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五島 綾子, 遠藤 文男, 伊藤 圭二
1977 年 25 巻 6 号 p.
1165-1173
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The gel filtration of a micellar solution on Sephadex G-50 was applied for the study of partition of methyl, ethyl and butyl parabens between the micellar and aqueous phases. When, after the gel layer having been pre-equilibrated with 8 mM sodium lauryl sulfate (SLS), SLS solutions solubilizing alkyl parabens were eluted with 8 mM SLS nearly equal to critical micelle concentration (cmc) as an eluent, decomposition of micelles might be prevented. In this case, however, liberation of alkyl paraben from a micellar phase was observed, accordingly to a property of alkyl paraben or a sample volume (correlated to the gel volume). It might therefore be difficult to investigate quantitatively the distribution state of alkyl paraben in micelles. It was tried that the gel pre-equilibrated with a large sample was eluted with water as an eluent (the so-called tail analysis). As a result, it was found from the elution curves of alkyl parabens obtained by the tail analysis that partition ratios of the alkyl parabens between the micellar and aqueous phases may be determined. These results correspond to the data from the solubility method. However, information from the solubility method is only obtained about the saturated solution from the nature of experiment. From gel filtration, on the other hand, it may be possible to get information not only about a partition ratio for a solute unsaturated in a detergent solution, but also about the state of detergent micelles.
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森脇 千秋, 藤森 広幸, 守屋 寛, 木付 和幸
1977 年 25 巻 6 号 p.
1174-1178
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The effect of a highly purified hog pancreatic kallikrein and synthetic bradykinin on the transport of valine across the rat small intestine was examined by an in vitro experiment with the sac of everted intestine and by an in situ mesenteric perfusion experiment. The flow of valine from the mucosal to the serosal side of everted intestine was stimulated significantly by the addition of kallikrein to the mucosal fluid in a concentration of 0.1 KU/ml, while bradykinin was effective only by its addition to the serosal fluid. In a perfusion experiment, valine transport into the vascular system was enhanced significantly by intra-intestinal administration of 0.02-20 KU of kallikrein. The maximum effect was obtained with 2 KU, and the absorption of valine was 1.9 times larger than that of the control. Bradykinin infusion into the mesenteric perfusion system in concentrations of 10
-2 to 10
2nM also increased the transport of valine. A bell-shaped dose-response curve, in which the maximum enhancement was achieved with 1 nM of bradykinin, was obtained similar to the case of kallikrein. This effect of kallikrein appeared soon after its administration into the intestinal lumen and usually lasted about 30 min under the present experimental conditions.
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尾崎 茂子, 枡井 雅一郎
1977 年 25 巻 6 号 p.
1179-1185
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The anodic oxidation of hydroxamic acids in acetonitrile were studied. These hydroxamic acids generally showed two or three waves at a glassy-carbon electrode and the E
p values were larger than those of the corresponding hydroxylamines. On oxidation, O-alkylated hydroxamic acids consumed one electrone per molecule and other hydroxamic acids consumed two. Aceto-and benzohydroxamic acids gave the corresponding carboxylic acids and nitrous oxide. N-Substituted hydroxamic acids gave the corresponding nitroso compounds and carboxylic acids. O-Alkylated hydroxamic acids underwent intramolecular rearrangement of acyl and O-alkyl group to give esters, acids and alcohol. In the presence of added amines, acyl groups were recovered as amides. From these results we proposed plausible chemical processes for the anodic oxidation of hydroxamic acids.
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宮崎 正三, 遠藤 ひとみ, 灘井 種一, 有田 隆一, 中野 真汎
1977 年 25 巻 6 号 p.
1186-1193
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The effect of various formulation additives on the dissolution behavior of three tetracycline antibiotics from compressed tablets (prepared by direct compression) was studied. In general, the dissolution of the antibiotics was found to be retarded by the addition of binding agents such as gelatin and acacia, when they were incorporated in compressed tablets. A study was also undertaken to determine the influence of gelatin and acacia dissolved in the test media. In dissolution experiments on compressed tablets and crystalline powders, a significant dissolution inhibition by the action of the dissolved additives was present, as in the study where additives were incorporated in compressed tablets. It was thought that the possible mechanisms for the retardation effect included the formation of a poor soluble complex between the drug and the additives and the increased viscosity of the medium. A blood level study was also conducted in rats using CTC-HCl and TC-HCl as test materials to determine whether gelatin and acacia affect the membrane permeability of drugs from solutions. Blood concentrations after intraduodenal administration of these two drug solutions with gelatin and acacia were compared to each control level produced by the drug given alone. These two additives resulted in lower blood levels compared to control values.
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渡辺 淳, 森 啓子
1977 年 25 巻 6 号 p.
1194-1201
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Small intestinal tracts of rats, guinea pigs, and rabbits were recirculated in situ with methylene blue (MB), and the average absorption ratios in 120 min were 54, 36, and 47%, respectively. Therefore the great species difference in MB absorption capacity was not observed in these three experimental animals. At the same time 7.7, 46, and 30% of the dose were found as leucomethylene blue (LMB) besides the unchanged methylene blue in the perfusate for rats, guinea pigs, and rabbits, respectively. In situ perfusion experiments revealed that the concentration of total MB (MB+LMB) in bile at 150 min was five times greater than the initial MB concentration in the perfusate, and that 8 and 12.8% of the total MB absorbed were excreted in bile and urine, respectively. The total excreted MB contained 96.8% LMB in bile, and 94.1% in urine. MB was reduced to LMB under anaerobic condition by incubation with everted sacs of the small intestines of guinea pigs and rats, and the reduction was not reversible in the incubation medium under the same condition in the sense of net reaction. In vitro absorption experiment employing the everted sacs of the small intestines of rats, guinea pigs, and rabbits suggested that LMB besides MB would be also absorbable from the small intestines of the experimental animals in situ.
