glucuronidation of the oxidized metabolite, 5-phenyl-5- (p-hydroxyphenyl) hydantoin, was not affected by isoniazid.View full abstractDownload PDF (793K) -
JULIANNA SZEMAN, HARUHISA UEDA, JOZSEF SZEJTLI, EVA FENYVESI, YOSHIHAR ...1987 Volume 35 Issue 1 Pages 282-288
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe complex-forming abilities of a water-soluble β-cyclodextrin-epichlorohydrin polymer (CDPS) and two different molecular weight fractions of CDPS were studied and compared with those of β-cyclodextrin (β-CyD) and dimethyl-β-cyclodextrin (DM-β-CyD).
CDPS was separated into two main fractions by gel chromatography. CDPS and its fractions formed inclusion compounds with several drugs and these complexes were readily soluble. The low-molecular-weight fraction formed rather stable complexes with small guest molecules. The high-molecular-weight fraction was found to be more efficient in binding larger substrates.View full abstractDownload PDF (938K) -
YUDI PADMADISASTRA, YOICHI SAWAYANAGI, TSUNEJI NAGAI, IGOR GONDA1987 Volume 35 Issue 1 Pages 289-293
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThis paper describes our attempts to prepare a direct compression excipient from bagasse (DICEB) and its properties, particularly as they pertain to tablet making. After a process somewhat similar to the manufacture of microcrystalline cellulose (MCC), a white powder was obtained which was used in compression studies. Variation of the compression pressure, particle size distribution and moisture content did not yield caffeine-containing DICEB tablets which would be of the same satisfactory quality in terms of mechanical stability and disintegration time as those prepared from commercial MCC. These findings were interpreted to be the result of poor water uptake by DICEB.Removal of residual wax from bagasse yielded a powder with promising properties as an excipient for direct compression of tablets.View full abstractDownload PDF (760K) -
TSU-HAN LIN, YASUFUMI SAWADA, YUICHI SUGIYAMA, TATSUJI IGA, MANABU HAN ...1987 Volume 35 Issue 1 Pages 294-301
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe permeability of the blood-brain barrier (BBB) of rats to 3H-imipramine (IMP) and 3H-desipramine (DMI) was measured by a tissue-sampling single-injection technique to examine the protein mediated transport. Increased concentrations of serum proteins added to the carotid injection solution resulted in decreases in the brain extraction and PSapp of 3H-IMP and 3H-DMI. The extraction ratio of 3H-IMP (0.92) was higher than that of 3H-DMI (0.24) in the case of the buffer injection solution. The values of in vitro binding activity (n/Kd) of 3H-IMP to bovine serum albumin (BSA), human serum albumin (HSA) and α1-acid glycoprotein (α1-AGP) were 4.52, 1.48 and 57.89 mM-1, respectively, and that of 3H-DMI to α1-AGP was 38.92 mM-1. On the other hand, the in vivo n/Kd values of the binding of 3H-IMP to BSA, HSA and α1-AGP estimated from the single-injection experiment were 0.597, 0.754 and 14.73 mM-1, respectively, and that of 3H-DMI to α1-AGP was 5.90 mM-1. The in vitro n/Kd values of the binding of 3H-IMP and 3H-DMI to various serum proteins were thus larger than the corresponding in vivo n/Kd values. A marked difference was found between the observed extraction ratios and what would be predicted if only the unbound 3H-IMP or 3H-DMI is transported, although the difference was not large in the case of HSA. These results suggest that protein mediated transport, previously found for propranolol and lidocaine with α1-AGP by Pardridge et al. (J. Clin. Invest., 71, 900 (1983)), also operates for 3H-IMP and 3H-DMI, and this phenomenon seems to be independent of both the species and the source of serum protein, at least for 3H-IMP. Further, the brain extraction ratio of 3H-DMI was much lower than that of the parent drug 3H-IMP, probably due to their different degrees of lipophilicity.View full abstractDownload PDF (1227K) -
TAMIKO SAKURAI, MOTOTAKA MATSUYAMA, SEISHI TSUCHIYA1987 Volume 35 Issue 1 Pages 302-307
