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Hiroshi Mitsuhashi, Masamichi Fukuoka
1966 Volume 14 Issue 8 Pages
809-816
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The synthesis of some C/D cis-15-ketopregnane derivatives from hecogenin is described. Hecogenin was degraded to II which in turn was converted to V via III. Catalytic hydrogenation of V affords the five reduction products, VIII to XIII. VIII was dehydrogenated with selenium but Jacobs' hydrocarbon was not obtained.
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Ikuo Suzuki, Toshiaki Nakashima, Natsuko Nagasawa
1966 Volume 14 Issue 8 Pages
816-823
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Cinnoline 2-oxide (I) gave 5-, 6-and 8-nitrocinnoline 2-oxides (II, III, and IV) on warming with nitric and sulfuric acids or potassium nitrate in sulfuric acid. The nitration of I with benzoyl nitrate afforded II. 5-, 6- and 8-Aminocinnolines (V, VI, VII), 6-and 8-aminocinnoline 2-oxides (VIII and IX), and 5-aminodihydrocinnoline (X) were synthesized for the determination of the structures of II, III and IV. The effect of 2-N-oxide of I in this reaction was affected by the concentration of sulfuric acid and the reaction temperature.
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Goro Tsukamoto, Kiyoshi Harada, Isamu Utsumi
1966 Volume 14 Issue 8 Pages
823-830
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Oxidation of O-benzoylthiamine disufide (I) with hydrogen peroxide in acetic acid yielded O-benzoylthiaminic acid (IIa) and its stereoisomerical compound (IIIa). It was confirmed that these two compounds were in the relation of geometrical isomers which have not yet been found in thiol-type thiamine derivatives : the compound obtained in this experiment was cis-2-(2-methy1-4-amino-5-pyrimidy) methylformamido-5-ben-zoyloxy-2-pentene-3-sulfonic acid (IIIa) of which olefin-CH
3 and SO
3- groups were in cis-configuration . Alkali decomposition of IIIa afforded cis-thiaminic acid (IIIb) corresponding to geometrical isomer of IIb. The configuration of these compounds was confirmed by elemental analyses, ultraviolet, infrared, nuclear magnetic resonance spectra and dissociation constants.
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Mieko Suzuki, Eiko Akaike, Kyosuke Tsuda, Nobuo Ikekawa
1966 Volume 14 Issue 8 Pages
830-833
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The quantitative analysis of sterols in the silkworm was carried out by means of gas chromatographic technique . The amount of sterol in whole body was 0.59mg. and sterol percentage of live weight was 0.066%, as an average, showing that sterol percentage in unfeeding silkworm was larger than that in feeding larva. Furthermore sterol percentage (0.024%) of blood in the silkworm was lower than that in mammals. The amount of cholesterol calculated from total sterol in the whole body was larger than threshold amount of brain hormone cholesterol in the silkworm for the induction of imaginal development On the other hand, the critical period of the brain hormone for the development was coincided with time of sudden increase of blood sterol.
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Nobuo Ikekawa, Mieko Suzuki, Masatoshi Kobayasi, Kyosuke Tsuda
1966 Volume 14 Issue 8 Pages
834-836
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Conversion of β-sitosterol to cholesterol in the silkworm was demonstrated using
3H-β-sitosterol. After ingestion of
3H-β-sitosterol in the larva, the ether extract of homogenized larva was fractionated on alumina. The sterol fraction was separated into cholesterol and β-sitosterol by gas chromatography and the radioactivity of each collected fraction was counted. The strong radioactivity of the larval cholesterol fraction suggested that larva is able to convert β-sitosterol in the diet to cholesterol. But in the pupa incorporation of
3H-β-sitosterol into cholesterol in free fraction was observed, while that in sterol ester fraction was not.
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Mieko Suzuki, Nobuo Ikekawa, Eiko Akaike, Kyosuke Tsuda
1966 Volume 14 Issue 8 Pages
837-842
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The chemical structure of hydrocarbons in the silkworm was shown as comparing with that in the mulberry leaf by means of gas chromatographic technique and mass spectrometry. The hydrocarbons from both the silkworm and mulberry leaf consisted of a mixture of odd-and even-numbered carbons and major hydrocarbons in the wings were C
34 to C
36 those in both blood and larva, C
21 to C
27, and those in mulberry leaf, C
16 to C
20. Large hydrocarbons, C
32, C
34, C
38, C
40 and C
41, were found in the wings.
