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Yoshihiro Nitta, Masaya Namekata, Eiichi Tomita, Yoshiharu Nawata
1962 Volume 10 Issue 3 Pages
159-167
Published: March 25, 1962
Released on J-STAGE: March 31, 2008
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In order to obtain the heparin-like active substances, the sulfates of oxidized starch, obtained by oxidation with nitric acid and its derivatives, were prepared by the reaction with formamide and chlorosulfonic acid. Sulfate of reduced product of oxidized starch, sulfates of oxidized starch amine, sulfates of methyl ester of reduced product of oxidized starch and its reduced product, and demethyl product were also prepared. Reduced product of oxidized starch is found more suitable as a starting material to prepare the heparin-like substances, because reduced product of oxidized starch having no carbonyl group is more stable against degradation during sulfation.
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Masaya Namekata, Sachiko Iwai
1962 Volume 10 Issue 3 Pages
167-171
Published: March 25, 1962
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Anticoagulant activity of synthetic heparinoids was determined and its relationship to the sulfur content and/or to the molecular size (viscosity) was investigated. Carboxyl residue at C-6 in the glucose unit was proved to weaken the toxicity. Heparin, oxidized starch sulfate and sulfate of the reduced product of oxidized starch were compared for their stability against acids and alkalis.
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Masaya Namekata
1962 Volume 10 Issue 3 Pages
171-176
Published: March 25, 1962
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The inhibitory effect of polysaccharide sulfates on the proteolytic action of pepsin is due to their sulfate group and is enhanced with the increasing sulfate group content. The effect of (DP)^^
- on the inhibitory activity is weaker than that of the sulfur content, but the minimum critical value is necessary for the appearance of inhibitory action. Inhibitory effect is influenced largely by (DP)^^
-, especially in samples with a small sulfur content, and slightly by samples with a large sulfur content. The inhibitory activity by polysaccharide sulfates is not correlated to their anticoagulant activity.
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Masaya Namekata
1962 Volume 10 Issue 3 Pages
177-181
Published: March 25, 1962
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Sulfates of oxidized starch and its reduced products were investigated for their protective effect on experimental peptic ulceration. 1) Both oxidized starch sulfate and sulfate of reduced product of oxidized starch with various sulfur content and viscosity showed protective effect on ulceration of Shay rats when administered in 30 mg. doses intra-esophageally, and the protective effect is enhanced with increasing sulfur content, just the same as their inhibitory activity on proteolytic action in vitro. 2) Their protective effect on ulceration is closely related to the loss of pepsin activity in gastric juice. The decrease in pepsin activity is proportional to the decrease in ulceration rate. From the fact that they had no protective effect on ulceration by subcutaneous administration, their protective effect may be caused by their direct inhibition of pepsin activity in gastric juice. 3) They had no protective effect on Takagi's stress rats by intra-esophageal administration.
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Masaya Namekata
1962 Volume 10 Issue 3 Pages
182-185
Published: March 25, 1962
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It was confirmed that the complex of pepsin with ROS-S and heparin is formed in an acid solution (pH 1.5∼4.4) and that the complex is dissociated at the pH above 5.2. The isolated complex has no proteolytic activity, but it was almost completely recovered by removing ROS-S or heparin as the barium salt or protamine complex. It was confirmed that the inhibitory action of polysaccharide sulfates on proteolytic action of pepsin is caused by the formation of inactive complex of pepsin with the sulfates.
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Masazumi Kawanishi
1962 Volume 10 Issue 3 Pages
185-190
Published: March 25, 1962
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A new synthesis of 1-alkyl-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo [a] quinolizin-2-ones (VIII) (5 specimens) was described. 3-(3, 4-Dimethoxyphenethylamino) propionitrile was acylated with the chloride of various ethyl alkylhydrogenmalonates followed by esterification to yield the corresponding diester-amides (V), which were cyclized by refluxing with phosphoryl chloride alone. The products were reduced to afford α-alkyl-2-(2-ethoxycarbonylethyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-1-isoquinoline acetates (VI). The latter were cyclized with sodium hydride in boiling toluene according to Dieckmann's method and the products were submitted to ketonic fission to yield the ultimate products in rather a poor yield. 6, 7-Dimethoxy-3, 4-dihydroisoquinoline was the common by-product produced during the ketonic fission reaction.