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSCommercially available Cu, Zn superoxide dismutase (SOD) from bovine erythrocytes was purified. Purified SOD was incubated with 1 M glucose at 37 °C for 14d under sterile conditions. Nonezymatic addition of glucose to SOD molecules increased linearly until 7 d, and then increased only slightly. The enzyme activity decreased to 88% after 7d and 60% after 14d. The glycated amino acid residue is not the N-terminal α-amino group but the ε-amino group of lysine. It seems that lysine at the active center, which assists the interaction of O2-and the SOD molecule, is affected during 14d.View full abstractDownload PDF (1045K) -
YASUO MATSUSHITA, JUNKO EIKI, MARIKO TSUKIORI, TATSUO SUZUKI, IKUO MOR ...1987 Volume 35 Issue 1 Pages 308-314
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe drug binding characteristics of pooled sera from patients with acute or chronic hepatitis and with chronic renal failure were investigated by means of equilibrium dialysis and ultracentrifugation, and were compared with those of healthy adult serum and human serum albumin. The drugs used were diazepam, naproxen, warfarin, and phenylbutazone. Serum from patients with renal disease showed markedly impaired binding with diazepam and naproxen at the primary binding site. However, almost no decrease of the binding was observed with warfarin and phenylbutazone. The impaired bindings of diazepam and naproxen were restored after active-charcoal treatment of the serum. This result suggested that, in the serum from patients with renal disease, the apparent decrease of the binding is probably due to the presence of some substance (s) which inhibit the binding of these drugs to the primary sites. On the other hand, no abnormal binding behavior was recognized in the serum from patients with liver disease. Thus, care is necessary when drugs binding to the diazepam site (such as diazepam and naproxen) are administered to patients with renal diseases, because a marked elevation of unbound drug concentration in the serum may occur.View full abstractDownload PDF (879K) -
MASAHIKO KIKUCHI, FUMITOSHI HIRAYAMA, KANETO UEKAMA1987 Volume 35 Issue 1 Pages 315-319
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSDegradation of carmoful (HCFU) in the solid state was significantly accelerated by β-cyclodextrin (β-CyD) complexation owing to the hygroscopic nature of β-CyD. The instability of HCFU in the solid complex was found to be markedly improved by the addition of some organic acids such as citric, L- (+) -tartaric and DL-malic acids, whereas DL-aspartic acid and neutral additives such as talc, lactose, cellulose and methyl cellulose had insignificant stabilizing effects. The results indicated that organic acids having lower pKa value and higher aqueous solubility are particularly useful to prevent the hydrolysis of HCFU by providing an acidic environment around the complex after moisture sorption.View full abstractDownload PDF (602K) -
YUKIHIKO ARAMAKI, JUN-JI NIIBUCHI, SEISHI TSUCHIYA, JUN-ICHI HOSODA1987 Volume 35 Issue 1 Pages 320-325
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe interactions of an aminoglycoside antibiotic, 3', 4'-dideoxykanamycin B (DKB), with submaxillary mucin were investigated by equilibrium dialysis and affinity chromatography.
DKB binds to mucin and forms a complex of low solubility. This binding was dependent on the pH and ionic strength. Scatchard plot analysis showed that mucin had one class of binding sites for DKB. The binding coefficient was 1.30×10-5M and the concentration of binding sites was 0.243 μmol per mg of mucin at 25°C. The binding of DKB to mucin was inhibited in the presence of Ca2+ or amines, such as ethylenediamine, spermidine and glucosamine. The N-pentaacetyl derivative of DKB did not bind to mucin. The binding of DKB to asialomucin was decreased. After binding to a DKB-conjugated Sepharose 4B column, a small amount of mucin was eluted with NaCl solution and a large amount of mucin was eluted with N-acetylneuraminic acid solution.
