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Volume 27, Issue 3
Displaying 1-43 of 43 articles from this issue
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MASAHIRO NAKANO, NAONORI KOHRI, YOSHIKO ARAKAWA, TAKAICHI ARITA1979 Volume 27 Issue 3 Pages 573-577
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe permeation of chlordiazepoxide, diazepam, oxazepam, lorazepam, nitrazepam, and nimetazepam through a dimethylpolysiloxane membrane and that of chlordiazepoxide, oxazepam, and nitrazepam through an ethylene-vinyl acetate copolymer membrane were investigated using a newly designed permeation cell. Large permeability values of diazepam and nimetazepam were attributed to their large partition coefficients. Large lag time values of chlordiazepoxide, oxazepam, and nitrazepam through the silicone membrane were rationalized by adsorption of these drugs on silica filler within the silicone membrane. Thus permeation data of these drugs can be interpreted on the basis of their physical properties.View full abstractDownload PDF (640K) -
KAZUNAGA FUKAWA, OSAMU IRINO, KOUICHI MARUYAMA, YASUTSUGU OHSAWA, KIYO ...1979 Volume 27 Issue 3 Pages 578-585
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe metabolism of pentazocine was studied in the rat following oral administration. After the enzymatic hydrolysis of the urine, eight metabolites including unchanged pentazocine were extracted with organic solvents and XAD-2 column, and isolated by preparative thin-layer chromatography. These metabolites were characterized by gas-liquid chromatography, and infrared, nuclear magnetic resonance and mass spectrometries. Unchanged pentazocine and three metabolites, 1, 2, 3, 4, 5, 6-hexahydro-8-hydroxy-α, 6 (eq), 11 (ax)-trimethyl-2, 6-methano-3-benzazocine-3-trans-2-buten-1-ol (trans-OH), 1, 2, 3, 4, 5, 6-hexahydro-8-hydroxy-α, 6 (eq), 11 (ax)-trimethyl-2, 6-methano-3-benzazocine-3-crotonic acid (trans-COOH) and norpentazocine were identified by comparison with corresponding authentic samples, and four other metabolites were characterized to be 1, 2, 3, 4, 5, 6-hexahydro-8-hydroxy-α, 6 (eq), 11 (ax)-trimethyl-2, 6-methano-3-benzazocine-3-cis-2-buten-1-ol (cis-OH), 9-methoxy pentazocine (or its 8-methoxyl-9-hydroxy isomer) and 8, 9 (or 9, 8)-methoxy hydroxy metabolites of cis-OH and trans-OH by spectral and chromatographic data. During 24 hr after oral administration, unchanged pentazocine was mainly excreted in the urine as the nonconjugated and conjugated forms. The amount of the other metabolites was found to be small.View full abstractDownload PDF (796K) -
YOKO KITAGAWA, YUKIO KUROIWA1979 Volume 27 Issue 3 Pages 586-591
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSWe investigated whether 3-methylcholanthrene (3MC) or phenobarbital (PB) which inhibit hepatocarcinogenesis of 3'-methyl-4-dimethylaminoazobenzene (3'-Me-DAB) block the decrease in intra- and extracellular pH (pHi and pHe) in the livers of rats on a diet containing 0.06% 3'-Me-DAB. In rats treated with 3MC or PB alone, pHe and pHi levels remained within normal limits. In rats on the 3'-Me-DAB diet, pretreatment with 3MC or PB prevented a pH decrease in the 1st and 5th weeks after inception of the 3'-Me-DAB diet. In partially hepatectomized rats on a basal diet, no pHe or pHi decrease in the regenerating liver was noted at 24 and 48 hr after hepatectomy. However, in partially hepatectomized rats on the 3'-Me-DAB diet, a significant pHi decrease in the regenerating liver was observed. In rats administered with 50 ppm diethylnitrosamine in place of drinking water, liver nodules developed. However, pHe and pHi dropped only slightly. The administration of CCl4 or bromobenzene effected no significant decrease in pHe or pHi, however, a dose-response correlation was found to exist for CCl4.View full abstractDownload PDF (742K) -
MASANORI KUROYANAGI, MASAMICHI FUKUOKA, KUNITOSHI YOSHIHIRA, SHINSAKU ...1979 Volume 27 Issue 3 Pages 592-601
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFour pterosins, illudoid sesquiterpenes, and nine pterosides, the glucosides, were isolated from the rhizomes of Pteridium aquilinum var. latiusculum. The stereostructures of the new compounds were elucidated by chemical and physical methods based on the structures established for the compounds obtained from the fronds.View full abstractDownload PDF (1120K) -
ATSUSHI NUMATA, KAZUKO HOKIMOTO, ATSUKO SHIMADA, HIDEO YAMAGUCHI, KIYO ...1979 Volume 27 Issue 3 Pages 602-608
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBiting responses were obtained in the larvae of the yellow butterfly, Eurema hecabe mandarina DE L'ORZA, to four chemical constituents of their host plant, Lespedeza cuneata G. DON, namely, D-fructose (II), myo-inositol (III), D-pinitol (IV), and 6, 8-di-C-pentosylapigenin (V).View full abstractDownload PDF (755K) -