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Masazumi Kawanishi
1962 Volume 10 Issue 3 Pages
191-200
Published: March 25, 1962
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The proposed structure for rotundine and dihydro-rotundine by Matsuno was proved untenable. The synthesized so-called rac-dihydro-rotundine (II) was dehydrogenated with mercuric acetate in methanolic solution to give the product as well-defined quaternary salt (XII). This was more advantageously prepared by dehydrogenating 2-oxo-3-methyl-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo [a] quinolizine (IX), the intermediate for (II), with mercuric acetate in 10% acetic acid solution to produce a phenolic quaternary salt (X) and methylating the latter with dimethyl sulfate and an excess of conc. potassium hydroxide solution, giving (XIV). Natural dihydro-rotundine, prepared by reducing the natural alkaloid, gave a dehydro-quaternary salt by a similar method, but the product showed ultraviolet and infrared absorption spectra different from those of (XII). Partial hydrogenation experiments of (XII) and (XIV) under a variety of conditions failed to afford a compound having the diene system, as was proposed for natural rotundine. The products isolated were rac-dihydro-rotundine-type of compound, whose three isomers (II, XV, and XVI) were characterized. In conformity with their structure they smoothly gave the ketone (IX) when treated with dil. hydrochloric acid, whereas the natural dihydro-rotundine was proved to be quite stable to hydrochloric acid even at an elevated temperature. Similar experiments were also conducted with synthetic rac-dihydro-isorotundine (I).
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Masuo Akagi, Isamu Aoki
1962 Volume 10 Issue 3 Pages
200-204
Published: March 25, 1962
Released on J-STAGE: March 31, 2008
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3, 5-Di-tert-butyl-4-hydroxy-benzoic acid, 4, 4'-ethylenebis (2, 6-di-tert-butylphenol), and unchanged α-hydroxy-2, 6-di-tert-butyl-p-cresol were isolated and characterized from the urine of a rabbit dosed with α-hydroxy-2, 6-di-tert-butyl-p-cresol. The isolated 3, 5-di-tert-butyl-4-hydroxy-benzaldehyde was identified as its 2, 4-dinitrophenylhydrazone. A glucuronide was isolated as its triacetyl-methyl ester. Antioxidative effect of 2, 6-di-tert-butyl-p-cresol and its derivatives on vitamin A was examined.
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Masao Shimizu, Fumihiko Uchimaru, Bumpei Kurihara
1962 Volume 10 Issue 3 Pages
204-210
Published: March 25, 1962
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High-pressure catalytic hydrogenation of N-substituted 3-nortropanones reported in Part I of this series and also of their methiodides was examined. In the case of tertiary amines, only the corresponding 3α-ols were obtained as the main product and the influence of N-substituents was not observed. Before the reduction of methiodides, the necessary infrared spectra were measured in order to establish the purity of the products and recovered materials. In reduction of methiodides, the more bulky the N-substituent became, the smaller did the amounts of 3α-ol methiodides. The possibility of a steric hindrance by fixed Na (piperidine side) substituents in the reduction was discussed.