These results suggest that the binding of DKB to mucin involves an ionic interaction between the amino groups of DKB and the carboxyl groups of the sialic acid residues of submaxillary mucin.View full abstractDownload PDF (901K) -
KYOKO TAKAHASHI, YASUKO FUJITA, TADANORI MAYUMI, TAKAO HAMA, TAKEO KIS ...1987 Volume 35 Issue 1 Pages 326-334
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSAdriamycin (ADM) inhibited the beating of cultured mouse embryo myocardial cells dose-and time-dependently and subsequently lysed the cells. Fifty percent inhibition of beating cell number was observed when cultures were exposed to 430-520 μm ADM for 0.5h, 70-100 μm ADM for 4h and 3.5 μm for 36 h. When cultures were exposed to 3.5μm 3H-ADM, the radioactivity in the cells reached almost the maximum within 8 h, and about 90% was recovered as ADM itself even after 72 h. However, the beating cell number and the beating rate did not appreciably decrease within 8 h, then decreased to 78.5 and 67.1% at 24 h, and 5.6 and 5.2% at 72 h, respectively. Lysis of the cells was conspicuous at 48 h or later. It was also supported with the decrease in cellular proteins and the release of lactate dehydrogenase. These results indicate that ADM stimulates lysis of the cytoplasmic membrane following inhibition of beating. When cultures were exposed to 70 μm ADM for 4 h and then incubated in ADM-free medium, about 50% of ADM in cells was released within 24 h. However, inhibition of beating and lysis of such cells still advanced at about the same rate as in continuously exposed cells. ADM also decreased the cellular adenosine triphosphate (ATP) content in the same fashion as antimycin A, which inhibited beating in advance of ATP reduction. These results suggested that the beating state of myocardial cells is a sensitive and reliable parameter in this system for studies on the cardiotoxicity of ADM. The system may be useful for studies not only on ADM but also on agents having effects on the heart.View full abstractDownload PDF (2121K) -
SHUU MATSUMOTO, MASAMI MORIYAMA, HIDEYO IMANISHI1987 Volume 35 Issue 1 Pages 335-343
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe effects of recombinant human interferon (IFN) -gamma (Met-Gln form), having the same amino acid sequence as that of natural human IFN-gamma except for the N-terminal Met residue, on the expression of Fc receptor (FcR) and Ia-like antigen in human monocytes and lymphocytes were comparatively investigated with those of natural human IFN-alpha and -beta. IFN-gamma (Met-Gln form) increased dose-dependently the number of FcRs binding to anti-chicken red blood cell (CRBC) immunoglobulin G on monocytes and the number of monocytes bearing the FcR, whereas the two natural IFNs did not. IFN-gamma (Met-Gln form) also enhanced the expression of Ia-like antigen on monocytes but the natural IFNs did not. On the other hand, IFN-gamma (Met-Gln form) had no effect on the expression of the FcR and Ia-like antigen on lymphocytes or on antibody-dependent cell-mediated cytotoxic activity against CRBCs, as was also the case with the natural IFNs. These results indicate that IFN-gamma (Met-Gln form) has a potent ability to induce or enhance the expression of FcR and Ia-like antigen on human monocytes though IFN-alpha and -beta do not, whereas IFN-gamma (Met-Gln form) has no effect on the expression on human lymphocytes, like the natural IFNs.View full abstractDownload PDF (1402K) -
KIYOMI KIKUGAWA, KUNITAROU KOGI1987 Volume 35 Issue 1 Pages 344-349
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSNitrogen dioxide at 100 ppm in air greatly accelerated the oxidation of methyl esters of linoleic and linolenic acid in both non-aqueous and aqueous systems. Nitrogen dioxide stimulated oxygen uptake, conjugated diene formation and increase in the peroxide value of methyl linoleate and methyl linolenate. The products formed from methyl linoleate were identified as four isomeric hydroperoxides ; the ratio of the amounts of the isomers was similar to that of the hydroperoxides formed by autoxidation. No nitrogen-containing products were formed. The products formed from methyl linolenate were identified as eight isomeric hydroperoxides that were also formed by autoxidation.View full abstractDownload PDF (945K) -
HIROMU NAGASHIMA, KIYOSHI UKAI, HIROHISA ODA, YUKIO MASAKI, KENJI KAJI1987 Volume 35 Issue 1 Pages 350-356
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSMethoxylation of 3, 4, 6-trichloropyridazine (1) with sodium methoxide was investigated in detail. Dimethoxylation of 1 afforded 6-chloro-3, 4-dimethoxypyridazine (5) and a molecular complex (M) which is composed of 5 and 3-chloro-4, 6-dimethoxypyridazine (6) in a ratio of 1 : 1. The nature of the complex (M) was examined by thermal and X-ray analyses. The molecular complex (M) was also obtained by monomethoxylation of 3, 6-dichloro-4-methoxypyridazine (3) with sodium methoxide.View full abstractDownload PDF (857K) -
SHIGEYUKI YOSHIFUJI, YUKIMI ARAKAWA, YOSHIHIRO NITTA1987 Volume 35 Issue 1 Pages 357-363
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSRuthenium tetroxide (RuO4) oxidation of N-alkyllactams proceeded regioselectively depending on the size of lactam ring, except for the seven-membered ring. Four- and eight-membered N-methyl- and N-ethyllactams were oxidized at the exocyclic α-carbon adjacent to nitrogen to produce the N-acyllactams and NH-lactams, while five- and six-membered lactams underwent endocyclic oxidation to yield the cyclic imides. Oxidation of seven-membered lactams yielded a mixture of products arising from both exocyclic and endocyclic oxidations. These regioselectivities were confirmed in the oxidation of substrates having a tertiary carbon at the oxidation position.View full abstractDownload PDF (1017K) -