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大杉 義征, 松野 隆, 高垣 善男
1977 年 25 巻 6 号 p.
1202-1208
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Based on the report that 2, 4-bis (2-hydroxybenzamido) benzoic acid (AB-23) inhibits immune hemolysis in vitro, the site of the action of this compound was studied. AB-23 had no effect on the binding of hemolysin to sheep erythrocytes (E). A high concentration of AB-23 was required for inhibition of higher dose C-induced hemolysis. E which escaped hemolysis in the presence of AB-23, were normally hemolyzed by readdition of fresh C after removal of the drug. Inhibition by AB-23 of C fixation to sensitized E was suggested from these results and confirmed by the finding that AB-23 interferes with immune adherence hemagglutination. The effect of AB-23 was apparently not due to chelation of Mg
2+ or Ca
2+. AB-23, but neither ethylene diamine tetraacetic acid nor ethylene glycol tetraacetic acid showed inhibitory activity even when added 8 or 15 min after C addition. This suggests that AB-23 inhibits the sequence of later components of C from C3 to C9. This possibility was strongly supported by the following finding that AB-23 prevents the consumption of C activity by zymosan via an alternative pathway. Additionally, 2, 4-bis (2-acetoxybenzamido) benzoic acid, which is easily changed to AB-23 in the body, inhibited the passive Arthus reaction in guinea-pigs and also prevented urinary protein excretion in rats after nephrotoxic serum injection in which complement is known to play an important role. These results suggest the anti-complement effect of AB-23 in vivo.
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栄田 和子, 蓮見 冨士夫, 西村 昇, 菊谷 元資
1977 年 25 巻 6 号 p.
1209-1214
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
In order to induce chromodacryorrhea observed in pantothenic acid-deficient rats and also to obtain informations on the regulation of porphyrin biosynthetic pathway in the rat Harderian gland, the effect of hepatic porphyria-inducing chemicals, especially chlorinated benzenes, on porphyrin biosynthetic pathway in the Harderian gland of rat was examined and the following results were obtained. None of the chemicals tested induced the expected chromodacryorrhea. The rat Harderian gland was resistant to the induction of δ-aminolevulinic acid (ALA)-synthetase by hepatic porphyria-inducing chemicals, expected for a few compounds such as lower CB compounds. There was a remarkable difference between the Harderian gland and the liver in the responsiveness of ALA-synthetase and ALA-dehydratase to hepatic porphyria-inducing chemicals.
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岩瀬 廣, 村井 朝夫
1977 年 25 巻 6 号 p.
1215-1219
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The fragmentation of 21 kinds of biochemically important amines after leading to N-trifluoracetyl-L-prolyl derivatives is investigated for the concurrent ultramicrodetermination or the selective identification of each amine. It was found that N-trifluoroacetyl L-prolylamine derivatives are useful for the concurrent determination of ultra microamounts (about 10
-10 g level) of amines by mass fragmentography or the selective identification of amines by monitoring the each diagnostic peaks.
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大塚 勝弘, 室田 誠逸, 森 陽
1977 年 25 巻 6 号 p.
1220-1224
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Administration of bleomycin (1 mg/rat/day) for 5 days into granuloma pouch resulted in significant increase of intercellular substances of the granulomatous tissue measured at the 5th day from the last injection of bleomycin, i.e., 130% for collagen, 261% for nonsulfated glycosaminoglycan, 129% for sulfated glycosaminoglycan and 153% for glycoprotein, while no significant alteration was observed in desoxyribonucleic acid and ribonucleic acid contents. The increment of these macromolecules caused by bleomycin treatment was inhibited by successive administration of D-penicillamine (60 mg/rat/day) for 5 days.
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松浦 勉, 国枝 武久, 滝沢 武夫
1977 年 25 巻 6 号 p.
1225-1229
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Telomers of vinylenecarbonate with tetrachloromethane, which possess the 4-chloro-1, 3-dioxolan-2-one structure as a terminal ring, underwent smooth and selective conversion with primary aliphatic amines into 5-substituted 4-hydroxy-2-oxazolidones whose chemical reactions with the aid of acids, dehydration and phenylation, led to the corresponding 4-oxazolin-2-ones and 4-phenyl-2-oxazolidones, respectively. Treatment of 5-trichloromethyl-2-oxazolidinone with zinc-methanol resulted in the exclusive formation of 5-dichloromethyl-2-oxazolidone, in contrast to the corresponding 1, 3-dioxolan-2-one system which suffered complete reductive ring-opening even under milder conditions.
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森本 俊明, 関屋 実
1977 年 25 巻 6 号 p.
1230-1236
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Reactions of imines with trichloroacetylating agents rely upon their structural differences. 3, 3-Dichloro-2-azetidinone formation was effected by the reaction of α-arylsubstituted N-benzylideneamines similarly to that of N-benzylideneamines. The imines, of which imino carbons are bound to alkyls possessing at least one hydrogen at C
1 of the alkyls, however, reacted with trichloroacetic anhydride and trichloroacetyl chloride to give β-trichloroacetylated enamines. In the reaction with trifluoroacetic anhydride in place of trichloroacetic anhydride N-trifluoroacetylenamines were obtained instead, but the products easily undergo N→C migration on heating in xylene to give β-trifluoroacetylated enamines. Acid-catalyzed quinoline ring-closures of the β-trihaloacetylated enamines obtained above are also described.