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M.E. Omar Abdul-Mohsen, Shun-ichi Yamada
1966 Volume 14 Issue 8 Pages
842-855
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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A new type of ring closure has been established for the synthesis of some 1-substituted-6, 7-dimethoxy-3, 4-dihydroisoquinoline derivatives through desulfurization of N- (3, 4-dimethoxyphenethyl) thioamides. Mercuric chloride proved to be the only effective desulfurizing agent which produces the optimum yield of cyclized products when three moles of it are used for each mole of thioamide in acetonitrile. A reaction mechanism was tentatively proposed from the intermediates. Several organic mercurial products such as II, VI and VII were also obtained.
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M.E. Omar Abdul-Mohsen, Shun-ichi Yamada
1966 Volume 14 Issue 8 Pages
856-861
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Three new N-[2-(3-indolyl)ethy1] thioamides (IIa∼c) and N-(methylthiocarbony1) tryptophan methyl ester (III) were conveniently prepared according to our general procedure of synthesizing thioamides. The cyclodesulfurization of IIa∼c was successfully accomplished in high yield to the corresponding 1-subsituted-3, 4-dihydro-9H-pyrido[3, 4-b]-indole derivatives (IVa∼c). In addition, III was cyclized to give a mixture of both 1-methy1-3, 4-dihydro-9H-pyrido[3, 4-b]indole-3-caroxylic acid (Vb), and its methyl ester (Va) in excellent yield.
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Eizo Hirai
1966 Volume 14 Issue 8 Pages
861-865
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The behavior of 4-amino-5-carboxy-2-methylpyrimidine (ACMP) was compared with those of 2-aminoisonicotinic acid (ANA) and 2-aminoisonicotinic acid (AINA) in water. The behaviors of these compounds were investigated spectrophotometrically by comparison with those of the corresponding ethyl ester and 1-methyl betaine. The Edsall-Blanchard equation was used to evaluate the equilibrium constants, K
z between zwitterion from and uncharged from in water. The evaluated K
z values indicated that ACMP, ANA and AINA existed almost completely in the zwitterion form in water, respectively. This result was in good agreement with the spectrophoto-chemical observations.
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Masuo Morisaki, Hiroko Izawa, Kyosuke Tsuda
1966 Volume 14 Issue 8 Pages
866-872
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Es wird die Aromatisierungsreaktion von 2 (oder 4)-Methylcholesta-1, 4-dien-3-on mittels Zinkstaub beschrieben. Bei 4-Methylcholesta-1, 4-dien-3-on verlauft die reduktive Aromatisierungsreaktion unter Abspaltung der C-C Bindung an C
10-C
19 oder C
10-C
9. Aber bei 2-Methylcholesta-1, 4-dien-3-on findet auβer der obenerwahnten reduktiven Aromatisierung noch die Dienon-Phenol-Umlagerungsreaktion statt.
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Hiroko Izawa, Masuo Morisaki, Kyosuke Tsuda
1966 Volume 14 Issue 8 Pages
873-877
Published: August 25, 1966
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Es wird die Aromatisierungsreaktion von Cholesta-2, 4-dien-1-on mittels Zinkstaub beschrieben. Dabei wird bewiesen, daβ die Reaktion auf analoge Weise wie die Dienon-Phenol-Umlagerung durch Angriff des Zink-Ions verlauft und schlieβlich 19-Nor-4-methylcholesta-1, 3, 5(10)-trien-3-ol ergibt.
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Hiroaki Matsuda
1966 Volume 14 Issue 8 Pages
877-883
Published: August 25, 1966
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A study of polyphenolic compounds and shikimic acid in the leaves of Rhus and Poupartia (Anacardiaceae), Sapium, Ricinus and Aleurites (Euphorbiaceae) have been undertaken. From the results obtained on the constituents of these plants, corilagin, an ellagitannin, proved to be common except in Rhus chinensis. Shikimic acid is also common except in Poupartia. Flavonoid compounds consisted of glycosides of flavonols and apigenin.