KEN-ICHI TANAKA, SHIGEYUKI YOSHIFUJI, YOSHIHIRO NITTA1987 Volume 35 Issue 1 Pages 364-369
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSOxidation of various N-acylalkylamines with ruthenium tetroxide (RuO4) was systematically investigated. N-Acylalkylamines having an electron-donating group at the α-or β-position with respect to amide nitrogen or an electron-donating alkyl function in the acyl group were smoothly oxidized to the corresponding imides in excellent yields. On the other hand, N-acylalkylamines having an electron-withdrawing group were not oxidized at all, and most of the starting material was recovered. It appears that the reactivity of N-acylalkylamines is closely correlated with the acidity of the carboxylic acid from which the N-acyl group is derived, and also with the electron density at the methylene moiety adjacent to the amide nitrogen atom.View full abstractDownload PDF (820K) -
KATSUYOSHI UCHINO, SADAO ISOZAKI, NAOMI TANAKA, YUKIYA SAITOH, FUJIO N ...1987 Volume 35 Issue 1 Pages 370-376
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSFurosemide (FD) and spironolactone (SP) were co-administrated to human volunteers, and the pharmacokinetics and time course of diuresis were examined. The time courses of FD plasma concentration and diuresis after a single co-administration of FD plain tablet and SP were similar to those in the case of FD plain tablet. However, the plasma concentration of SP metabolites (determined as canrenone) during the 2-6 h period after a single co-administration of FD plain tablet and SP was about 0.05-0.15μg/ml higher than that after administration of SP. The steady-state distribution volume of SP metabolites after co-administration of FD plain tablet and SP was about 30% less than that after administration of SP, while the elimination rate constant of SP metabolites was about 1.5-fold greater. The diuresis during 24 h after a single administration of SP was 0.1-0.31.
After multiple administration of SP, the plasma concentration of SP metabolites during the 2-6 h period after co-administration of FD plain tablet and SP was also about 0.1-0.3μg/ml higher than expected from the time course of SP metabolites simulated by using the data obtained after a single administration of SP. The elevation of SP metabolites concentration in plasma was prevented without any change of diuresis over 24 h by using FD retard capsule instead of FD plain tablet.
We concluded that the phenomenon of elevation of SP metabolites concentration in plasma was caused by FD plain tablet, which induced strong diuresis and considerable loss of body fluids within a short time.View full abstractDownload PDF (1164K) -
KEISHIRO MIYAKE, FUKIKO KITAURA, NOBUYASU MIZUNO, HIROSHI TERADA1987 Volume 35 Issue 1 Pages 377-388
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe availability of porous polymer gel as a stationary phase in high-performance liquid chromatography (HPLC) for determination of the partition coefficient between octanol and water (Poct), and the acid dissociation constant (pKA) was examined for a wide variety of compounds.
The log of capacity factor k' increased linearly with increase in log Poct, when the hydrogen bonding ability of compounds was taken into account. However, aromatic compounds that possess an amino group such as procaine, anilines and sulfonamides showed anomalous chromatographic behavior from the viewpoint of the hydrogen-bonding ability. Furthermore, quinolines and pyridines also were anomalous. With these chromatographic characteristics in mind, log Poct can be determined very accurately for various compounds by HPLC over a wide range of pH.
Since this stationary phase is stable over a wide range of pH, HPLC could be run in the alkaline region, in contrast to the octadecyl silica (ODS) column, which is unstable above pH 7. From the capacity factor k' at various pH, pKA values of various acids, bases and amphoteric compounds were determined very accurately.
In conclusion, the porous polymer gel can be used as a stationary phase in HPLC in a range between acidic and alkaline regions. This stationary phase is effective for determining Poct and pKA values simultaneously or separately.View full abstractDownload PDF (1607K) -
KOICHIRO MIYAJIMA, MASATOSHI IKUTO, MASAYUKI NAKAGAKI1987 Volume 35 Issue 1 Pages 389-393
Published: January 25, 1987
Released on J-STAGE: October 19, 2009
JOURNAL FREE ACCESSThe formation constants of short chain alkylammonium salt-cyclodextrin complexes in aqueous solutions were investigated by conductometry for various values of alkyl chain length and the number of alkyl groups attached to the nitrogen atom. α-Cyclodextrin (α-CD), β-CD and γ-CD form complexes with alkylammonium salts having alkyl groups longer than n-butyl, n-hexyl and n-decyl, respectively. The formation constants of n-alkylammonium salts with α-CD increase with the number of alkyl groups attached to the nitrogen atom. The entropy change of complex formation was negative. The effect of the terminal group on the complex formation is discussed in relation to the formation constants of alkanol-CD complexes.View full abstractDownload PDF (644K)