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中野 三郎, 吉田 友彦, 御子 柴和男, 谷口 寛一
1977 年 25 巻 6 号 p.
1237-1242
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Nitrate reacts with 2-phenylbenzothiazole in concentrated sulfuric acid to form 6-nitro-2-phenylbenzothiazole, which changes to 6-amino-2-phenylbenzothiazole by the irradiation with ultraviolet light in an ammoniacal dioxane solution and the 6-amino-2-phenylbenzothiazole gives the intense fluorescence with excitation maximum at 358 nm and emission maximum at 457nm. By using this reaction, 0.01-3.0μg/ml of nitrate ion can be determined fluorophotometrically. In the application of this method for the analysis of tap water, the interferences from nitrite ion, residual chlorine and chloride ion can be eliminated by using sulfamic acid, sodium sulfite and silver sulfate, respectively.
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児島 昭次, 濱田 千鶴子, 田中 立子
1977 年 25 巻 6 号 p.
1243-1248
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The effect of sodium cholate on the absorption of strongly basic drug, buformin, was studied in the in situ rat small intestinal loops. In cases of either jejunum or ileum, the absorption of buformin significantly increased above the critical micelle concentration of sodium cholate. Since sodium cholate had little effect on the physico-chemical property such as the apparent partition coefficient of buformin, it became evident that the enhancement of buformin absorption was not caused by the intraluminal effect of the bile salt. The absorption of buformin was also enhanced in the jejunal and ileal loops pretreated with sodium cholate. On the absorptive surface, sodium cholate did not increase the affinity of buformin to the intestinal mucosal surface. In addition, the release of membrane components such as protein, total phosphorus, and phospholipid from the intestine was accelerated to greater extent by sodium cholate. From these results, it is suggested that sodium cholate alters the composition of the in situ rat intestinal membrane by producing a release of membrane components from the intestinal tissues, resulting in an increase in the permeability of the small intestine to buformin.
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伊藤 一男, 田中 斉, 鹿山 正人
1977 年 25 巻 6 号 p.
1249-1255
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Several sulfonamides (IIIa-c and IVa-c) were synthesized for the investigation of benzyne reaction. The benzyne reaction of IIIa-c and IVa-c with sodium dimethylsulfinyl carbanion in dimethyl sulfoxide resulted in the formation of the corresponding indolines (Va-c and VIa-c) besides thioether phenol compounds (VIIa-c and VIIIa-c). These structures were respectively established from infrared and nuclear magnetic resonance spectra. On the other hand, the same reaction of phenethylamines (IIa, IIb and IIc) with sodium dimethylsulfinyl carbanion afforded XIIa, XIIb and XIIIc, respectively.
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浜名 政和, 竹尾 聡, 野田 浩司
1977 年 25 巻 6 号 p.
1256-1264
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The orientation of nitration of 2-phenylquinoline 1-oxide (1) with potassium nitrate and sulfuric acid was found to be principally governed by the concentration of sulfuric acid independently of the reaction temperature. Thus, whereas the reaction in concentrated sulfuric acid gave 3'-nitro derivative (3) as the main product, the use of 70-75% sulfuric acid was favorable for the formation of 4-nitro derivative (2). Further nitration of 2 and 3 readily produced 3', 4-dinitro compound (4). The Reissert-Henze reaction of 2-(4-methoxyphenyl) quinoline 1-oxide (7) afforded 1-benzoyloxy-4-cyano-1, 4-dihydroquinoline (12) besides 4-cyano (9), 6-benzoyloxy- (10) and 8-benzoyloxy-quinolines (11). From the reaction of 2-(4-nitrophenyl) quinoline 1-oxide (8), the corresponding 1, 4-dihydroquinoline (15) was also isolated together with 6-and 3-benzoyloxyquinolines (13 and 14). The mechanism of the formation of benzoyloxy derivatives was discussed.
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桐山 典城, 樋口 善博, 山本 譲
1977 年 25 巻 6 号 p.
1265-1272
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
New compounds, 6-hydroxytoluquinol-hydrate (3, 4) (VI), terremutin-hydrate (VII), and 4-chloro-3, 6-dihydroxytoluquinone (II) were isolated from Aspergillus terreus ATCC 12238 together with terreic acid, terremutin, 3, 6-dihydroxytoluquinone, and terrein. The metabolic relationships among the metabolites were studied by administration experiments using
14C-compounds and the metabolic scheme was proposed. The metabolic pattern of"epoxy compounds (terreic acid and terremutin)→quinone (3, 6-dihydroxytoluquinone) or its quinol→hydroaromatic compound (VI)"was essentially the same as observed in Aspergillus fumigatus DH 413 and IFO 4399.
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北本 六良, 亀尾 一弥, 寺島 孜郎, 山田 俊一
1977 年 25 巻 6 号 p.
