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Yasuhiko Sato, Shiro Nishioka, Osamu Yonemitsu, Yoshio Ban
1963 Volume 11 Issue 7 Pages
829-834
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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(+)-3-Oxocyclopentanecarboxylic acid was chemically correlated with (+)-3-carboxyadipic acid and with (+)-3-methylcyclopentanone, both of which are of known absolute configurations. This correlation established that the natural sarkomycin, (-)-2-methylene-3-oxocyclopentanecarboxylic acid, is represented by the formula (XXXII), of which C-1 is S.
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Shigeharu Tanayama, Michio Ui
1963 Volume 11 Issue 7 Pages
835-842
Published: July 25, 1963
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A salicylaldehyde method for microdetermination of blood ketone bodies was extensively studied. A wide variety of factors influencing the oxidation of keto acids to acetone and color development was examined, and a simple and sensitive method was standardized by which periodical analysis of ketone bodies on 0.1 ml. of rat whole blood can be routinely performed.
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Setsuo Kiryu, Sadao Iguchi
1963 Volume 11 Issue 7 Pages
843-845
Published: July 25, 1963
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It was definitely found that dehydroacetic acid had two kinds of crystals, one of which was α-form (monoclinic), stable at a low temperature, and the other was β-form (triclinic), stable at a high temperature. Transition from α-form to β-form occurred at 80°. Lattice constants and other crystal data of these two kinds of crystals were reported.
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Yasuo Makisumi
1963 Volume 11 Issue 7 Pages
845-850
Published: July 25, 1963
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Ten kinds of alkoxy-s-triazolo [1, 5-a] pyrimidines were synthesized by reaction of the corresponding chloro derivatives with sodium alkoxides and the transetherification reaction of these compounds was investigated. It was clear that the alkoxyl group at 7-position was transetherified more easily than that at 5-position in s-triazolo [1, 5-a]-pyrimidines.
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Yasuo Makisumi
1963 Volume 11 Issue 7 Pages
851-859
Published: July 25, 1963
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Thermal rearrangement of 5-methyl-7-allyloxy-s-triazolo [1, 5-a] pyrimidine (II) was investigated and seven kinds of products ; an unknown oil, 5-methyl-s-triazolo [1, 5-a] pyrimidin-7-ol (III), its 6-allyl derivative (IV), 3-and 4-allyl-5-methyl-s-triazolo [1, 5-a] pyrimidin-7 (3H and 4H)-ones (IIIb and IIIa), and their 6-allyl derivatives (IVb and IVa) were obtained. In order to confirm the structure of these products, the condensation of ethyl acetoacetate or its 2-allyl compound with N-allyl derivatives (Va and Vb) of 5-amino-s-triazole was examined. On the other hand, allylation of III and IV afforded the 3- and 4-allylated products which were respectively identified with the compounds (IIIa, IIIb and IVa, IVb) obtaining by the thermal rearrangement of II. The mechanism of the above thermal rearrangement reaction was discussed.
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Yasuo Makisumi
1963 Volume 11 Issue 7 Pages
859-866
Published: July 25, 1963
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The thermal rearrangement of 7-allyloxy-5, 6-dimethyl-s-triazolo [1, 5-a] pyrimidine (III) was carried out and five kinds of rearrangement products ; 3- and 4-allyl-5, 6-dimethyl-s-triazolo [1, 5-a] pyrimidin-7 (3H and 4H) -ones (Ib and Ia), 5- (3-butenyl) -6-methyl-s-triazolo [1, 5-a] pyrimidin-7-ol (IV), and its 3- and 4-allyl derivatives (IVb and IVa) were obtained. Among these products, the out-of-ring Claisen rearrangement product (IV) was obtained in 66% yield. This reaction is the first example of out-of-ring migration of an allyl group to an active methyl group.
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Kenichi Takeda, Hitoshi Minato, Satoko Nosaka, Ichiro Ishizuka
1963 Volume 11 Issue 7 Pages
867-871
Published: July 25, 1963
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When α-guaiene (II) was hydrogenated with palladium charcoal as a catalyst under neutral or acid conditions, it gave a mixture of α-dihydroguaiene (IV) and its double bond isomer. The constitution of the latter was established as V.
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Toyozo Uno, Hiroyuki Yasuda, Yutaka Sekine
1963 Volume 11 Issue 7 Pages
872-875
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Metabolic product of sulfadiazine excreted in the urine after its oral administration was examined chiefly through paper chromatography and paper electorophoresis. It was thereby found that the substances excreted are sulfadiazine, N
4-acetylsulfadiazine, sulfadiazine-N
4-glucuronide, sufladiazine-N
4-sulfonate and sulfanilamide.
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Hitoshi Minato, Ariyoshi Shimaoka
1963 Volume 11 Issue 7 Pages
876-881
Published: July 25, 1963
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In order to find a proto-sapogenin of luvigenin (III), the structural investigation of the unknown sapogenins from Metanarthecium luteo-viride MAXIM was attempted. Isonarthogenin (Va), narthogenin (VIa) and neonogiragenin (XIIIa) were isolated, and the former two sapogenins were established to be steroidal sapogenins having a hydroxyl group at C-27.
