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Morio Ikehara, Tohru Ueda, Kyoichi A. Watanabe
1960 Volume 8 Issue 8 Pages
661-667
Published: August 25, 1960
Released on J-STAGE: March 31, 2008
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Various para-substituted benzyl phosphates were subjected to debenzylation reaction with sodium iodide in acetone or methyl ethyl ketone. Reaction of para-substituted benzyl diphenylphosphates was investigated kinetically and relative easiness of debenzylation was found to be in the decreasing order of p-nitro-, p-bromo-, unsubstituted, and p-methyl-benzyl groups. Evidences for S
N2 mechanism are described.
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Taichiro Komeno
1960 Volume 8 Issue 8 Pages
668-671
Published: August 25, 1960
Released on J-STAGE: March 31, 2008
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Treatment of 11β, 12β-epithiocholane-3α, 24-diol (I) with acetic anhydride and p-tolu-enesulfonic acid gave 12β-acetylthio-9(11)-olefin (II), structure of which was assumed by its chemical conversion into the 9(11)-ene or 9(11)-en-12-one compound and also by comparison of molecular rotation differences between the 12-mercapto-9(11)-ene and the corresponding alcohols.
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Taichiro Komeno
1960 Volume 8 Issue 8 Pages
672-679
Published: August 25, 1960
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Ring-opening of steroidal 5β, 6β-epoxide by thiocyanic acid gave 5α-thiocyanato-6β-hydroxy compound, which was further converted to the 5α, 6α-episulfide via the 5α-thio-cyanato-6β-mesyloxy compound. Reduction of this episulfide with lithium aluminium hydride mainly gave cholesterol and a small amount of 5α-mercapto-3β-ol. Acetylation and saponification reaction of the latter proceeded in a different manner from those of 3β, 5α-diol. Treatment of the 5α, 6α-epoxide with thiocyanic acid or thiolacetic acid gave the 5α-hydroxy-6β-thiocyanato or 5α-hydroxy-6β-acetylthio compound, respectively.
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Taichiro Komeno
1960 Volume 8 Issue 8 Pages
680-687
Published: August 25, 1960
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Some 16α, 17α-epoxy-steroids were converted to the corresponding thiocyanato-hydrins, (II), (IVa), (IVb), and (VI). Oxime-formation reaction of 3β, 17α-dihydroxy-16β-thiocyanato-5-pregnen-20-one 3-acetate (IVb) yielded a mixture of the oxime-thiol (IXa) and the oxime-disulfide (IX). These structures were assumed by identification of the Beckmann rearrangement products, (X) and (XI). Dehydration of the Beckmann rearragement by-product (XI) gave a base (XVI), which was assumed to be 2'-methylthiazolo [5', 4'-16, 17] androsta-5, 16-dien-3β-ol 3-acetate from the consideration of the mechanism of the Beckmann rearrangement. From the normal. product (X), 16β-mercapto-17β-hydroxy-4-androsten-3-one 16, 17-acetonide (XIX) was synthesized in three steps.
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Takao Murakami, Yoshihiro Nishikawa, Toshio Ando
1960 Volume 8 Issue 8 Pages
688-691
Published: August 25, 1960
Released on J-STAGE: March 31, 2008
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Puerarin, C
21H
20O
9 m.p. 187°(decomp.), and the substance f, which were isolated from Pueraria root were studied to establish their structure. puerarin was proved to be 8-D-glucopyranosyl-4', 7-dihydroxyisoflavone (=8-D-glucopyranosyldaidzein) by oxidation of its dimethyl ether with sodium iodate to 8-formyl-4', 7-dimethoxyisoflavone and by ozonolysis of puerarin to D-glucose and D-arabinose. On hydrolysis with sulfuric acid, the substance f yielded puerarin and D-xylose.
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Masatomo Hamana, Bunsuke Umezawa, Yoshinobu Gotoh, Kanji Noda
1960 Volume 8 Issue 8 Pages
692-697
Published: August 25, 1960
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1-(1-Oxido-2-pyridylmethyl) pyridimium iodide (I) was prepared by the king reaction of 2-picoline 1-oxide. Anomalous chemical poperties of (I) towards acid, which cagused deoxygenation of (I) without difficulty, and alkali are presented. The formation of N-(ρ-dimethylaminophenyl)-α-(1-oxido-2-pyridy) nitrone and α-(ρ-dimethylaminophenyl-imino)-2-pyridineacetonitrile 1-oxide is also described.
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Bunsuke Umezawa
1960 Volume 8 Issue 8 Pages
698-705
Published: August 25, 1960
Released on J-STAGE: March 31, 2008
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The aldonitirone function of N-(p-dimethylaminophenyl)-α-(1-oxido-2-pyridyl) nitrone (I) was shown to undergo facile rearrangement with various reagents, such as sulfur dioxide, thionyl and sulfuryl chloride, phosphorus trichloride, phosphoryl chloride, triphenyl phosphate, and acetic anhydride. To elucidate some of these rearrangement, a cyclic mechanism was postulated.