MIYOKO SUZUKI, YOSHIO SASAKI1979 Volume 27 Issue 3 Pages 609-619
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe complex formation molar ratio of methyl orange and cyclodextrin, position and freedom of motion after inclusion were examined by nuclear magnetic resonance (NMR). 1) Methyl orange forms 1 : 1 complexes with α- and β-cyclodextrin. 2) Methyl orange is included predominantly from the N, N-dimethylamino group side. α-Cyclodextrin includes firmly methyl orange at the N, N-dimethylaniline side and β-cyclodextrin includes methyl orange at the benzenesulfonate side with little perturbation. 3) The data of 1H NMR showed that α- and β-cyclodextrin include methyl orange in the whole of the cavity and the results of 13C NMR showed that deformation at the linkage positions of glucose is detectable.View full abstractDownload PDF (1014K) -
FAROUK H. AL-HAJJAR, AHMAD Y. KASSIM1979 Volume 27 Issue 3 Pages 620-624
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIonization constants, pKa, for a set of six monothiodiacylmethanes have been determined in 50 vol% ethanol-water mixture at 25°±0.1. Excellent linear correlations are obtained when pKa values are plotted against the substituent constant, σx, and the polar substituent constant, σ*xC6H4, for substituted phenyl groups. The regression lines are : pKa=8.00-1.47 σx and pKa=8.92-1.195 σ*xC6H4, respectively. The pKa values are also correlated with the extended Hammett equation. The correlation follows the equation : pKa=7.717-1.330σI, x-1.248σR, x The rate of the oxidation of (Ie) with hexacyanoferrate (III) was discussed at different pH values.View full abstractDownload PDF (599K) -
AKIHIKO ISHIDA, SHIGEYOSHI SAIJO, KATSUYUKI NOGUCHI, MASAO WADA, OSASI ...1979 Volume 27 Issue 3 Pages 625-632
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSynthesis of 10-oxa-11-deoxyprostaglandin E1 (2b) and related compounds (2a, 17b, and 20) was successfully accomplished starting from nonanedioic acid (3). Decarboxylation of 3, 3-di-tert-butoxycarbonyl-2-(6-methoxycarbonyl) hexyl-4-butanolide (6) by heating gave predominantly trans-3-carboxy-2-(6-methoxycarbonyl) hexyl-4-butanolide (7a). Conversion of 7a into the hydroxymethyl lactone (13) and the Pfitzner-Moffatt oxidation of 13 provided trans-3-formyl-2-(6-methoxycarbonyl) hexyl-4-butanolide (14) which served as a key intermediate. The Wittig reaction of 14 with dimethyl 2-oxoheptylphosphonate gave enone (15) which was converted to 10-oxa-11-deoxy PGE1 methyl ester (16b) by NaBH4 reduction. Alkaline hydrolysis of 16b and relactonization of the resulting diacid (17b) gave 2b as crystals in a good yield.View full abstractDownload PDF (945K) -
HIROYUKI MASAYASU, MASANORI YOSHIOKA, ZENZO TAMURA1979 Volume 27 Issue 3 Pages 633-637
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS^3H-Epinephrine is used as the substrate for the assay, and 3H-metanephrine, the product, is efficiently separated by an adsorption column chromatography on amberlite XAD-4. This radiochemical assay method is simple, highly sensitive, and quantitative, and put to practical use of the measurement of the activity of catechol-O-methyltransferase in red blood cells.View full abstractDownload PDF (591K) -
SHOJI OZEKI, KIKUO TEJIMA1979 Volume 27 Issue 3 Pages 638-646
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe binding of basic compounds to bovine serum albumin (BSA) was studied by the fluorescence method, using N-phenyl-1-naphthylamine (NPN) and 1-anilinonaphthalene-8-sulfonate (ANS) as fluorescent probes. The spectral property of these probes was used for an indirect measurement of the binding of basic compounds to BSA. The compounds used in the present investigation were chlorpromazine, diazepam, chlordiazepoxide, nitrazepam, aniline, and acetanilide. Its results demonstrated that these compounds bind to the hydrophobic regions on the albumin molecule. It appeared that these compounds may be located at least near a tryptophan residue of albumin and two probes may bind at the same site. In the case of chlorpromazine, this drug competed with NPN but not with ANS in binding to BSA. Competitive binding between these compounds, except chlorpromazine, and the probes was observed. The significance of these results was discussed in relation to various types of binding forces. NPN is a useful probe in the evaluation of interactions of basic compounds to serum albumin, but the usefulness of the probe technique may be limited in that binding studies are related only to the site to which the probe binds.View full abstractDownload PDF (968K) -
KAZUO T. SUZUKI, TAMIO MAITANI, SHINJI TAKENAKA1979 Volume 27 Issue 3 Pages 647-653
