Chemical and Pharmaceutical Bulletin

Steroid Series. XIX. Rearrangement Reactions of 3β-Acetoxy-6, 19-dioxo-5α-steroids

Ryozo Hayashi

1967 Volume 15 Issue 2 Pages 139-150
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.139

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3β-Acetoxy-6, 19-dioxo-5α-steroid (II) was found to rearrange, under acidic conditions, into 1β, 4β-oxido-A-homo-19-nor-Δ⁵⁽¹⁰⁾-6-oxo-steroid (III), and in alkaline medium, into 3β, 6α-dihydroxy-5α-steroid-19-oic acid, 3, 19-lactone (XV). Possible reaction mechanisms involving the same intermedial 3β, 19-hemiacetal of initially formed 3β-hydroxy-6, 19-dioxo-5α-steroid (IV) were proposed. Anisotropic effects of 19-formyl and 3β, 19-lactone carbonyl groups on the chemical shift of 18-methyl protons were also discussed.

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Studies on Plant Growth Regulators. I., Isolation of Indole-3-acetamide, 2-Phenylacetamide, and Indole-3-carboxaldehyde from Etiolated Seedlings of Phaseolus

Yo Isogai, Toshiko Okamoto, Toru Koizumi

1967 Volume 15 Issue 2 Pages 151-158
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.151

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Plant growth promoting substances, indole-3-acetamide and phenylacetamide and related compound, indole-3-carboxaldehyde were isolated from the aqueous extract of etiolated seedlings of Phaseolus mungo.

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Studies on Plant Growth Regulators. II. Isolation of Indole-3-acetic Acid, Phenylacetic Acid, and Several Plant Growth Inhibitors from Etiolated Seedlings of Phaseolus

Toshihiko Okamoto, Toru Koizumi, Yo Isogai

1967 Volume 15 Issue 2 Pages 159-163
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.159

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Methyl indoleacetate and methyl phenylacetate were isolated from the methylated F-2 fraction of Moyashi aqueous extract. And three methylated plant growth inhibitors were also isolated.

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Studies on Plant Growth Regulators. III. Isolation of Indole-3-acetonitrile and Methyl Indole-3-acetate from the Neutral Fraction of the Moyashi Extract

Toshiko Okamoto, Toru Koizumi, Hisako Fujishiro, Hisako Isogai, Yaeko ...

1967 Volume 15 Issue 2 Pages 163-168
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.163

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Methyl indole-3-acetate and indole-3-acetonitrile were identified in the neutral fraction of Moyashi (F-1 AcOEt fraction) by thin-layer chromatography and vapor phase chromatography.

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Stereochemistry of Decahydroisoquinolines and Related Compounds. V. Syntheses of 2-Methyl-decahydro-8-isoquinolinols

Masao Okamoto

1967 Volume 15 Issue 2 Pages 168-172
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.168

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Three isomeric bases of 2-methyl-decahydro-8-isoquinolinol (XIVa, XIVb, XIVc) were prepared by catalytic hydrogenation of 2-methyl-5-chloro-1, 2, 3, 4-tetrahydro-8-isoquinolinol (VIII) and also of 2-methyl-1, 2, 3, 4-tetrahydro-8-isoquinolinol (XIII). The configuration of the ring juncture of these alcoholic bases and the configuration of their hydroxyl groups were clarified on the basis of chemical evidences and NMR informations and the rates of chromic acid oxidation and so on.

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Absorption and Excretion of Drugs. XXIX. Effect of Surface-active Agents on Rectal Absorption of Sulfisoxazole from Oily Base

Kiichiro Kakemi, Hitoshi Sezaki, Shozo Muranishi, Hidefumi Matsui

1967 Volume 15 Issue 2 Pages 172-178
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.172

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Effect of various types of surface-active agents on the rectal absorption of sulfisoxazole from cocoa butter was investigated by the blood level determination with rabbits. Blood levels were in general increased with increase of surface-active agent, and decreased by addition of the large amount. Surface-active agent accelerated the release of the drug from the base to dissolution medium. On the other hand, surface-active agent reduced the absorption rate of the drug from aqueous solution. These results suggest that the increase of the drug absorption at the low concentrations of surface-active agents is due to release acceleration, but the reduction effect on drug absorption in their higher concentrations is due to predominance of absorption reduction over release acceleration. Cetyltrimethyl ammonium bromide especially stimulated the drug absorption in the very low concentrations.

