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HIROAKI NOMURA, YASUO NOGUCHI, HIDEYUKI HIRANO, KATSUAKI MIYATA
1968 Volume 16 Issue 10 Pages
1867-1875
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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A new type of acid soluble cellulose derivatives, in particular cellulose acetate N, Ndibutylaminohydroxypropyl ether (CABP), have been prepared by the reaction of 1-dialkylamino-2, 3-epoxypropanes with the hydroxyl groups in partially hydrolyzed cellulose acetate. The CABP, besides being soluble in a number of common organic solvents, is also soluble in buffer solutions below pH 5.0 but not in neutral aqueous solutions. The compound, therefore, has been found a use in the film coating of tablets which are disintegrated in gastric juice. Water vapor permeability, tensile strength and percent elongation of the free film were tested in comparison with that of cellulose acetate phthalate. The practical coatings on tablets and the disintegration testings were carried out. These results, especially good film forming property, ease of handling and good stability of the film indicated that the CABP was practically useful as a tablet coating agent.
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HISASHI NOGAMI, JUN HASEGAWA, TOHORU MATSUOKA, TADAAKI RIKIHISA
1968 Volume 16 Issue 10 Pages
1876-1880
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The hydrolysis of phthalylsulfathiazole at 60° was studied. The pH-rate profile was similar to that of phthalamic acid in acidic region, and rate constant of intramolecular reaction was 1.12×10
-3 sec
-1. In strong alkaline region the rate was proportional to hydroxide ion concentration and the rate constant was 3.80×10
-6 liter·mole
-1 sec
-1. Reaction species were discussed in relation to observed rate constants and the rate expression was presented. ΔH
≐̸ was 18.1 kcal/mole and ΔS
≐̸ was -17.9 e.u.
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SHOJI TAKEMURA, KAZUO OTSUKI, KATSUKO OKAMOTO, YOSHIO UENO
1968 Volume 16 Issue 10 Pages
1881-1884
Published: October 25, 1968
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Reaction of N, N-dibromobenzenesulfonamide with dihydropyran in 1 : 1 molar ratio was investigated. In the first step, unstable N-bromo addition product (III) was formed ; then the bromine atom at nitrogen was reduced by the treatment with ethanol or water and a mixture of stereoisomers (IV and V) was obtained. The structures of IV and V were established.
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KAZUO OTSUKI, SHOJI TAKEMURA, KATSUKO OKAMOTO, YOSHIO UENO
1968 Volume 16 Issue 10 Pages
1885-1888
Published: October 25, 1968
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The reaction of N, N-dibromobenzenesulfonamide (I) with over two molar excess of dihydropyran (II) was investigated. Contrary to the result of the previously reported reactions of I with cycloalkenes, bis adducts, trans-trans and trans-cis types of N, N-(bis-3-bromotetrahydropyranyl-2) benzenesulfonamide (VI and VII) were obtained. And when N-methyl-N-bromobenzenesulfonamide (X) was made to react with II, addition reaction predominantly occurred, giving N-methyl-N-(3-bromotetrahydropyranyl-2) benzenesulfonamide (XI).
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SADAO OHKI, MITSUO AKIBA, HIROKO(MASUMOTO) SHIMADA, KAZUE KUNIHIRO
1968 Volume 16 Issue 10 Pages
1889-1899
Published: October 25, 1968
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The four kinds of stereoisomers of perhydrobenzo [c] quinolizine were isolated as picrates of mp 203-205°, mp 182-184°, mp 171°, and mp 155°, whose stereostructures were elucidated as IIIa, IIIb, IIIg, and IIId (or IIIh), though the last one was not determined conclusively due to the minute quantity available.
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HIROSHI HIKINO, KEITARO AOTA, TSUNEMATSU TAKEMOTO
1968 Volume 16 Issue 10 Pages
1900-1906
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The sesquiterpenoid sugetriol, the triacetate of which was isolated from nutgrass, Cyperus rotundus (Cyperaceae), has been shown by spectral and degradative studies to be I.
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KAZUO TOMITA, MITSUO NAGANO
1968 Volume 16 Issue 10 Pages
1907-1910
Published: October 25, 1968
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The reaction of sodium xanthates of prim-α-acetylenic alcohols and methyl iodide in an aprotic solvent gave corresponding xanthates. But in the case of propargyl alcohol, in addition to propargyl xanthate, dipropargyl thioncarbonate and dimethyltrithiocarbonate could be isolated.