1273-1284
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Asymmetric reduction of several kinds of 2-alkyl-1, 3, 4-cyclopentanetriones (1) by the use of lithium aluminum hydride (LAH) partially decomposed by optically active β-aminoalcohols (7), was studied. It was found that the reduction of 2-propyl derivative (1c) with LAH decomposed by 3.0 eq. of (-)-N-methylephedrine (7a), in THF at -70°for 3 hr, followed by acetylation, gave (R)(-)-4-acetoxy-2-propyl-1, 3-cyclopentanedione ((R) (-)-3c), 58% e.e., in 42% yield. When the same reduction procedure was applied to 2-allyl derivative (1b), (R) (-)-4-acetoxy-2-allyl derivative ((R) (-)-3b), 55% e.e., was obtained in 48% yield. Recrystallization of (R)(-)-3b from ether could improve the optical purity up to 97% e.e. The absolute configuration and optical purity of (R) (-)-3b and (R) (-)-3c were established by the chemical correlation with (R) (-)-allethrolone ((R) (-)-5). When 2-(6-carbomethoxyhexyl)-1, 3, 4-cyclopentanetrione (1a) was treated by the exploited reduction condition, the corresponding (R) (+)-alcohol ((R) (+)-2a), 54±6% e.e., from which PGE
1 had been synthesized, was prepared in 58% yield.
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水谷 彰, 水谷 隆治, 郭 伯峰
1977 年 25 巻 6 号 p.
1285-1288
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The amino-terminal sequence of a hypocalcemic protein purified from bovine parotid gland was determined as Lys-Leu- by the dansyl-Edman method in the presence of sodium dodecyl sulfate (SDS). The amount of amino-terminal lysine was quantified as 0.85 mole per mole of protein. A carboxyl-terminal sequence was analyzed by use of carboxypeptidase A and it was deduced to be-Thr-Val-Leu. Furthermore, the carboxylterminus was confirmed to be leucine alone by the hydrazinolysis method. On SDS gel electrophoresis, this protein failed to show the evidence of dissociation or association. From these results, the hypocalcemic protein was concluded to consist of a single polypeptide chain.
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町田 實, 牛島 信行, 高橋 哲夫, 金岡 祐一
1977 年 25 巻 6 号 p.
1289-1294
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Nitration of 7-dimethylaminocoumarin (1) afforded three isomers of the nitrocoumarins, two of which were by way of the amines converted to the corresponding maleimides and succinimides. Their absorption and fluorescence spectra were measured, and it was found that N-(7-dimethylamino-4-methyl-3-coumarinyl) maleimide (5a) has the requisite properties for serving as an useful fluorescence thiol reagent with regard to the fluorescent intensity, excitation wavelength, water solubility and the reactivity. Thus dimethylaminocoumarin is one of candidate fluorogenic groups of choice to be employed in organic fluorescence reagents.
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後藤 義一, 吉岡 晃一, 平賀 謙太郎, 三木 卓一
1977 年 25 巻 6 号 p.
1295-1301
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Four epimeric 17-hydroxy-16-ethylestr-4-en-3-ones (11) having potent antiandrogenic activity were prepared stereoselectively starting from 16α-ethyl-16β, 17β-diol monoacetate (2). The nuclear magnetic resonance spectra of the four epimers and other 16-substituted estranes and androstanes were investigated in order to elucidate the possibility for the assignment of the unknown configurations at the positions of 16 and 17. The data of the coupling constants (J
16, 17) and the chemical shifts (13-methyl protons and 17-proton) can be used for the determination of the configuration at the positions of 16 and 17.
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沢田 洋介, 谷山 兵三
1977 年 25 巻 6 号 p.
1302-1305
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Racemomycin-C was semi-synthesized from racemomycin-A by condensation with diZ-β-lysine-OSU followed by catalytic hydrogenation. Racemomycins B, D and E were also prepared in the similar manner. Among these antibiotics, racemomycin-B containing three β-lysine residues in one molecule showed the strongest antibacterial activity against B. subtilis.
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徳竹 伯夫, 米野 太一郎, 武田 健一
1977 年 25 巻 6 号 p.
1306-1311
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Some estrone and epiandrosterone derivatives having a sulfur function at C
16 were prepared by substitution reaction of 16α- and 16β-bromo-17-ketosteroids with sulfur nucleophiles. The reaction proceeds with inversion at C
16. Equilibration experiments on some of the products indicate that the 16β-substituted steroids are thermodynamically more stable than the corresponding α-isomers and the 16-acetylthiosteroids are epimerized faster than the 16-ethylthiosteroids. The proton signals at C
16 of the products show characteristic splitting patterns according to their configuration.
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際田 弘志, 森田 要, 林 正弘, 粟津 荘司, 花野 学
1977 年 25 巻 6 号 p.
1312-1318
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
A new numerical calculation method of the deconvolution specialized for the linear compartment analysis of pharmacokinetics was presented. In this method, the deconvolution was carried out from numerical data of precursor obtained directly in unequal interval of time and an empirical exponential equation for successor. From the assumption for the integrated weight function to be simple increasing function, the divergence of calculation was protected completely. In the experiment of model calculation, the accuracy and the precision were proved to be practically sufficient for pharmacokinetic studies.
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古川 潮, 大川原 正, 寺脇 由里子
1977 年 25 巻 6 号 p.
1319-1325
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Asymmetric syntheses of β-amino acids were achieved by the addition of chiral amines, R (+)- and S (-)-α-methylbenzylamines (1b and 1c), to crotonitrile, methyl crotonate (5a), l-menthyl crotonate (5b), ethyl cinnamate (5c), and methacrylonitrile, and by the addition of benzylamine (1a) to 5b, in the range of 2-19% optical purities. Among them, the configuration of the resulting β-amino acids was same as 1b and 1c used, in the reactions with crotonitrile and 5c, but was different in the cases of 5a and 5b and methacrylonitrile.
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平内 三政, 天野 為之
1977 年 25 巻 6 号 p.