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Haruaki Yajima, Koichi Kawasaki, Masao Koida
1966 Volume 14 Issue 8 Pages
884-890
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The N-acetyl group of melatonin was replaced with a histidylphenylalanylarginyl moiety . The product, N-(histidyenylalanylarginy1)-5-methoxytryptamine, reversed the darkening action of α-melanocyte-stimulating hormone (MSH) on frog-skin in vitro in contrast to the closely related tetrapeptide, histidylphenylalanylarginyltryptophan which exhibits intrinsic MSH activity. The synthetic intermediates, N-arginy1-5-meth-oxytryptamine and N-(phenylalanylarginyl)-5-methoxytryptamine also reversed the action of α-MSH. The color lightening potency of these compounds was about one millionth that of melatonin.
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Hiroshi Hikino, Keitaro Aota, Tsunematsu Takemoto
1966 Volume 14 Issue 8 Pages
890-896
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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Cyperotundone, the constituent of nutgrass (Cyperus rotundus (Cyperaceae)), has been shown to have the stereostructure I as follows : Spectral determinations of it and its derivatives revealed the presence of a 2-methyl-3-substituted cyclopent-2-enone system with a methylene αto the carbonyl. The carbon skeleton was established by transformation to the isopatchoulane (VI) derived from patchouli alcohol (VII). The absolute configuration of the C-11 bridge was deduced from the above transformation and a positive Cotton effect of the optical rotatory dispersion of the ketone (X) and that of the C-10 methyl from examination of the NMR methyl signals.
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Nobuko Kataoka, Akira Imamura, Yutaka Kawazoe, Goro Chihara, Chikayosh ...
1966 Volume 14 Issue 8 Pages
897-902
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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UV-irradiation of 4-nitroquinoline 1-oxide in solutions, that is, in dioxane, in benzene, and in hexane, induced stable radicals which were investigated by ESR spectroscopy. Hyperfine structures of spectra thus obtained are different from each other depending on the sort of the solvents used. Determination of these radical structures were carried out by help of isotope-containing 4-nitroquinoline 1-oxides and, in particular, the structure of dioxane type radical was proposed, based on spectral changes by isotope replacement.
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Shigeharu Inouye
1966 Volume 14 Issue 8 Pages
902-909
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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The preparation of the title compounds from the respective methyl 3-acetamido-3-deoxy-α-D-hexopyranosides was described. Introduction of an amino group at C
6 was confirmed by nuclear magnetic resonance spectroscopy and dissociation constants. De-N-acetylation of methyl 3-acetamido-6-azido-3, 6-dideoxy-α-D-glucopyranoside by hydrazine was accompanied with reduction of the azido group to give directly methyl 3, 6-diamino-3, 6-dideoxy-α-D-glucopyranoside. Treatment of methyl 3-acetamido-3-deoxy-2, 6-di-O-p-tolylsulfonfl-α-D-glucopyranoside with sodium azide afforded, via an 2, 3-oxazolinium intermediate, methyl 3-acetamido-6-azido-3, 6-dideoxy-α-D-mannopyranoside. The isolation of a new compound, methyl 3-amino-3-deoxy-β-L-glucopyranoside from nitromethane condensation products was added.
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Kenji Suzuki
1966 Volume 14 Issue 8 Pages
909-914
Published: August 25, 1966
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The synthesis of three peptides related to the C-terminus of B-peptide of ox cofibrin (positions 16∼21, 15∼21, and 13-21) is described. The biological activity of the peptides on isolated mouse ileum is reported.
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Katsuichi Shuto, Kimiko Matsuo, Masamichi Tsuboi
1966 Volume 14 Issue 8 Pages
915-916
Published: August 25, 1966
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Takeo Naito, Toru Yoshikawa
1966 Volume 14 Issue 8 Pages
918-921
Published: August 25, 1966
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Shun-ichi Yamada, Kiyoyasu Ishikawa, Kazuo Achiwa
1966 Volume 14 Issue 8 Pages
921-924
Published: August 25, 1966
Released on J-STAGE: March 31, 2008
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