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

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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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