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Akira Takamizawa, Kentaro Hirai, Yoshio Hamashima
1963 Volume 11 Issue 7 Pages
882-887
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Direct introduction of substituents of organic groups to the hydroxyl group of thiamine was achieved by the use of phosgene. O-Chlorocarbonylthiamine (VI) thus prepared was converted into O-carbamoylthiamine and O-alkoxycarbonylthiamine. The free bases of O-carbamoyl derivatives were assigned dihydrothiochrome structures (XV) and (XVI). S-Carbamoylthiamine derivatives were also prepared. Application of S→O rearrangement of the carbamoyl group gave various O, S-bis substituted thiamine derivatives.
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Minoru Sekiya, Keiichi Ito
1963 Volume 11 Issue 7 Pages
888-891
Published: July 25, 1963
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N-Benzylidene-α-acetamidobenzylamine reacted with dialkylamines in the presence of methylamine or ammonia affording compounds of new benzylidenediamine type, N- (α-dialkylaminobenzyl) acetamides. By using piperidine, morpholine, dibenzylamine, and N-methylbenzylamine as the secondary amine reactant the corresponding products were obtained. A mechanism for this reaction was suggested.
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Minoru Sekiya, Keiichi Ito
1963 Volume 11 Issue 7 Pages
892-894
Published: July 25, 1963
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The catalytic hydrogenolysis of some compounds that are classified as N-hydroxy-methylamides, N-dialkylaminomethylamides, and N- (α-dialkylaminobenzyl) amides was carried out using Raney nickel catalyst under high pressure of hydrogen. It was found in every case that the hydrogenolysis took place at the carbon bond connecting to nitro gen in the amide group.
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Minoru Sekiya, Akira Hara
1963 Volume 11 Issue 7 Pages
895-901
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Catalytic hydrogenation of some azomethines, such as N-benzylideneaniline, N-benzylidenebenzylamine, and N- (4-methoxybenzylidene) phenethylamine in the presence of amide was examined under high pressure of hydrogen. The reaction resulted in conversion, ArCH=NR+2R'CONH
2+H
2→ArCHNHCOR'+RNHCOR'+NH
3, particularly in excellent yields with formamide. With regard to this reaction path, it was recognized that the initiating essential reaction between azomethine and formamide would be the reaction, ArCH=NR+HCONH
2→ArCH=NH+RNHCHO (NH
3 acts as a catalyst), which was demonstrated by using N-benzylidene-4-sulfonamidobenzylamine as azomethine. Based on this reaction, the whole pathway for the above hydrogenation reaction was proposed. Mechanism for hydrogenation reaction of nitriles, oximes, and ammoniaaldehyde mixtures in the presence of formamide was also suggested.
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Minoru Sekiya, Akira Hara
1963 Volume 11 Issue 7 Pages
901-905
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Formation of N-arylmethylene-1-acylamino-1-arylmethylamine resulted in some cases when aromatic aldehyde-ammonia mixture or hydrobenzamide was allowed to react with amide. In the light of this fact the mechanism comprehensive for all the reactions which lead to the formation of N-arylmethylene-1-acylamino-1-arylmetylamine was proposed.
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Koji Yamakawa, Hisao Ochi, Kiichi Arakawa
1963 Volume 11 Issue 7 Pages
905-911
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Oxidation of 1, 1'-diacetylferrocene with sodium hypochlorite and iodine-pyridine gave 1, 1-ferrocenedicarboxylic acid (III) and 1-acetyl-1'-ferrocenecarboxylic acid (VI), respectively. The polyester polymer of ferrocene was obtained from dimethyl-1, 1'-ferrocenecarboxylate (V) and ethylene glycol. 1, 1'-Bis (1-hydroxyethyl) ferrocene (VIII) was converted to 1, 1'-(1, 1'-epoxydiethyl) ferrocene (IX) by chromatographic method or with p-toluenesulfonyl chloride. Stereochemistry of the cyclic dimethyl ether (IX) is discussed. Treatment of 1, 1'-ferrocenedicarboxylic acid with N, N'-dicyclohexylcarbodiimide gave N, N'-dicyclohexyl-N. N' -bis (cyclohexylcarbamoyl) -1, 1'-ferrocenedicarboxamide (XIV).
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Takeo Ueda, Tadakazu Tsuji, Hiroko Momona
1963 Volume 11 Issue 7 Pages
912-917
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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The replacement of 4-hydroxyl group of aminopyrimidinols by sulfhydryl in one step, through the action of phosphorus pentasulfide in triethylamine or 3-picoline. 5-Acylamino-6-amino-4-pyrimidinols were treated with phosphorus pentasulfide in pyridine, to yield thiazolo [5, 4-d] pyrimidine and 6-purinethiol compounds. The yield of both two type compounds were changed according to a functional group in the starting substance. These products, in addition, other 6-purinethiol and related compounds were screened as to their antiviral activities on poliomyelitis virus. Any of the compounds, however, did not exert a significant activity on the virus.