1326-1329
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
4-Homosulfanilamide was found to react with 4-fluoronitrobenzene to form N
4-(4'-nitrophenyl)-4-sulfamoylbenzylamine which strongly phosphoresced in ethanoldimethyl sulfoxide solution (9 : 1, v/v). This observation was successfully used to determine microamounts of 4-homosulfanilamide. A linear relationship between the phosphorescence intensity and amine concentration was observed in the range of 2×10
-6-2×10
-4M. This phosphorimetric method was 5-25 times more sensitive than colorimetric methods.
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長沢 金蔵, 磐井 くに子, 西村 成子
1977 年 25 巻 6 号 p.
1330-1334
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
1, 2-Naphthoquinone 1-oxime O-sulfate (1) was synthesized by sulfation of 1-nitroso-2-naphthol with chlorosulfonic acid and N, N-dimethylaniline. The sodium salt of 1 was decomposed to form inorganic sulfate and 1-nitroso-2-naphthol in neutral (pH 4.9, 80°) and acidic (0.1N HCl, 40°) conditions, with their half-lives of 380 and 140 min, respectively. In an alkaline medium (0.1N NaOH, 20°), the salt was instantaneously decomposed to give a quantitative amount of inorganic sulfate and a ring-cleaved product of 1, 2-naphthoquinone 1-oxime moiety, and this product was identified as o-cyano-cis-cinnamic acid (2). The effect of Cu (II) on the hydrolysis of 1 was more accelerative in a neutral condition than in an acidic condition, resulting in the reduction of its half-life to 60 min. It was also observed that polar organic solvents such as pyridine, dioxan, and tetrahydrofuran markedly accelerated the hydrolysis of the triethylammonium salt of 1, in both neutral and acidic conditions. Reactivity of the triethylammonium and the pyridinium salts of 1 in trans-sulfation was examined in Me
2SO·pyridine (4 : 1), with or without Cu (II). As estimated by the formation of sulfated products from riboflavin, 1 had a much smaller reactivity than 8-quinolyl sulfate reported previously, although the effect of Cu (II) was accelerative on the reaction.
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北尾 和彦, 矢田 登, 鎌田 皎
1977 年 25 巻 6 号 p.
1335-1342
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Analysis of pyrithioxin (I) and its metabolites in blood and urine by thin-layer chromatography and high-performance liquid chromatography was described following single oral doses of pyrithioxin dihydrochloride (I·2HCl) to beagle dogs. Pyrithioxin glucuronide (I-G), 5'-desoxy-5'-methylsulfinylpyridoxol (II) and its glucuronide (II-G) were found as metabolites in the urine. 5'-Desoxy-5'-methylthiopyridoxol (III), which was reported in the literature as one of main metabolites of I in the urine, was found to be a reduced product of II during the storage of excreted urine at room temperature. An analytical method of these metabolites in blood and urine was established employing a high-performance liquid chromatography with a cation-exchange resin column.
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北尾 和彦, 矢田 登, 久保 一義, 藤原 裕美, 鎌田 皎
1977 年 25 巻 6 号 p.
1343-1349
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
After single oral and intravenous administration of pyrithioxin (I) to beagle dogs, the blood levels of 5'-desoxy-5'-methylsulfinylpyridoxol (II), one of the main metabolites of I in blood and urine, were measured with a high-performance liquid chromatography. The existence of I was not detected in blood samples for 24 hr after an oral administration of I at dose levels less than 100 mg of I/kg. But, it was detected in the first blood sample collected 1 min after intravenous injection at dose levels of 10 and 5 mg/kg, but not in the sample collected 3 min after injection. After oral and intravenous administrations of I, non-first-order disappearance of II in blood was observed. The results suggest a possible enterohepatic cycling of I-glucuronide (I-G). A study was made on the metabolites in the urine samples after two routes of administration, demonstrating the existence of I-G, II, and II-glucuronide (II-G). Likewise, II and II-G were found in the urine following oral and intravenous administrations of II·HCl. A total amount of II in mole percent of dose excreted in the urine after oral administration of I·2HCl filled in hard gelatin capsules decreased significantly with an increase of dose suggesting change of bioavailability with change of the dose. The results were seemed to be partially subjected to the poor absorbability at the intestinal tract owing to the low solubility of I at the physiological pH of 4-7.5. Mucosal-to-serosal permeation of I across the everted rat intestine in vitro was found to proceed without metabolism during and after permeation. Thus, it may be considered that the metabolism of I takes place after absorption, mainly in the liver.
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北尾 和彦, 矢田 登, 山崎 勝, 岩根 順一, 鎌田 皎
1977 年 25 巻 6 号 p.
1350-1356
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
An attempt was made to determine and compare oral absorption characteristics of ester derivatives of pyrithioxin (I) filled in hard gelatin capsules after administration to dogs. Ester derivatives of I studied were pyrithioxin-tetraacetate dihydrochloride (I-A·2HCl), pyrithioxin-tetrapropionate dihydrochloride (I-P·2HCl), pyrithioxin-tetra-n-butyrate dihydrochloride (I-B·2HCl), and pyrithioxin-4, 4'-disuccinate dihydrochloride (I-S·2HCl). Blood concentrations of 5'-desoxy-5'-methylsulfinylpyridoxol (II) and urinary excretions of metabolites of I were studied following oral administration of esters. The values of area under the blood concentration-time curve (AUC) and total urinary excretion in terms of mole percent of dose were used as provisional bioavailabilities of the ester and compared with those of I·2HCl. The bioavailability of I-P·2HCl significantly increased with the maximum blood concentration 1.63 times larger and the total urinary excretion 1.47 times larger than those of I·2HCl. There appeared to be a close relationship between the improved bioavailability of I-P·2HCl and its large partition coefficients of n-octanol/pH 6.5 buffer. The insufficient bioavailability of I-S·2HCl appeared to be closely correlated with its low partition coefficient of 0.094 and incomplete hydrolysis of ester during absorption. The esters were considered to be hydrolyzed in intestinal fluid and/or in the intestinal membrane and the parent drug, I, permeated through the intestinal tract. The uptake of
14C-labelled glucose into the brain of the mouse was preliminary studied with I-A·2HCl and I-S·2HCl. I-A·2HCl indicated a significant increase of glucose through the blood-brain barrier similar to that of I·2HCl, but not with I-S·2HCl.