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIsolated rat liver metallothionein was injected intraperitoneally into female rats to find whether or not the injected metallothionein was recovered from the kidneys with high copper content as in the case of rat kidney metallothionein induced by exposure to inorganic cadmium ion. The distribution patterns of cadmium and zinc among protein fractions in the kidney supernatants changed dramatically within one day after the injection. The changes were explained by the degradation and re-synthesis of the injected metallothionein in the kidneys. Copper was not found as a major metal in any metal-lothionein fractions obtained from the kidney supernatants. This is in marked contrast to cadmium ion-exposed rat kidney metallothionein. The relationships between the selective and profound toxicity of the injected metallothionein to the tubular lining cells and the changes of the chemical forms of cadmium were also discussed.View full abstractDownload PDF (777K) -
KAZUYUKI KIZUKI, HIROSHI MORIYA, CHIAKI MORIWAKI1979 Volume 27 Issue 3 Pages 654-661
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSome enzymatic properties of the new potent kinin inactivating enzyme (named as Shimeji kininase) which was purified from a mushroom Tricholoma conglobatum (Shimeji, in Japanese) were studied. This enzyme inactivated bradykinin, kallidin and Met-Lys-bradykinin by the ratio of 1.0 : 1.0 : 1.5, respectively, calculated as the molar ratio, and its Km value for bradykinin hydrolysis was 1.9 μM. Isoelectric point and molecular weight of the enzyme were 4.5 and 6.6×104, respectively. Optimum pH of this enzyme was 7.4 and it was comparatively stable at pH 6-9. This enzyme was thermolabile, i.e., more than 50% of the activity vanished by heating at 45° for 10 min and completely vanished at 60° for 10 min. The chelating agents, trasylol, SBTI and bradykinin potentiator B had no detectable influence upon the kininase activity of the enzyme. TLCK, TPCK and DFP weakly inhibited the enzymatic activity. The mercurials strongly inhibited the enzymatic activity of it and the inhibited activity was restored by adding excess amount of 2-mercaptoethanol. Accordingly, sulfhydryl groups in the enzyme molecule are requisite for its kininase activity and this enzyme may be classified as the thiol enzyme. The enzyme hydrolyzed the amino terminal substituted peptides such as Bz- and Z-derivatives while N-terminal free di- or tri-peptides were hardly hydrolyzed by it.View full abstractDownload PDF (866K) -
KAZUYUKI KIZUKI, HIROSHI MORIYA, CHIAKI MORIWAKI1979 Volume 27 Issue 3 Pages 662-669
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe suppression of kinin action in the body by Shimeji kininase was studied in rat. This enzyme was purified from a mushroom Tricholoma conglobatum (Shimeji, in Japanese) and had the highest kinin inactivating activity among the ever known kininases from plants. The enzyme was stable in rat plasma for a long time in vitro. The enzyme also maintained the activity in the plasma in vivo and the loss of activity from the rat vascular system was too small even 1 hr after the intravenous injection of it. This enzyme markedly suppressed the hypotensive effect of bradykinin and the capillary permeability increase induced by bradykinin. In contrast with this, the hypotension caused by acetylcholine and the capillary permeability increase by histamine and serotonin were not suppressed by this enzyme. From these observation, this enzyme was considered to be able to block the kinin action in the body for a certain period due to the rapid kinin destruction by it. The enzyme also had the potent anti-inflammatory activity on the rat paw edema induced by carrageenin.View full abstractDownload PDF (936K) -
HIROSHI TOMISAWA, HIROSHI HONGO, HIDEKI KATO, TAKAFUMI NARAKI, REIKO F ...1979 Volume 27 Issue 3 Pages 670-675
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThese studies have been made to get the Diels-Alder adducts having one substituent based on dienophiles. Reaction of 1-methyl-2 (1H)-pyridone (I) with methyl acrylate was carried out. The main product of this reaction followed by hydrolysis was 2-methyl-3-oxo-2-azabicyclo [2. 2. 2] oct-7-ene-6-endo-carboxylic acid (V). When the reaction of I with acrylonitrile was carried out, the products obtained were 7-endo-cyano-2-methyl-3-oxo-2-azabicyclo [2. 2. 2] oct-5-ene (XI), 7-exo-cyano-2-methyl-3-oxo-2-azabicyclo [2. 2. 2] oct-5-ene (XII), and 8-exo-cyano-2-methyl-3-oxo-2-azabicyclo [2. 2. 2] oct-5-ene (XIII).View full abstractDownload PDF (754K) -
YASUMITSU TAMURA, HIROSHI KIYOKAWA, YASUYUKI KITA1979 Volume 27 Issue 3 Pages 676-681