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Kazuya Kunugi
1963 Volume 11 Issue 7 Pages
918-921
Published: July 25, 1963
Released on J-STAGE: March 31, 2008
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Concerning with the alcoholyses reactions of methyl stearate by sucrose, rate study was carried out. Sucrose and methyl stearate were alcoholized in dimethylformamide at various molar ratios. The rates of reactions were analyzed assuming that they were of the second order, and the validity of this assumption was proved. The velocity constant at any molar ratio gave a good accordance and was determined to be 0.3∼0.4 L. mole
-1 hr
-1.
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Kazuya Kunugi
1963 Volume 11 Issue 7 Pages
922-925
Published: July 25, 1963
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As one of the important problems in purifications of sucrose fatty acid ester, a new food-additive, its deacidification was investigated. The method of ion exchange in a non-aqueous medium was carried out, and it was concluded that the deacidification of sucrose ester was performed by treatment with anion exchange resin after treatment with cation exchange resin or inorganic acid. A small amount of water contained in the solvent was effective to accelerate the exchange reaction. Decoloration by the ion exchange resins was also observed.
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Shoji Shibata, HsuchChing Chiang
1963 Volume 11 Issue 7 Pages
926-930
Published: July 25, 1963
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The structure of grayanic acid, C
23H
26O
7, m.p. 186∼189°which was isolated from Cladonia Grayi MERRILL has been established to be an orcinol-type depsidone as formulated (II).
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Yutaka Asahi
1963 Volume 11 Issue 7 Pages
930-938
Published: July 25, 1963
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Thioacetazone gives 2 steps of 2-electron reduction waves in acid media, which are ascribed to a reductive cleavage of the N-N bond in the protonated thioacetazone and a saturation of the -CH=N- group, respectively. Precedence of the protonation of base on the electrode causes in a kinetic current. In alkaline media, thioacetazone gives other reduction wave due to a 2-electron reduction of the -CH=N- group in the free base, and an anodic wave which are ascribed to the formation of a mercurous complex on the electrode. The reduction waves of benzaldehyde thiosemicarbazone and p-acetamidobenzaldehyde semicarbazone and the first reduction wave of S-methylthioacetazone are also ascribed to the reaction as similar as that of thioacetazone. The second reduction wave of S-methylthioacetazone as well as the reduction waves of S-methylisothiourea and S-ethylisothiosemicarbazide are assumed to be due to the reduction of the RSC=NH group. p-Acetamidobenzaldehyde shows 2 steps of 1-electron reduction waves at pH about 4, which overlap together and diminish at higher pH. Thiosemicarbazides in alkali give and anodic wave due to a reaction with mercurous ion.
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Shunji Ishikura, Keiko Yokota
1963 Volume 11 Issue 7 Pages
939-942
Published: July 25, 1963
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A simple, sensitive analytic method for measuring to differentiate inorganic mercury and phenylmercury acetate has been developed. The method is found useful for analysis of mercurials used extensively as drug in medical and agricultural fields. An acidified sample solution was extracted with dithizone-carbon tetrachoride solution, the carbon tetrachloride layer was chromatographed on an alumina column, and the separated dithizonate solutions were measured by photoelectric colorimeter. By means of the method here reported, organic and inorganic mercury can be separately determined at levels to 0.02 p.p.m. with an error not exceeding 5%, using a minute amounts of materials and without subjecting it to the tedious procedure of preliminary oxidative degradation. This method is not disturbed by other metal ions. Stabilization of dithizonates is described.
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Hisashi Nogami, Yoshio Kanakubo
1963 Volume 11 Issue 7 Pages
943-947
Published: July 25, 1963
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The hydrolysis of sodium octyl (SOS), myristyl (SMS) and cetyl sulfate (SCS) as sodium lauryl sulfate (SLS) homologue and that of sodium pentadecane-8-sulfate (SPS) as secondary alcohol sulfate in hydrochloric acid solution were studied. 1) It was recognized that the sodium alkyl sulfates were relatively stable below their critical micelle concentration (CMC) and less stable above their CMC as well as SLS. Accordingly, this phenomenon was ascribed to the micellization and the ionic atmosphere around the micelle of the sodium alkyl sulfate. 2) The sodium normal alkyl sulfate with the longer alkyl chain length was less stable than the shorter chain length. It was thought that the micelle with the longer alkyl chain length was more affected by gegen-ion than the shorter chain length.
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Seigoro Hayashi, Hiroshi Ueki, Yoko Ueki, Hiroyuki Aoki, Kanji Tanaka, ...
1963 Volume 11 Issue 7 Pages
948-951
Published: July 25, 1963
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Sixteen of the quinone derivatives were examined for the antitumor activity against Ehrlich ascites tumor cell by the cylinder agar plate method and for the antibacterial activity against Staphylococcus aureus TERASHIMA and Esherichia coli. Any relationship were not found between the antitumor and the antibacterial activity.
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Fumio Yoneda, Takayuki Ohtaka, Yoshihiro Nitta
1963 Volume 11 Issue 7 Pages
954-956
Published: July 25, 1963
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Kazuo Tori, Tetsuo Tomita, Hiroshi Itazaki, Masayuki Narisada, Wataru ...
1963 Volume 11 Issue 7 Pages
956-959
Published: July 25, 1963
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