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友田 正司, 金子 幸子, 江端 峰子, 永倉 照代
1977 年 25 巻 6 号 p.
1357-1362
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
A representative mucous polysaccharide, named Althaea-mucilage O, has been isolated from the roots of Althaea officinalis L. It was homogeneous on glass-fiber paper electrophoresis and by ultracentrifugal analysis, and its water solution gave the high intrinsic viscosity value of 50.0. It was composed of L-rhamnose : D-galactose : D-galacturonic acid : D-glucuronic acid in the molar ratio of 3 : 2 : 3 : 3, and molecular weight of its ammonium salt was estimated to be 34000. The O-acetyl groups in it were identified and the content was 0.7%. The mucilage has been subjected to the reduction of carboxyl groups, and the results of methylation analysis of the original and the carboxyl-reduced polysaccharides revealed the structural features of the backbone and side chains in the mucilage.
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竹内 彰, 伊藤 敬一, 関屋 実
1977 年 25 巻 6 号 p.
1363-1367
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Chemical behaviors of 1, 1'-diacetyl-1, 1', 4, 4'-tetrahydro-4, 4'-bipyridine toward organic hydrogen acceptors such as nitrosobenzene, p-benzoquinone, dibenzoyldiimide, and 5-benzylidene-1, 3-dimethylbarbituric acid were examined to demonstrate its ability in donating hydride and acetylium ion. Reduction processes of these substrates are described and, with the latter two, reductive acetylations of a new fashion are disclosed.
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村瀬 清志, 間瀬 年康, 井田 昶, 高橋 孝三, 村上 増雄
1977 年 25 巻 6 号 p.
1368-1377
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
New β-adrenergic stimulants, 3-acylamino-4-hydroxy-α-(N-substituted aminomethyl)-benzyl alcohols (VIII) were prepared via 3-amino-4-benzyloxy-α-(N-substituted aminomethyl) benzyl alcohols (V) in several steps. These agents were catecholamine derivatives, in which m-phenolic OH was replaced by acylamino and substituted acylamino groups. Terbutaline analogues (XIXa, b, XX), in which one or both of two phenolic OH were replaced by formamido or methoxycarboxamido groups were synthesized, too. Compounds (VIIIa, c, 1-q) bearing formylamino group in the meta position showed potent β
2-stimulant activity in vitro. In these, N-phenylalkyl series were more potent β
2-stimulant than N-alkyl series. Several compounds, which bear two asymmetric centers, were separated into two racemates and the β
2-stimulant activity of them were different. From these compounds, 3-formamido-4-hydroxy-α-(N-(p-methoxy-α-methylphenethyl) aminomethyl)-benzyl alcohol ·1/2 fumarate (VIIIn-A) (BD-40-A) was selected as the best compound.
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吉本 昌文, 上岡 利春, 宮寺 哲男, 小林 晋作, 高木 弘, 太刀川 隆治
1977 年 25 巻 6 号 p.
1378-1390
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Quantitative structure-activity relationships (QSAR) for benzodiazepinooxazoles were formulated in 9 equations correlating chemical structure with 9 types of biological activities. The equations describing the relationships are log 1/C=aπ-7+bF-3+cF-4+dI-1+eI-2+fI-3+g where C is the molar concentration causing 50% biological activity, π-7 is the hydrophobic constant for substituents on the N
7 position of 1, 4-diazepine (II), F-3 and F-4 refer to the electronic effects of R
3 and R
4, respectively, and the indicator variable I-1, I-2 and I-3 refer to the methyl function of the R
3, R
9 and R
10, respectively.
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李 燕梅, 斎藤 洋, 高木 敬次郎, 柴田 承二, 庄司 順三, 近藤 紀子
1977 年 25 巻 6 号 p.
1391-1398
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Pharmacological properties attributed to Panacis Japonici Rhizoma (PJR) in Chinese medicine in Japan in terms of its usage as a drug for gastroenteric disorders, antipyretic, antitussive, expectorant and antiinflammatory drug, were studied. Chikusetsusaponin III was especially remarkable as it had antipyretic, antitussive, expectorative and antiedemic activities, increased intestinal motility, and prevented stress ulcers. Chikusetsusaponin IV showed expectorative action, protection against stress ulcers and acceleration of intestinal motility. Chikusetsusaponin V showed antiedemic activity. The substance giving protective effect against gastric secretion was found in the butanol layer but was not recognized in the saponins. Increased effect of intestinal motility was recognized in aqueous extract.
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松尾 光芳, 松本 茂信
1977 年 25 巻 6 号 p.