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhotolysis of mono-and di-β-ketovinyl sulfones in benzene solution caused an extrusion of sulfur dioxide to give the corresponding β-phenyl enone and bis-enones in moderate yields, respectively, and that of di-β-ketovinyl sulfide and sulfoxide was also examined.View full abstractDownload PDF (715K) -
HIROTUGU YAMASHITA, KEIICHI ITO, YOSHIYASU TERAO, MINORU SEKIYA1979 Volume 27 Issue 3 Pages 682-687
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA superior method for generation of diazomethane and several other gaseous diazoalkanes has been provided by alkali treatment of N-[(N-nitrosoalkylamino) methyl]-carbamates, especially their isopropyl esters, which react smoothly in high yields (81-82% for diazomethane).View full abstractDownload PDF (698K) -
MASAYASU YAMAMOTO, TOYOZO UNO1979 Volume 27 Issue 3 Pages 688-690
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSQuinonedichlorodiimide (I) reacts with aromatic secondary and tertiary amines to yield green colored compounds. The chemical structure of these colored compounds is investigated from the spectral data (infrared, ultraviolet, nuclear magnetic resonance, mass) and the chemical reactions. The color of the reaction product of I and N-ethyl-m-toluidine (II) or N, N-diethyl-m-toluidine (III) is changed mutually between green and violet by oxidation and reduction. These results and the spectral data suggest that these reactions are electrophilic displacement reactions in the ortho or para position of the alkylamino group and I reacts with II or III at the rate of 1 : 2.View full abstractDownload PDF (428K) -
TOSHIO TSUJIMOTO, CHIZUKO KOBAYASHI, YOSHIO SASAKI1979 Volume 27 Issue 3 Pages 691-695
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS^<13>C and 1H nuclear magnetic resonance chemical shifts of 5-substituted pyrimidine derivatives were measured. The linear correlations of the chemical shifts between 5-substituted pyrimidines vs. monosubstituted benzenes, 3-substituted pyridines or substituent constants were revealed, and the chemical shift of pyrimidine derivatives can be predicted by the additivity rule.View full abstractDownload PDF (496K) -
SUSUMU TSUSHIMA, MICHIYUKI SENDAI, MITSURU SHIRAISHI, MASAYASU KATO, N ...1979 Volume 27 Issue 3 Pages 696-702
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSNew compounds 3-acetoacetoxymethyl-7β-acylaminoceph-3-em-4-carboxylic acids (4) were synthesized from deacetylcephalosporin C (3a), after N-protection of the amino-adipoyl group followed by acetoacetylation of the 3'-hydroxyl with diketene and acyl exchange at the 7-position. They underwent a facile nucleophilic displacement of the 3'-acetoacetoxy group with heterocyclic thiols to afford 7β-acylamino-3-heterocyclicthio-methylceph-3-em-4-carboxylic acids (6) including SCE-963 (6e) in good yields.View full abstractDownload PDF (843K) -
YOSHIKAZU MATSUSHIMA, YOSHIHARU KARUBE, AKIRA KONO1979 Volume 27 Issue 3 Pages 703-709
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe analyses of the electronic absorption spectra and the band assignments to the molecular species were carried out on the methanol solutions of the Schiff bases of pyridoxal (PL), pyridoxal N-methochloride (PLM), and related aromatic aldehydes with α, β-, β, γ-, and γ, δ-unsaturated amino acids and their methyl esters. The Schiff bases of PL with propargylglycine, allylglycine, and vinylglycine had spectra similar to those with a saturated amino acid, showing the unsaturated bond is not conjugated with the azomethine bond. In neutral and alkaline solutions of the Schiff bases of PLM with esters of alanine, propargylglycine, and allylglycine, 2-4% of the Schiff bases was deprotonated at the α-carbon atom, forming a quinoid species absorbing at 500 nm. With ester of vinylglycine, a species absorbing at 534 nm was formed, indicating the quinoid structure with an extended conjugation. It is suggested from the spectral analysis of the Schiff bases of methyl dehydrovalinate that in species protonated at the phenolate or the azomethine the molecule is not planar and the planarity is achieved through the metal chelation.View full abstractDownload PDF (740K) -
MICHIYA KIMURA, YOSHITAKA JIN, TAKUJI SAWAYA1979 Volume 27 Issue 3 Pages 710-714