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KAZUO TOMITA, MITSUO NAGANO
1968 Volume 16 Issue 10 Pages
1911-1917
Published: October 25, 1968
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The reaction of sodium sec- and tert-α-acetylenyl xanthate with methyl iodide afforded corresponding α-acetylenyl xanthate in a few cases, and other products such as allenic dithiolcarbonate, thioncarbonate and cyclic compound were isolated in case by case. Nevertheless, in all cases, dimethyl trithiocarbonate (IV) was obtained. A certain correlation between the formations of α-acetylenyl xanthate, allenic dithiolcarbonate, and dimethyl trithiocarbonate (IV) was observed.
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ZENICHI HORII, TAKESHI IMANISHI, SANGWON KIM, ICHIYA NINOMIYA
1968 Volume 16 Issue 10 Pages
1918-1926
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The Michael condensation of ethyl 2-oxo-5-methylcyclohexanecarboxylate with acrolein proceeded stereospecifically to afford, upon intramolecular Aldol-type cyclization followed by dehydration, ethyl 3β-methyl-9-oxobicyclo (3, 3, 1) non-6-ene-1-carboxylate (IV), which was hydrogenated to 3β-methyl-9-oxobicyclo (3, 3, 1) nonane-1-carboxylate (V). The corresponding 3α-methyl derivative (XIX) was obtained from the Michael adduct of ethyl 2-oxocyclohexanecarboxylate with methacrolein. Configurations and conformations of the compounds prepared were established from the consideration of chemical and NMR evidences.
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HISAO YAMAMOTO, MASARU NAKAO, TADASHI OKAMOTO
1968 Volume 16 Issue 10 Pages
1927-1931
Published: October 25, 1968
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1-Heteroaroyl-2-methylindole-3-acetic acid derivatives are prepared by reacting the corresponding N
1-heteroaroylphenylhydrazine derivatives with levulinic acid. And these indole derivatives are also prepared by some other procedures. In one of these compounds, 1-nicotinoyl-2-methyl-5-methoxyindole-3-acetic acid, the existence of its dimorph is suggested by the infrared spectrum. The indole derivatives show a remarkable experimental anti-inflammatory activity having extremely low toxicity.
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SHOJI SHIBATA, TAMOTSU SAITOH
1968 Volume 16 Issue 10 Pages
1932-1936
Published: October 25, 1968
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A new isoflavan derivative, licoricidin, C
25H
32O
5, mp 161-162.5°, [α]
22.5°D+20° (MeOH) was isolated from licorice root. According to the results mostly deduced from nuclear magnetic resonance and mass spectral analyses, licoricidin would be represented as being 3', 6-diisopentenyl-2', 4', 5-trihydroxy-7-methoxyisoflavan (IXa).
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YASUNAO OGAWA, YUKIO KOMETANI, YOSHIKO BABA
1968 Volume 16 Issue 10 Pages
1937-1941
Published: October 25, 1968
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Although the effects of various agents on glutamic oxalacetic transaminase (GOT) in tissue have been studied, the presence of isoenzymes, which have different characters, showed the lack for quantitativity in many of assay methods and the possibility of misleading results. In this report, the assay procedure for this enzyme activity in liver homogenate of rats was modified respect to the existence of isoenzymes. One procedure is a modified manometric method consisting of a coupled-system with chemical decarboxylation of oxalacetate to eliminate the inhibitory action of mitochondrial enzyme (m-GOT), and the other is a new type of spectrophotometric procedure. The latter could also be employed for the approximate calculation of isoenzyme levels in homogenates in combination with electrophoretic procedures for isoenzymes ratio with cellulose acetate film.
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YASUNAO OGAWA, YUKIO KOMETANI, YOSHIKO BABA
1968 Volume 16 Issue 10 Pages
1942-1947
Published: October 25, 1968
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A new technique of mild denaturation of glutamic oxalacetic transaminase on the surface of cellulose acetate film was introduced as an application for an assay procedure of enzyme activity in crude materials. This treatment modified the enzymatic character of mitochondrial enzyme in the presence of phospholipids in crude preparations after which the isoenzymes were estimated quantitatively using a concentration of substrate adequate for the enzyme in the soluble fraction which was a minor component in rat liver.