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Synthesis of Some 3, 5-Diene-2, 7-dioxosteroids

Kikuo Yasuda, Hiromu Mori

1967 Volume 15 Issue 2 Pages 179-185
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.179

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tert-Butyl chromate oxidation of some steroidal 3, 5-dienes was examined. The oxidation proceeded first at C-7 and then at C-2 irrespective of what substituent was at C-3. Thus some 3, 5-diene-2, 7-diones were obtained by reoxidation of 3, 5-dien-7-one. 1, 6-Addition of methylmagnesium iodide to 17β-acetoxyandrosta-3, 5-dien-7-one afforded 17β-hydroxy-3α-methylandrost-4-en-7-one, which was converted to 17β-acetoxy-3α-methyl-androst-5-en-7-one by treatment with acetic acid and concentrated hydrochloric acid. Similarly 17β-acetoxy-3, 3-dimethylandrost-5-en-7-one was obtained from 17β-acetoxy-3-methylandrosta-3, 5-dien-7-one.

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Further Preparation of Steroidal Diosphenols. II. Synthesis of 2, 16α, 17β-and 2, 16β, 17β-Trihydroxy-4, 4-dimethylandrosta-1, 5-dien-3-ones

Kenyu Shibata, Joji Yamada, Hiromu Mori

1967 Volume 15 Issue 2 Pages 186-193
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.186

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2, 16β, 17β-Trihydroxy-4, 4-dimethylandrosta-1, 5-dien-3-one (VI) was prepared from 2, 16β, 17β-trihydroxyandrost-5-ene 16, 17-acetonide in 4 steps. 2, 16α, 17β-Trihydroxy-4, 4-dimethylandrosta-1, 5-dien-3-one (XVIII) was prepared form 2, 17β-dihydroxy-4, 4-dimethylandrosta-1, 5-dien-3-one (VII) in 8 steps. It was found that the 2, 3-ketol was converted to the 2, 3-diketone by autoxidation without influence on 16, 17-glycol.

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Pachysandra Alkaloids. II. Structure of Pachysandrine-A, a New Pregnane Type Alkaloid

Masao Tomita, Shoichiro Uyeo, Tohru Kikuchi

1967 Volume 15 Issue 2 Pages 193-207
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.193

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Structure and stereochemistry of pachysandrine-A, one of the major alkaloids isolated from the weakly basic alkaloid fraction of Pachysandra terminalis SIEB. et ZUCC. (Buxaceae), was discussed and assigned to the formula Ia. This presents the first example of 4-oxygenated 3, 20-diamino-5α-pregnane alkaloid discovered in nature source.

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Pachysandra Alkaloids. III. Structures of Pachysandrine-B, -C, and -D

Tohru Kikuchi, Shoichiro Uyeo

1967 Volume 15 Issue 2 Pages 207-213
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.207

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Structures of pachysandrine-B, -C, and -D isolated from Pachysandra terminalis SIEB. et ZUCC., a Buxaceous plant, were investigated and their structures were proved to be IIIa, II, and Va, respectively.

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Stereochemistry in Solution. II. Factors influencing the Relaxation Time T₁ of ¹⁴N-Nucleus in Quaternary Amine Cations

Yutaka Kawazoe, Mitsuhiro Tsuda, Masako Ohnishi

1967 Volume 15 Issue 2 Pages 214-219
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.214

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It was shown that the relaxation time of ¹⁴N nucleus was strongly dependent on the nature of solvent, temperature and stereochemical structure of N, N-dimethylpiperidinium derivatives.

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Oxidation Reaction of Carcinogenic 4-Hydroxyaminoquinoline 1-Oxide

Nobuko Kataoka, Sachiko Shibata, Akira Imamura, Yutaka Kawazoe, Goro C ...