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Makoto Suzuki
1960 Volume 8 Issue 8 Pages
706-712
Published: August 25, 1960
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The condensation of cis-d-2, 4-dimethylcyclohexanone with para-substituted benzal-dehyde was carried out using tetramethylammonium hydroxide (aldol condensation) or N-methylanilinomagnesium bromide (Nielsen's condensation) as a basic condensation agent. Aldol and Nielsen's condensation gave the stereoisomeric hydroxycarbonylation products, ketol-As and ketol-Ns, respectively, the former showing positive [α]
D values and the latter, negative values.
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Makoto Suzuki
1960 Volume 8 Issue 8 Pages
713-716
Published: August 25, 1960
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The chemical correlations were examined of optically active 2, 4-dimethyl-6-(α-hydroxy (ρ-substituted) benzyl) cyclohexanones whose preparations were reported in the preceding paper. From the present experiments, tohether with the previous informations, following facts were noticed. 1) All of the optically active 2, 4-dimethyl-6-(α-hydroxy (ρ-substituted) benzyl)cyclohexanones prepared by Nielsen's condensation procedure had the same configuration, whereas those by aldol condensation had not always the same one. 2) Some of Nielsen's condensation products were converted chemcially into more stable isomers of positive [α]
D value and some of the converted products tallied with the product obtained by aldol condensation procedure.
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Makoto Suzuki
1960 Volume 8 Issue 8 Pages
717-726
Published: August 25, 1960
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Absolute configurations of optically active 2, 4-dimethyl-6-(α-hydroxy(ρ-substituted)benzyl) cyclohexanones were elucidated and compared with those of cycloheximides, the findings being summarized in Table III. Reaction mechanisms of aldol condensation were discussed.
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Hideaki Shirai, Noriichi Oda
1960 Volume 8 Issue 8 Pages
727-731
Published: August 25, 1960
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In a study on phenanthrene series, 2-methoxy-5, 6-methylenedioxyphenanthrene (XVII) and 2-methoxy-6, 7-methylenedioxyphenanthrene (XI) were prepared through the condensation of 2-nitro-5-methoxybenzaldehyde (II) with sodium salt of 6-bromohomopiperonylic acid or homopiperonylic acid (I) as the starting materials.
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Morizo Ishidate, Yoshio Sakurai, Isao Aiko
1960 Volume 8 Issue 8 Pages
732-737
Published: August 25, 1960
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Fourteen kinds of 2-chloroethyl derivatives of amino acids, indluding N
6, N
6-bis(2-chloroethyl)-DL-lysine (No.539) and N
5, N
5-bis (2-chloroethyl)-DL-ornithine (No.536), were newly synthesized and examined for their anti-tumor activity on Yoshida sarcoma in vivo and in vitro.
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Hiroshi Mitsuhashi, Yuzuru Shimizu
1960 Volume 8 Issue 8 Pages
738-740
Published: August 25, 1960
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Cynanchogenin was dehydrogenated with selenium and two crystalline hydrocarbons were separated. As one of them seems to be Jacobs' hydrocarbon, the carbon skeleton of cynanchogenin was supposed to be c-nor-D-homopregnane.
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Tetsuji Kametani, Yukio Nomura
1960 Volume 8 Issue 8 Pages
741-744
Published: August 25, 1960
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1-Methyl- or 1-ethyl-2(1H)-pyridone was formed by alkaline treatment from their corresponding 1-alkyl-2-chloropyridimium salt of 2-iodo derivative.
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Hideaki Shirai, Noriichi Oda
1960 Volume 8 Issue 8 Pages
744-745
Published: August 25, 1960
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Norio Sugimoto, Yoshio Kowa, Ko Higaki, Shigeru Nakamura, Shigeru Yasa ...
1960 Volume 8 Issue 8 Pages
745-748
Published: August 25, 1960
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Kuniyoshi Tanaka, Mikio Honjo, Yasushi Sanno, Hiroki Moriyama
1960 Volume 8 Issue 8 Pages
749-750
Published: August 25, 1960
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Mikio Honjo, Yoshiyasu Furukawa, Kin-ichi Imai, Hiroki Moriyama, Kuniy ...
1960 Volume 8 Issue 8 Pages
750-752
Published: August 25, 1960
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Yasushi Sanno, Kuniyoshi Tanaka
1960 Volume 8 Issue 8 Pages
753-754
Published: August 25, 1960
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Shigeo Tomomatsu, Jiro Kitamura
1960 Volume 8 Issue 8 Pages
755
Published: August 25, 1960
Released on J-STAGE: March 31, 2008
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