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA model reaction was studied for the interaction between cholesterol (1) and molecular oxygen in biological matrices. An aqueous colloidal solution (60 ml) of 1 (2.7×10-4 mol) dispersed with sodium stearate (1.8×10-4 mol) was adjusted to pH 8 and energetically stirred at 85° without air-bubbling. Relative amounts of the sterols present in the reaction mixtures were determined every one hour by quantitative TLC and time-course of the oxyfunctionalization of 1 was followed for 9 hours. The major product in the early period was the 7-hydroperoxide (2) as an epimeric mixture of α : β≒1 : 2. The amounts of the 7-ketone (3) and 7-hydroxide (4) increased with decrease in that of 2 which was regarded as the intermediate. After passage of 7 hours the autoxidation system arrived at an apparent final state where consumption of 1 and formation of products were suspended and 2 was no longer detectable. More than 70% of 1 was likely to be consumed and the relative amounts of the oxygenated products (3, 4, and the 5, 6-epoxide) and the unchanged substrate (1) were in an approximate ratio of 45 : 25 : 5 : 25. The induction period was lost when a small amount (1×10-5 mol) of the 7α-hydroperoxide (2a) was initially present in the reaction mixture. From these results, the autoxidation of 1 under the conditions was assumed to have an ordinary pattern of the chain reaction initiated by the decomposition of hydroperoxide.View full abstractDownload PDF (657K) -
KOZO TAKAYAMA, NAOKI NAMBU, TSUNEJI NAGAI1979 Volume 27 Issue 3 Pages 715-720
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe interaction of sulfonamides with 18-crown-6 (1, 4, 7, 10, 13, 16-hexaoxacyclooctadecane) was studied, observing the effect on the spectroscopic properties of sulfonamides in chloroform solution. From the ultraviolet (UV) absorption spectra and the nuclear magnetic resonance (NMR) spectra, the stoichiometry and the stability constant K of the formation of complex were calculated. The measurement of K values according to the NMR method gives excellent results compared with that according to the UV method. On the other hand, it was observed that the binding mechanism was the inclusion of the primary amino group of 4-position of sulfonamides in the anionic cavity of 18 crown-6, and the hydrogen bonding might be a primary force of the formation of these complexes.View full abstractDownload PDF (591K) -
TSUKASA TAKAMURA, TAKU CHIBA, SETSUZO TEJIMA1979 Volume 27 Issue 3 Pages 721-725
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new synthetic route of N-acetyllactosamine is described. This starts from 2-O-tosylate or 2, 3'-di-O-tosylate of 1, 6-anhydro-4', 6'-O-benzylidene-β-lactose (1), which is the primary or the secondary major product of partial tosylation of compound 1 as reported in Part VIII of this series (T. Takamura and S. Tejima, Chem. Pharm. Bull. (Tokyo), 26, 1117 (1978)). The final product is isolated in about 10% yield from compound 1 via the following series of reaction : 1), monoepoxide formation, 2), azidolysis of the epoxide, 3), acetolysis of the azido sugar, 4), reduction of the azido group to amino group, followed by acetylation, and 5), de-O-acetylation.View full abstractDownload PDF (712K) -
TAKASHI HARAYAMA, MUNEO TAKATANI, YASUO INUBUSHI1979 Volume 27 Issue 3 Pages 726-730
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Diels-Alder reaction of 2-(3-acetoxypropyl)-5-methylcyclohex-2-en-1-one (9) with butadiene in the presence of aluminum chloride was examined. Inspection of the stereostructure of the adduct (8) indicated that addition of butadiene to the dienophile (9) took place stereoselectively from the side opposite to a secondary methyl group at C5 of the dienophile and that this type of Diels-Alder reaction is useful for synthesis of 8-deoxyserratinine type alkaloids. The dienophile (9) was regioselectively prepared from the ketone (10) by two routes. The first route involved the Claisen rearrangement of 12 obtained from 10 via 11. Subsequent conversions of the rearrangement product (13 ; yield, 60% from 11) gave the dienophile (9 ; yield, 26.5% from 14) via 14, 15, 16, 17, 18, and 19. The second route consisted in conversion of the acetal (20) obtained from the ketone (10) and acrolein diethyl acetal into the dienophile (9 ; yield, 70% from 20) via 21 and 22.View full abstractDownload PDF (685K) -
MASANORI KUROYANAGI, MASAMICHI FUKUOKA, KUNITOSHI YOSHIHIRA, SHINSAKU ...1979 Volume 27 Issue 3 Pages 731-741
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPterosins and pterosides, 1-indanone derivatives isolated from bracken (Pteridium aquilinum var. latiusculum), and the derivatives exhibit CD Cotton effects associated with n→π* transition of conjugated ketones in the range of 310-370 nm. Snatzke's rule was applied to the compounds and the conformations of the indanones were discussed from the observations by the CD. The conformation of pterosin A type compounds having a hydroxymethyl group at the 2-position is affected by the intramolecular hydrogen bonding. In pterosin C and L type compounds bearing a hydroxyl group at the 3-position, the hydroxyl group exists in pseudoaxial conformation irrespective of the configuration at the 2-position. The results obtained by the compounds of the established stereochemistry by chemical methods were applied for the determination of the absolute configurations of pterosin D type compounds.View full abstractDownload PDF (910K) -