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Tadakazu Tsuji, Taka Nakata, Takeo Ueda
1962 Volume 10 Issue 3 Pages
210-219
Published: March 25, 1962
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1-Acyl-2-sulfanilylhydrazine, 1-acyl-2-(4-amino-1-naphthylsulfonyl) hydrazine and their acyl derivatives were synthesized and their antimicrobial activity was examined. Among the derivatives of 1-acyl-2-sulfanilylhydrazine series, several compounds showed a weak in vitro activity on tubercle bacilli, but none of the compounds exerted any antibacterial or antiviral activity. On the contrary, there were found one compound having activity against tubercule bacilli comparable to that of INAH and dihydrostreptomycin, and two compounds having in vivo effect on Japanese B encephalitis virus equal to that of N-(4-amino-1-naphthylsulfonyl) dodecanamide, among the derivatives of 1-acyl-2-(4-amino-1-naphthylsulfonyl) hydrazine, but none of the compounds showed any activity against Escherichia coli communi or Staphylococcus aureus.
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Kuniyoshi Tanaka, Mikio Honjo, Yasushi Sanno, Hiroki Moriyama
1962 Volume 10 Issue 3 Pages
220-225
Published: March 25, 1962
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Reaction of the dicyclohexylguanidinium salt of adenosine 5'-phosphoramidate (I) with tribenzyl pyrophosphate (II) in o-chlorophenol, and reductive debenzylation of the reaction mixture resulted in the formation of adenosine 5'-triphosphate (ATP). The guanidinium salt was reacted with bis-triethylammonium pyrophosphate (V) in a mixture of tricresol and acetonitrile, and ATP was isolated as its barium salt from the reaction mixture by ion-exchange chromatography. The overall yield of ATP from (I) was 43%. Reaction of the dicyclohexylguanidinium phosphoramidates of uridine, cytidine, and desoxyadenosine with (V) also gave uridine, cytidine, and desoxyadenosine 5'-triphosphates in a good yield.
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Mikio Honjo, Yoshiyasu Furukawa, Kinichi Imai, Hiroki Moriyama, Kuniyo ...
1962 Volume 10 Issue 3 Pages
225-231
Published: March 25, 1962
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Uridine 5'-phosphoramidate (I) was allowed to react with α-glucuronic acid 1-phosphate (II), and α-uridine diphosphate glucuronic acid (α-UDPGA) (III) was isolated from the reaction mixture by ion exchange chromatography. Likewise, β-UDPGA (V) was produced from (I) and β-glucuronic acid 1-phosphate (IV). Formation of (III) was also observed by the oxidation of α-uridine diphosphate glucose (VI) in the presence of platinum oxide catalyst. Ability of (III) and (V) to form o-aminophenolglucuronide was examined with the transferase in microsomes of a guinea pig liver ane only (III) was found to be active. This fact indicated that natural UDPGA takes the same configuration as (III).
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Yasushi Sanno, Kuniyoshi Tanaka
1962 Volume 10 Issue 3 Pages
231-237
Published: March 25, 1962
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Reaction of cytidine diphosphate (CDP) (II) with ethyleneimine (III) produced CDP-ethanolamine (IV), and methylation of the product with methyl iodide yielded CDP-choline (IX).
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Fumihiko Uchimaru
1962 Volume 10 Issue 3 Pages
238-240
Published: March 25, 1962
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The infrared spectral behaviors of 8-(2-hydroxyethyl)-3-nortropanone and related compounds in dilute nonpolar solution were examined. From the values of C=O and OH stretching frequencies it was concluded that all these compounds form intramolecular hydrogen bond of a type OH····N. The data obtained also agreed with those of OH····N hydrogen bond appearing in recent literature.
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Mitsuko Asai, Komei Mizuno, Satoru Kuwada
1962 Volume 10 Issue 3 Pages
243-244
Published: March 25, 1962
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Tanezo Taguchi, Toshisuke Takatori, Masaharu Kojima
1962 Volume 10 Issue 3 Pages
245-246
Published: March 25, 1962
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Kyosuke Tsuda, Susumu Ikuma, Masaaki Kawamura, Ryuji Tachikawa, Yoshih ...
1962 Volume 10 Issue 3 Pages
247-249
Published: March 25, 1962
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