1399-1403
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
^<13>C Nuclear magnetic resonance (
13C-NMR) spectra of 16 phenolic compounds were recorded and the Eu (fod)
3 and triethylamine induced shifts of their carbon resonances were measured. Generally, these shift reagents are useful for analyzing
13C-NMR spectra of phenols. By means of Eu (fod)
3, aromatic carbons of phenols were shifted in the order ; ortho, meta and para carbons to a phenolic group. Some anomalous shifts were observed on using Eu (fod)
3, the upfield shift for the C-6 nucleus in 2-methoxyphenol and the relatively large downfield shifts for the C-6 nuclei in ortho-alkylphenols. Triethylamine induced a downfield shift for the C-1, C-2 and C-6 nuclei, and an upfield shift for the C-3, C-4 and C-5 nuclei of phenols with exception of 2-methoxyphenol.
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高井 誠, 劉 勝彦, 荻原 幸夫, 飯高 洋一
1977 年 25 巻 6 号 p.
1404-1407
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The crystals of sodium lucidonate dihydrate were isolated from the fruits of Lindera erythrocarpa MAKINO (Lanraceae) and its structure was determined by X-ray analysis. The crystals are orthorhombic with space group P2
12
12
1 and unit cell dimensions are a=15.164 (7), b=15.980 (7), c=6.242 (3) Å, Z=4. The structure was solved by the direct method and refined by the block-diagonal least-squares method. The final R value for 770 observed structure factors was 0.065. The molecules are linked together by the coordination of oxygen atoms to the sodium ion and by the hydrogen bonds. The coordination number of sodium ion is six.
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北川 勲, 池西 裕二, 吉川 雅之, 任 光植
1977 年 25 巻 6 号 p.
1408-1416
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Following the previously described two selective cleavage methods (i.e. photolysis and lead tetraacetate degradation) for the glucuronide linkage in the oligoglycosides, it has been found that acetic anhydride and pyridine treatment is also an effective method to selectively cleave the glucuronide-saponin at the glucuronide moiety. The degradation method has been shown to be different from ordinary acetolysis and by the present method, the glucuronide-saponin, which possesses a free carboxyl function and two carbohydrate residues at C-2'and C-4'in its glucuronide moiety, is decomposed to furnish the acetylated derivatives of the genuine sapogenol and those of the carbohydrate residues. The reaction pathway initiated by mixed anhydride formation and decarboxylative elimination has been presumed.
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進藤 英世, 駒井 亨, 河合 賢司
1977 年 25 巻 6 号 p.
1417-1425
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
L-5-Hydroxytryptophan (5-HTP) and L-3, 4-dihydroxyphenylalanine (DOPA) were comparatively investigated of their mechanisms of intestinal absorption, metabolism in the intestine and liver tissues and mechanisms of passage through the blood-brain barriers, by means of in vitro and/or in situ techniques using rat tissues. The corresponding D-isomers were also investigated for comparison. L-5-HTP, but not the D-isomer, was found to be absorbed from the intestine by an active transport mechanism in the same way as L-DOPA. In vitro studies using rat brain cortex slices proved that both L-5-HTP and L-DOPA, but not their D-isomers, are taken up by the brain tissues by an active transport mechanism which is saturable, energy-dependent and competitive. There was no substantial difference between L-5-HTP and L-DOPA in the rate of intestinal absorption and that of brain uptake. It was indicated, however, that L-5-HTP was decarboxylated in the intestine to a much less extent than L-DOPA during the absorption and the decarboxylation activity of rat intestine and liver homogenates was found to be about four and seven times higher for L-DOPA than for L-5-HTP, respectively. The latter results suggest that the oral dose of L-5-HTP can be much more easily transferred into the circulating blood without being suffered from decarboxylation in the peripheral organs than L-DOPA, resulting in a more efficient penetration of L-5-HTP into the brain as a serotonine precursor.
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高尾 楢雄, 岩佐 衣子, 上垣内 みよ子, 杉浦 真喜子
1977 年 25 巻 6 号 p.
1426-1435
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Analyses of CMR spectra at room temperature of the free bases, N-methosalts, and N-protonated salts of tetrahydroprotoberberines indicated that in the chloroform solution, the amount of the B/C-cis form in comparison with the B/C-trans form increases in the order of the alkaloids (such as tetrahydropalmatine (1)) in group I, those (such as capaurine (9)) in group II, and those (such as mesocorydaline (16)) in group III. The equilibrium of the B/C-trans and B/C-cis forms was confirmed by analyses of CMR spectra at low temperatures of tetrahydroprotoberberines in deuteriomethylene-chloride solution and the approximate proportion of the two conformations was determined in acetylcapaurine (13), diacetylcapaurimine (14), and capaurimine di-p-bromobenzoate (15).
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百瀬 雄章, 内田 秀治, 山足 典子, 今西 武
1977 年 25 巻 6 号 p.
1436-1442
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
7-Hydroxyquinoline (X) was hydrogenated over 5% rhodium on alumina to give the trans-amino-alcohol (XIa) as a main product along with other possible diastereomeric isomers. Separation of four isomers from the row product was achieved after conversion to the N-benzyl derivatives, XIIIa, XIIIb, XIIIc and XIIId. Configurations of them were assigned from chemical and physical evidences. A possible mechanistic pathway to the trans-fused ring system on hydrogenation was also discussed.
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伊藤 磯雄, 植田 泰誠, 加藤 福実
1977 年 25 巻 6 号 p.