HIROSHI HOSODA, YASUO SAKAI, HIROKO YOSHIDA, SHINICHI MIYAIRI, KAZUO I ...1979 Volume 27 Issue 3 Pages 742-746
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe N-hydroxysuccinimide esters of testosterone and cortisol were prepared from the corresponding carboxylic acid derivatives by a carbodiimide method. These activated esters were covalently linked to bovine serum albumin in organic solvent/phosphate buffer (pH 7.4) employing various molar ratios of the steroid to protein. The results indicated that the activated ester method would be useful for enzyme labeling in enzyme immunoassay of steroids in respects of simplicity and reproducibility.View full abstractDownload PDF (579K) -
SHIRO TERASHIMA, CHUNGCHYI TSENG, KENJI KOGA1979 Volume 27 Issue 3 Pages 747-757
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSWith an aim to further explore the utility of L-α-amino acids (I) in the synthesis of optically active compounds, the reaction of optically active α-tosyloxy acids and their derivatives (III) readily obtainable from I, with several types of organocopper reagents were studied. Although there still remain some ambiguity in the formation of unusual reaction products such as the β-keto ester (dl-6) and the vicinal diol ((R)(+)-13) and in lower yields for the substitution products, it has become evident that when optically active α-tosyloxy acids prepared from L-phenylalanine, L-alanine, and L-leucine, respectively, are treated with lithium dialkyl- or diarylcuprates, the substitution reactions can proceed with almost full inversion to give corresponding optically active α-alkyl or α-aryl acids in max. 63% yield.View full abstractDownload PDF (1373K) -
SHIRO TERASHIMA, CHUNGCHYI TSENG, MASAJI HAYASHI, KENJI KOGA1979 Volume 27 Issue 3 Pages 758-764
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of (S) (-)-α-tosyloxy acid ((S)(-)-3) with methyl- or n-butyllithium was found to afford (R)(+)-vicinal (vic)-diol ((R)(+)-4) in an excellent yield with almost full inversion. On the other hand, when (S)(-)-α-hydroxy acid ester ((S)(-)-5) was allowed to react with methyl- or n-butyllithium, (S)(-)-vic-diol ((S)(-)-4) was obtained in an excellent yield with full retention. Since (S)(-)-3 and (S)(-)-5 are both derivable from L-phenylalanine (L-1), it has become possible to obtain an enantiomeric pair of vic-diols from L-1. Plausible formation mechanism for (R)(+)-4 from (S)(-)-3 was proposed. The utility of optically active vic-diols in natural product synthesis was also visualized by preparing the novel synthetic intermediate for epoxyterpene synthesis ((S)(-)-6) from (S)(-)-4a.View full abstractDownload PDF (841K) -
AKIRA SATO, RYOJI IMAI, NOBUHIRO NAKAMIZO, TADASHI HIRATA1979 Volume 27 Issue 3 Pages 765-770
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSGuanine and xanthine nucleoside derivatives (3, 4 and 6) bearing nitrosourea functional groups were synthesized from guanine nucleoside ureas (2) obtained by the reaction of 2'-deoxy-2'-aminoguanosine (1) with isocyanates and their antitumor activity against sarcoma-180 solid tumor and leukemia L-1210 were determined. Among the compounds tested, 2'-deoxy-2'-[3-(2-chloroethyl)-3-nitrosoureido]-xanthosine (4b) found to have the most potent activity. Moreover, very slight decrease in white blood cells of mice bearing sarcoma-180 solid tumor was observed after administration of 4b.View full abstractDownload PDF (764K) -
SHUNICHI HASHIMOTO, SHUNICHI YAMADA, KENJI KOGA1979 Volume 27 Issue 3 Pages 771-782
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe 1, 4-addition of Grignard reagents to the chiral α, β-unsaturated aldimines (3d, e), prepared from α, β-unsaturated aldehydes (1) and optically active tert-leucine tert-butyl ester (2d), afforded, after hydrolysis, optically active β-substituted aldehydes (4) in 91-98% enantiomeric excess. The present method has advantages in giving aldehydes (4) in high enantiomeric purities, allowing easy preparation of the aldimines as well as easy recovery of optically active tert-leucine tert-butyl ester (2d) without any racemization for reuse, and exhibiting general utility. The possible mechanism of the reaction, by which the absolute configuration of the aldehydes (4) is unequivocally predictable, is proposed.View full abstractDownload PDF (1288K) -
TOSHIAKI MIURA, HIDETOSHI TAKAGI, MICHIYA KIMURA1979 Volume 27 Issue 3 Pages 783-788