1967 Volume 15 Issue 2 Pages 220-225
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.220

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An amphoteric compound 4-hydroxyaminoquinoline 1-oxide(4-HAQO) was oxidized by oxygen to lose one electron from NHOH group of the molecule and to produce a stable free radical. This oxidative radical production was accelerated by addition of several kinds of oxidants. The UV-absorption of the free radical thus produced, showed its maximum at 455mμ. On the other hand, the oxidation of 4-HAQO was protected by the presence of such a reducing agent as ascorbic acid. As a result, the presence of such a reducing agent made it possible to record the UV spectrum of 4-HAQO in alkaline media.

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Constituents of Convallaria. VI. Isolation of Convallatoxol

Michiya Kimura, Masahiko Tohma, Itsuo Yoshizawa

1967 Volume 15 Issue 2 Pages 226-228
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.226

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A steroidal glycoside, C₂₉H₄₄O₁₀, m.p. 168∼169°, was isolated from the flowers of Japanese lily of the valley, Convallaria keisukei MIQ. and was identified as convallatoxol(I). A nitrogen compound, C₁₆H₂₄O₈N₄, m.p. 189.5∼190.5°(II), was also isolated.

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Syntheses of 3-Aminopropylguanidine Derivatives

Takeo Ueda, Kumi Ishizaki

1967 Volume 15 Issue 2 Pages 228-232
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.228

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The fourteen compounds of 3-(substituted amino)propylguanidine were synthesized by reacting S-methylisothiourea sulfate with 3-(substituted amino)propylamine : 3-(substituted amino) propylamine having an aliphatic substituent group at 3-position were synthesized by reacting the aliphatic amine with acrylonitrile and by reducting with lithium aluminum hydride, while 3-(substituted amino)propylamine having an aromatic substituent group at 3-position, synthesized by the Ing-Manske modification of the Gabriel synthesis of primary amines.

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The Partial Demethylation of Flavones. II. Formation of Isocryptomerin

Hiroshi Miura, Nobusuke Kawano

1967 Volume 15 Issue 2 Pages 232-235
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.232

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Partial demethylation of cryptomerin B (II) with hydrogen iodide formed a new compound, isocryptomerin (III).

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Dissociative Behavior of High-Density Lipoprotein of Egg Yolk

Tatsuzo Fujii, Toshiko Shimano, Tomio Fujii

1967 Volume 15 Issue 2 Pages 235-238
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.235

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Reaction of Amide Homologs. XVII. Catalytic Hydrogenolysis of N, N'-Benzylidenebisamides

Minoru Sekiya, Masayasu Tomie

1967 Volume 15 Issue 2 Pages 238-240
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.238

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Chemistry of Sodium Borohydride and Diborane. III. Synthesis of (+)-Lupinine by Hydroboration Reaction

Takehisa Kunieda, Shunichi Yamada

1967 Volume 15 Issue 2 Pages 240-242
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.240

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Isolation and Identification of the Antifungal Active Substance in Walnuts

Tetsuro Ikekawa, E.Lin Wang, Masa Hamada, Tomio Takeuchi, Hamao Umezaw ...

1967 Volume 15 Issue 2 Pages 242-245
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.242

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The substance in walnuts of Juglans regia LINN. and J.Sieboldiana MXIM. exhibiting growth inhibition of Trichophyton mentagrophytes has been isolated, and it is confirmed that the active substance is identical with juglone (5-hydroxy-1, 4-naphthoquinone).

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Studies on Digitalis Glycosides. The Structure of Digiprogenin. partial Synthesis of Dihydro-α-digiprogenin Acetate

Daisuke Satoh, Setsuko Kobayashi

1967 Volume 15 Issue 2 Pages 248-250
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.248

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Structure of Serratine

Yasuo Inubushi, Hisashi Ishii, Takashi Harayama

1967 Volume 15 Issue 2 Pages 250-252
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.250

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Recovery of Biologically Active Peptides from Their 1-Dimethylaminonaphthalene-5-sulfonyl Derivatives

Zenzo Tamura, Takenori Tanimura, Hisanobu Yoshida

1967 Volume 15 Issue 2 Pages 252-253
Published: February 25, 1967
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.15.252

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