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YASUNAO OGAWA, YUKIO KOMETANI, YOSHIKO BABA
1968 Volume 16 Issue 10 Pages
1948-1952
Published: October 25, 1968
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Glutamic oxalacetic transaminase (GOT) is one of main transaminase in liver. This enzyme has not been induced so active by glucocorticoids as other transaminases. However, the presence of isoenzymes and their characteristics were investigated and the same hormonal sensitivity to glucocorticoids was observed in the enzyme localized in the soluble fraction (s-GOT). In our present paper, the regulation by adrenal hormones was proven to be exist not only in s-GOT but also in the mitochondrial enzyme (m-GOT) which is major component in rat liver. Furthermore, it is suggested that catecholamines would play a role on defining of isoenzyme level in liver and leakage of enzyme from tissue.
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SHIRO TERASHIMA, SHUNICHI YAMADA
1968 Volume 16 Issue 10 Pages
1953-1971
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The thermal and photochemical decompositions of three types of optically active alkyl azidoformates (III) were attempted, and it was found in both cases, that optically active 2-oxazolidinones (VI) were obtained with nearly complete retention of configuration. The yield of VI was very low (5%) in the thermal decomposition and moderate (25-30%) in the photochemical one. Considering the relationship between stereospecificity and spin mutiplicity of alkoxycarbonyl nitrene (I), a mechanism was proposed suggesting that the singlet state alkoxycarbonyl nitrene (XXX) generated from III, either by heating or by irradiation, had been inserted into the intramolecular optically active C-H bond through the transition state (XXXII). Moreover, in the course of these studies, the absolute configuration of α-methylphenylglycine (2-amino-2-phenylpropionic acid) was determined using thermal decomposition. Preliminary experiments using racemic compounds were also reported.
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SADAO HIROTA, SATOSHI OSUGI, TAIZO HAYASHI, SHINICHIRO KAGA, YASUMITSU ...
1968 Volume 16 Issue 10 Pages
1972-1981
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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Lacey's theory, concerning a gas-solid reaction rate is applied to a stability study of a pharmaceutical solid. An accelerated air oxidation of ascorbic acid is analysed to predict its shelf life at room temperature as an example. The temperature dependence of the diffusion constant is found to be 48 kcal/mole, and that of the chemical reaction rate, 26 kcal/mole. The diffusion constant, and 2nd order reaction rate constant at 25° are estimated to be 1.6×10
-12cm
2/hr, and 4.3×10
-4 liter/mole-hr, respectively. The 1% degradation life of ascorbic acid in a disk of mannitol conglomerate containing 10% ascorbic acid is estimated to be about 200 years in the absence of moisture.
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SADAO HIROTA
1968 Volume 16 Issue 10 Pages
1982-1993
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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A new kinetical equation for a gas-solid reaction which is convenient for use in predicting the degradation of a pharmaceutical solid is derived, and a procedure of analyzing accelerated storage data is proposed. The procedure is applied to the air oxidation degradation of ascorbic acid in a mannitol conglomerate. The result of the analysis was consistent with that obtained by Lacey's procedure. With the proposed procedure, operational difficulties met in Lacey's procedure were overcome. The temperature dependence of diffusivity is found to be 56 kcal/mole, with an activation energy for the chemical reaction of 26 kcal/mole. The rate constant for the chemical reaction at 25° is estimated to be 3.3×10
-6 hr
-1, a value which is consistent with the results of Tardif, which were obtained from a different point of view.
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AKIRA AKAHORI, ISAMU OKUNO, TAMETO OKANISHI, TORU IWAO
1968 Volume 16 Issue 10 Pages
1994-1996
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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Steroidal sapogenins were extracted from the seeds and the female flowers of D. tokoro MAKINO. The sapogenins isolated as crystals from the female flowers were diosgenin, yonogenin, tokorogenin and a new sa pogenin, igagenin, and that from the seeds was tokorogenin. Marked differences between the seeds and the female flowers were found in regards to the sorts and the amounts of sapogenins.