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMechanism was investigated for the chromogenic reaction of testosterone (I) with sulfuric acid. Dication (II in Chart 1) produced at the primary stage of the reaction was transformed into the chromophoric χ-484 (XIIa in Chart 4) via its conjugate base (VIII in Chart 4) by acid-base catalyzed isomerization. The conjugate base of the χ-484 (XIIb), 17, 17-dimethyl-18-norandrosta-4, 6, 8 (14)-trien-3-one (XIb), was isolated in 40% yield in the reaction of the epoxide (V in Chart 2) with sulfuric acid. Sulfuric acid solution of the trienone (XIa, b) showed a maximum absorption at 484 nm (ε=42000). The pKa value of XIIa was also determined.View full abstractDownload PDF (618K) -
HARUHIKO YAMAMOTO, HITOSHI TAKEI, TOSHIO YAMAMOTO, MICHIYA KIMURA1979 Volume 27 Issue 3 Pages 789-792
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Fe3+-catalyzed decomposition of hydrogen peroxide has been investigated in mediums composed of water and acetonitrile in various ratios. The ratios of the amount of decomposed hydrogen peroxide to that of oxygen evolution are in proportion to the average ratios of acetonitrile concentration to hydrogen peroxide in the low acetonitrile content. It shows that the oxidant produced on the Fe3+-catalyzed decomposition of hydrogen peroxide is hydroxyl radical. The linear relationship could not be found in high acetonitrile concentration. The oxidant produced on the Fe3+-catalyzed decomposition of hydrogen peroxide in high acetonitrile concentration was discussed in relation to the oxidant (ferryl ion) produced in hemoprotein catalyzed decomposition of hydrogen peroxide.View full abstractDownload PDF (499K) -
HARUO SAIKACHI, TOKUJIRO KITAGAWA, HIDEAKI SASAKI, ALBERTM.VAN LEUSEN1979 Volume 27 Issue 3 Pages 793-796
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of tosylmethyl isocyanide (2) with heteroaromatic aldehydes, i.e., 2-furaldehyde (1a), 5-nitro-2-furaldehyde (1b) and 5-methoxycarbonyl-2-furaldehyde (1c) ; thiophene-2-carbaldehyde (1d) and 5-nitrothiophene-2-carbaldehyde (1e) ; 1-methylpyrrole-2-carbaldehyde (1f) ; 2-, 3- and 4-pyridinemonocarbaldehyde (1g, 1h and 1i) in the presence of an equimolar amount of potassium carbonate in refluxing methanol afforded the corresponding 5-substituted oxazoles (3a-i). However, a similar treatment of pyrrole-2-carbaldehyde (4) with 2 gave 3-tosylpyrrolo [1, 2-c] pyrimidine (6) instead ; a mechanism for this reaction is proposed.View full abstractDownload PDF (463K) -
MASAKO MAEDA, AKIO TSUJI1979 Volume 27 Issue 3 Pages 797-800
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA high performance liquid chromatography method for the determination of copperoxinate in plant tissues was developed. The method involves isolation of the residue by extraction with acetone, decomposition of extracted residue to 8-hydroxyquinoline by masking copper (II) ion with potassium cyanide followed by high performance liquid chromatography with a fluorimetric detector. Non-fluorescent 8-hydroxyquinoline separated from copper-oxinate was converted to a highly fluorescent chelate and eluted from the column by the eluent containing Al (III) ion. The lowest limit of detection and recoveries from plant tissues sample were about 0.01 ppm and 86.1-103.1%, respectively.View full abstractDownload PDF (540K) -
KAZUHIKO SAGARA, KONOMI IKUNAGA, KOHJI KASUYA, TSUNETOSHI KAITO, TOSHI ...1979 Volume 27 Issue 3 Pages 800-803
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA simple gas-liquid chromatographic method was developed for the determination of inositol in multivitamin preparation containing large amounts of sugars. Sample multivitamin preparation was trimethylsilylated and separated on a 2% OV-101 column. The quantitations were achieved by the peak height ratio method using methyl arachidate as an internal standard. Inositol in 13 synthetic mixtures containing large amount of various sugars (200 to 1000-fold amount) was determined successfully by the present method.View full abstractDownload PDF (514K) -
YOSHITAKA AKASAKA, TOSHIAKI MORIMOTO, MINORU SEKIYA1979 Volume 27 Issue 3 Pages 803-805
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe present paper describes our finding that diazoalkanes react with N, N-dialkylaminomethyl arenesulfonates affecting the insertion of alkylidenes into the methylene carbon-oxygen bond.View full abstractDownload PDF (475K) -
HIROSHI YAMANAKA, MINAKO KOMATSU, SHIGERU OGAWA, SHOETSU KONNO1979 Volume 27 Issue 3 Pages 806-809