1443-1446
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
A novel bicyclic ring, pyrazolo [3, 4-b] [1, 4] oxazepine was synthesized. The Mannich reaction of 3-hydroxy-5-methyl-1-phenyl pyrazole (I) with p-substituted aniline gave 3-hydroxy-5-methyl-1-phenyl-4-(p-substituted anilino) methyl pyrazoles (II, III, IV, V), which were reacted with chloroacetyl chloride to give 3-methyl-2-phenyl-5-(p-substituted)-phenyl-4, 5, 6, 7-tetrahydro-2H-pyrazolo [3, 4-b] [1, 4] oxazepin-6-ones (VI, VII, VIII, IX). The reduction of VI, VII, and VIII with lithium aluminum hydride gave 3-methyl-2-phenyl-5-(p-substituted) phenyl-4, 5, 6, 7-tetrahydro-2H-pyrazolo [3, 4-b] [1, 4] oxazepines (X, XI, XII) and ring-opened products (XIII, XIV, XV).
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中江 裕子, 潮海 泰子, 村西 昌三
1977 年 25 巻 6 号 p.
1447-1449
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The activities of three bile canalicular enzymes, alkaline phosphatase, 5'-nucleotidase and ATPase, and protein concentration in bile were significantly elevated by the intrabiliary retrograde infusion of Triton X-100. The results suggest that a part of the bile canalicular site of the liver plasma membrane was solubilized by the treatment. This explains the fact that the active biliary excretion of organic anions and cations was markedly inhibited by the same treatment.
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板谷 泰助, 田中 孚美子, 藤井 澄三 /, NELSON J. LEONARD
1977 年 25 巻 6 号 p.
1449-1452
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
1-Benzyl- (IIIa), 1-(3-methyl-2-butenyl)-(IIIb), and 1-allyladenine (IIIc) were prepared in 77, % 44%, and 69% yield, respectively, by alkylation of adenosine (I) followed by heating the resulting 1-substituted adenosine hydrobromides (IIa, b, c) in acetic acid.
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大谷 敏夫, 石丸 くるみ, 中村 昭四郎, 亀井 敏夫, 鈴木 肇
1977 年 25 巻 6 号 p.
1452-1455
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Total and free serum cholesterol was determined by using a new cholesterol oxidase preparation obtained from Streptomyces. Cholesterol esters were hydrolyzed by cholesterol esterase, and free cholesterol was oxidized to cholest-4-en-3-one with the simultaneous production of hydrogen peroxide, which oxidatively coupled with 4-aminoantipyrine and phenol to form the quinoneimine dye. The produced color was measured by its absorption at 500nm. The results of serum cholesterol determination correlate well with those obtained by Zak-Henly and Kiliani method. Moreover, this enzymatic method is simpler and more sensitive than the conventional method.
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加納 慎蔵, 横松 力, 江幡 勉, 渋谷 皓
1977 年 25 巻 6 号 p.
1456-1459
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The 5, 6, 12, 13-tetrahydro-7-methyl-7H-dibenz [b, f] azonines (1), (10) and (11) were heated in the presence of mercuric acetate to yield the corresponding N-demethylated derivatives (8), (13) and (14), respectively.
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藤本 貞毅, 中川 力, 石光 進, 小原 晃
1977 年 25 巻 6 号 p.
1459-1462
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The violet-colored acid phosphatase was purified from leaves of spinach (Spinacia oleracea). The purified preparation was found to be homogeneous by electrophoresis and ultracentrifugation. Concentrated solution of the enzyme had an intense violet color with a broad absorption band between 410 nm and 700 nm. The peak was at around 530 nm. The molecular weight of the enzyme was approximately 92000. The enzyme was composed of two subunits of equal size and contained manganese. The result of staining of the enzyme in disc electrophoresis gel by periodic acid-Schiff reagent indicated that the enzyme was glycoprotein.
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井上 謙一郎, 塩原 義則, 井上 博之
1977 年 25 巻 6 号 p.
1462-1468
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Methods for the preparation of [3'-
2H]-4-(2'-carboxyphenyl)-4-oxobutanoic acid and [4, 8-
2H
2]-2-carboxy-4-hydroxy-α-tetralone (CHT) starting from 3-methoxyphthalic anhydride have been demonstrated as model experiments for the preparation of several
3H-labeled compounds necessary for the elucidation of the biosynthetic pathways of prenylnaphthoquinone congeners occurring in Catalpa ovata.
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吉井 英一, 小泉 徹, 林 市裕, 広井 靖子
1977 年 25 巻 6 号 p.
1468-1470
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
The reaction of conjugated enones and dienones with trimethyl- or triethyl-silane in the presence of titanium tetrachloride followed aqueous workup produced the corresponding α, β-saturated ketones. This particular Lewis acid catalysis has advantage over Rh (I) complex catalysis which fails for sterically hindered substrates.
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増田 克忠, 安立 準, 野村 敬一
1977 年 25 巻 6 号 p.
1471-1474
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
Synthesis and 1, 3-dipolar cycloaddition of the mesoionic ring system, anhydro-5-hydroxy-1, 3-oxathiolium hydroxide, were studied. Acylthioglycolic acids (IIa, b) afforded the mesoionic products (IIIa, b) in the reaction with trifluoroacetic anhydride. In the case of α-substituted thioglycolic acids (IId, e), the mesoionic intermediates which couldn't be isolated were trapped with dimethyl acetylenedicarboxylate in situ.
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平内 三政, 増田 佐智子
1977 年 25 巻 6 号 p.
1474-1478
発行日: 1977/06/25
公開日: 2008/03/31
ジャーナル
フリー
A simple and rapid fluorodensitometric method for simultaneous determinations of siomycin A, siomycin B, and siomycin D
1 in siomycins was established. The method is based on the fluorescence reaction of siomycins with sulfuric acid after separation on thin-layer chromatographic plate, and can be applied satisfactorily to simultaneous determinations in the concentration range of 5-1000ng per spot.
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