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KENJI SUZUKI, TAKASHI ABIKO
1968 Volume 16 Issue 10 Pages
1997-2004
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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[6-O-Acetyl-L-serine]-bradykinyl-glycyl-L-valyl-L-glutamine, glycylglycyl-L-lysylbradykinin, and bradykinylglycine were synthesized for the elucidation of structure activity relationship of bradykinin and their properties as substrates for bradykininreleasing enzymes. The p-nitrophenyl ester method and stepwise elongation procedure were extensively used for the peptide synthesis.
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MASAYUKI ONDA, KAORU ABE, KYOKO YONEZAWA
1968 Volume 16 Issue 10 Pages
2005-2010
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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When anhydroprotopine was treated with dilute hydrochloric acid, it gave the different compounds from the "Perkin's compound". Their structures were identified to contain the spiro-type skeleton by the nuclear magnetic resonance spectroscopy, and two of them (VI and VII) were assigned to be the stereoisomers by the successive reactions and also physico-chemical investigation.
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YOSHIHISA MIZUNO, SETSUKO TAZAWA, KUNIO KAGEURA
1968 Volume 16 Issue 10 Pages
2011-2017
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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4-Hydroxy-1-(β-D-ribofuranosyl)-1H-imidazo [4, 5-c] pyridine (3-deazainosine, XIV) was prepared by use of the corresponding 4-chloro derivative (IX) as a key intermediate. It was found that the reaction of IX with hydrazine afforded either 1-(β-D-ribofuranosyl)-1H-imidazo [4, 5-c] pyridine (XIII) by de-chlorination or 4-hydrazino-1-(β-D-ribofuranosyl)-1H-imidazo [4, 5-c] pyridine (X) depending upon conditions employed. Improved synthesis of IX was achieved by an adaptation of Yamaoka, Matsuda and Aso's method. In addition to X and XIV, a number of other 4-substituted ribonucleosides and nucleotides having imidazo [4, 5-c] pyridine (3-deazapurine) ring system, such as XII, XV, XVI and XVII were prepared.
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KIICHIRO KAKEMI, HITOSHI SEZAKI, TAKAYOSHI MITSUNAGA, MASAHIRO NAKANO
1968 Volume 16 Issue 10 Pages
2018-2022
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The effect of pyridine, aniline, hydrocinnamic acid, phenethylamine, propionic acid, or theophylline on the solubility of 8-methoxycaffeine was compared with that of the respective salt at 25°. In most cases the free acids or bases showed greater binding tendencies toward 8-methoxycaffeine than the corresponding ionic forms. Reduction in solubilizing capacity of the ionic forms may be attributed mainly to prevention by the solvent shell from complex formation rather than just the salt-out effect due to the change in the activity coefficient of 8-methoxycaffeine in the presence of organic salts. Theophylline was, on the other hand, unusual in a sense that its ionic form (theophylline ion) bounds 8-methoxycaffeine with a greater stability constant than its free form. Theophyllinate ion was demonstrated to interact more strongly than theophylline with another structurally similar compound. The structural similarity between the two interactants in aqueous media may be responsible for this reverse phenomenon.
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AKIRA HANAKI
1968 Volume 16 Issue 10 Pages
2023-2031
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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The potentiometric titration of radiation-protective aminoalkylisothiuronium salt, such as AET or APT, was carried out in various conditions with a recording titrator. The method for the selective determination of each component in the mixtures containing the isothiuronium salt, the transguanylation and cyclization products was established first. By using this technique, it was clarified that AET was mainly transguanylated and partly cyclized during the titration and that the molar ratio of those two reaction products depends on the titration speed and temperature. APT was transguanylated nearly quantitatively without repsect to the titration speed. Both reactions may proceed through the ionized isothiuronium salt. The rate of the transguanylation was extremely fast. In the presence of 0.5 equivalent alkali, the degree of the transguanylation at 25° was as follows ; AET : 0.77 in 0.5 min, 0.94 in 2 min, APT : 0.82 in 0.5 min, 0.94 in 2 min. The pH dependence of the transguanylation was postulated and discussed quantitatively.