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to introduce a carbon substituent to the α-position of the quinoline ring, the condensation of quinoline 1-oxide (VII) with the primary enamines, such as ethyl 2-ethoxycarbonyl-(IIIb), ethyl 2-benzoyl-(IIId), ethyl 2-cyanoacetimidate (IIIe), and 2-ethoxycarbonylacetamidine (IIIc), was investigated. The reaction of VII in the presence of benzoyl chloride afforded the following products : ethyl 2-ethoxycarbonyl-2-(2-quinolyl) acetimidate (VIII), 65% ; ethyl 2-benzoyl-2-(2-quinolyl) acetimidate (X), 54% ; ethyl 2-cyano-2-(2-quinolyl) acetimidate (XI), 29% ; ethyl 2-diaminomethylene-2-quinolylacetate (XII), 62%. The similar reaction proceeded in the case of isoquinoline 2-oxide.View full abstractDownload PDF (578K) -
HIROSHI TOMISAWA, HIDEKI KATO, REIKO FUJITA, HIROSHI HONGO1979 Volume 27 Issue 3 Pages 810-812
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Diels-Alder reaction of 4-cyano-1-methyl-2 (1H)-pyridone (I) with 2, 3-dimethyl-1, 3-butadiene (II) was carried out. The products obtained were cis and trans-4a-cyano-4a, 5, 8, 8a-tetrahydro-2, 6, 7-trimethyl-1 (2H)-isoquinolone (III and IV) and 2, 6, 7-trimethyl-1 (2H)-isoquinolone (V).View full abstractDownload PDF (481K) -
SHINZO TANABE, TAKEICHI SAKAGUCHI1979 Volume 27 Issue 3 Pages 813-815
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA simple and specific method for the determination of moroxydine in serum was established by the use of ion-exchange chromatography and a modified Voges-Proskauer colorimetric reaction. Moroxydine over the range of 5 to 70 μg was determined by the measurement of absorbance at the absorption maximum (520 nm) of the colored product formed in the reaction of moroxydine with diacetyl-3, 5-dihydroxybenzoic acid reagent in alkaline solution. An anion-exchange column chromatography (carboxylate resin) was effectively used to remove the interferences present in the serum. The rabbit serum containing moroxydine was applied directly to the column, without pretreatment, and the column was eluted first with 0.01M NaOH, followed by 0.2M NaOH. The recovery of moroxydine added to serum was between 99 and 102% and the coefficient of variation was between 1.49 and 2.27%.View full abstractDownload PDF (456K) -
NORIO MINAMI, SHIZUMASA KIJIMA1979 Volume 27 Issue 3 Pages 816-820
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIt was found that the ethoxycarbonyl derivative (2) of salicylic acid (1) was reduced to o-cresol (3) with sodium borohydride in good yield and the best reaction conditions were the use of 4 molar equivalents of sodium borohydride in tetrahydrofuran-H2O at 5-15.°p-Hydroxybenzoic acid (4) and m-hydroxybenzoic acid (6) did not give the corresponding cresols in this procedure, and o-hydroxyphenylacetic acid (8) did not give o-ethylphenol. These results show that the existence of o-hydroxy group is necessary to reduce the carboxyl groups to the methyl groups and only the carboxyl groups which are directly attached to aromatic nuclei are reduced to the methyl groups. Several o-hydroxybenzoic or -naphthoic acids (1, 10, 12, 15, 17, 19 and 24) were reduced to the corresponding o-methylphenols in good yields. It was found that all hydrogen atoms of the methyl group were introduced from sodium borohydride.View full abstractDownload PDF (536K) -
AKIRA SATO, RYOJI IMAI, NOBUHIRO NAKAMIZO, TADASHI HIRATA1979 Volume 27 Issue 3 Pages 821-823
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS9-(2-Deoxy-2-amino-β-D-arabinofuranosyl) adenine (IIIa) and guanine (IIIb) were synthesized from the corresponding azide compounds (II) obtained by nucleophilic substitution of tosyloxy groups of 2'-O-p-toluensulfonyladenosine (Ia) and guanosine (Ib), respectively. Their antitumor activity against sarcoma-180 solid tumor and cytotoxic activity against HeLa-S3 cells were determined.View full abstractDownload PDF (488K) -
TAKEFUMI MOMOSE, SHOHGO ATARASHI1979 Volume 27 Issue 3 Pages 824-828
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Baeyer-Villiger oxidation, which is known to be unsuccessful with the bicyclo [3. 3. 1] nonan-3-one system, was shown to proceed smoothyl with the 3, 7-dioxo compounds 1 and 6. The particular steric factors affecting the reaction of these and related systems are discussed.View full abstractDownload PDF (648K) -
YOSHINORI KIDANI, KENJI INAGAKI, TAMOTSU YASHIRO, TAZUKO TASHIRO, SHIG ...1979 Volume 27 Issue 3 Pages 829-830
Published: March 25, 1979
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDichloro-trans-(dl)-1, 2-cyclopentanediamineplatinum (II) and its derivatives, mixed ligand complexes with oxalato, malonato, or sulfato, were synthesized and tested against Leukemia P-388. All of these complexes have high antineoplastic activity. Among them sulfato-trans-(dl)-1, 2-cyclopentanediamine revealed a very high therapeutic index and is more effective than the corresponding complex of 1, 2-cyclohexanediamine.View full abstractDownload PDF (362K)
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