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SHIGEO SUZUKI, TAKESHI SAITO, MITSURU UCHIYAMA, SHICHIRO AKIYA
1968 Volume 16 Issue 10 Pages
2032-2039
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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In order to confirm the chemical entities of the anti-tumor substances in the extract of the leaves of a sort of bamboo, Sasa senanensis (FR. et SAV.) REHD, a series of fractionation was carried out on the macromolecular constituents of the extract. Two hemicelluloses were isolated as homogeneous states both in free boundary electrophoresis and ultracentrifugal analysis. One of them was a neutral polysaccharide which was precipitable with alkaline copper solution and consisted of L-arabinose, D-xylose and D-glucose, while the other contained D-galactose in addition to the three sugar components mentioned above and showed weak acidity due to a small amount of uronic acid. Both polysaccharides showed over 90% tumor-inhibitions when injected intraperitoneally into mice bearing Sarcoma-180 solid tumor.
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SUSUMU ISHIGURO, SETSUZO TEJIMA
1968 Volume 16 Issue 10 Pages
2040-2045
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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1, 2-Dideoxy-1, 2-dithioimidocarbonyl-β-D-mannopyranose (III) was prepared in 76% yield by treatment of 1, 2-dideoxy-1, 2-(N, N-dimethylammonium) dithiocarbonyl-β-D-mannopyranose methanesulfonate (II) with methanolic ammonia. Some acyl derivatives of III were also described. Treatment of a suspension of III in ethanol containing glacial acetic acid with hydrogen sulfide afforded 1, 2-dideoxy-1, 2-trithiocarbonyl-β-D-mannopyranose (XII) in 78% yield. The product was also obtainable in 98% yield from II with the same procedure. Acetylation of XII gave triacetate (XIII) which was also prepared in 61% yield by reflux of II and potassium thiolacetate in acetone, followed by acetylation.
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YOSHIKAZU MATSUSHIMA
1968 Volume 16 Issue 10 Pages
2046-2055
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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Reactions of amino acids and related amines with pyridoxal in methanol were studied by the changes of electronic absorption spectra. Most amino acids and amines formed Schiff bases, which existed in keto-enamine and enol-imine forms. Equilibrium between the two tautomeric forms was affected by the nature of amino acids or amine residues. Amino acids having a secondary amino group formed carbinolamine derivatives with pyridoxal. Cysteine and cysteamine gave products which had thiazolidine rings, while histidine, and 5-substituted tryptophans formed tetrahydropyridine derivatives asultimate products. The spectral properties, solution equilibria in methanol and band assignments of the Schiff bases and other products formed were described.
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YASUSHI SANNO, AKIRA NOHARA
1968 Volume 16 Issue 10 Pages
2056-2059
Published: October 25, 1968
Released on J-STAGE: March 31, 2008
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NORIO TAKAMURA, SHIRO TERASHIMA, SHUNICHI YAMADA
1968 Volume 16 Issue 10 Pages
2059-2064
Published: October 25, 1968
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SHIRO TERASHIMA, SHUNICHI YAMADA
1968 Volume 16 Issue 10 Pages
2064-2067
Published: October 25, 1968
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SATOSHI OSUGI, TAIZO HAYASHI, SADAO HIROTA
1968 Volume 16 Issue 10 Pages
2067-2069
Published: October 25, 1968
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TOSHIAKI TOMIMATSU, MITSUKO HASHIMOTO, JACKL. BEAL
1968 Volume 16 Issue 10 Pages
2070-2073
Published: October 25, 1968
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YOSHIO ARATA, SHINGO YASUDA, KOICHI YAMANOUCHI
1968 Volume 16 Issue 10 Pages
2074-2077
Published: October 25, 1968
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SHUNICHI HATA, SUIICHI TOMIOKA
1968 Volume 16 Issue 10 Pages
2078-2079
Published: October 25, 1968
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AKIO HOSHI, KEIKO KUMAGAI, KAZUO KURETANI
1968 Volume 16 Issue 10 Pages
2080-2083
Published: October 25, 1968
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SADAO OIDA, EIJI OHKI
1968 Volume 16 Issue 10 Pages
2086-2088
Published: October 25, 1968
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TERUMI NAKAJIMA
1968 Volume 16 Issue 10 Pages
2088-2089
Published: October 25, 1968
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ITIRO YOSIOKA, TSUTOMU NAKANISHI, SATOKO IZUMI, ISAO KITAGAWA
1968 Volume 16 Issue 10 Pages
2090-2091
Published: October 25, 1968
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