Hypognavin enthalt eine Atomgruppierung eines β-vinyl-sec-alkohols, welcher bei der katalytischen Reduktion mit Pd-Kohle zum Teil sich in eine isomere Methylke obase umlagert und zum Teil in zwei stereoisomere α-Methylcarbinolbasen hydriert wird. Dieselbe Methylketobase entsteht auch in kleiner Menge, wenn man Hypognavin in 10%-iger Schwefelsaure erhitzt.

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The Reformatsky reaction of ethyl o-acetylbenzoate (II) with ethyl bromoacetate gave ethyl 3-methylphthalide-3-acetate (IIIa) as the product, which was led to 3-(o-car-boxyphenyl) butyric acid (I) via 3-(o-carboxyphenyl) crotonic acid (IVa). The structures of (IIIa) and (IVa) were established by means of their chemical properties and the ultraviolet and infrared absorption spectra, and it was shown that the method was valuable for the verification of each structure of the tautomerism represented by the following general formulae : [chemical formula]

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From the bark of Phellodendron amurense RUPR. (Rutaceae), four other quaternary alkaloids, guanidine, magnoflorine, phellodendrine (a new base), and an unknown base were isolated, besides those of the berberine type such as berberine and palmatine.

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Methylpyridines possessing chlorine in 2 (or 4)-position were derived to the corresponding 2 (or 4)-cyano-methylpyridines by heating with sodium sulfite in water in an autoclave at 150∼220°for 10 hours and heating the sodium sulfonate thereby obtained with potassium or sodium cyanide to fusion.

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Tablets were compressed during a short period, its weight variation was evaluated as coefficient of variance in percentage, and the effect of four factorials was examined. From the results obtained, following conclusions were drawn : 1) Significant difference was not recongnized among tablet bases A, B, and C. 2) Decrease of diameter of punch increased the weight variation of tablets quadratically. 3) Increase of the granulated sieve mesh decreased weight variation of tablets, and linear relation was proved between them. 4) The degree of decrease was different for each punch. 5) Significant difference was not recognized between two compression rates, 76 and 42 tabs./min. 6) Without considering variation of mean weight for a long-period operation of a tabletting machine, from the OC-curve obtained by Dunnett and Crisafio, and 95% and 99% confidence limits of regression line for each punch, compression of tablets under the conditions listed in Table IV is recommended. The lot manufactured under such conditions may be accepted by U.S.P. test in probability of 0.95×0.95=0.90 and 0.99×0.95=0.94.

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Effect of repeated mechanical work on peanut oil-aluminum stearate gel system was indicated rheologically to be more fluid and to give gentler curve of rigidity vs. setting time. By obtaining flow curve of the gel, effect of storage at various temperatures on gel was also investigated. When stored at a higher temperature (37°), the gel became gradually fluid and finally behaved like a linear flow. In the course of storage, there appeared an initial stage, where the values of both viscosity immediately after stirring and rigidity 10 minutes after stirring the sample increased up to the maximum. On the other hand, when stored at a lower temperature (-3°to + 2°), similar increase of fluidity did not occur so rapidly and its initial stage was also delayed much longer. The cooling effect on the gel, which had been fluid, were also observed in restoration of its gelation properties, but the initial effect was always predominant thereafter.

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The green fluorescent substance (G compound) isolated from the mycelium of Ere-mothecium ashbyii was presumed to be a ribityl derivative of 6, 7-dimethyllumazine and already reported in the previous paper. In the present work 6, 7, 8-trimethyllumazine was synthesized, and from the complete agreement of ultraviolet spectrum between this product and G compound, the position of the ribityl group in G compound was confirmed to be the nitrogen at 8-position.

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The anthrone color of glucose was shown to have the maximum intensity when the reaction was carried out for 20 minutes at 85∼90°in 70% (v/v) of sulfuric acid. The absorption maximum of the blue-green color shifted to a longer wave length region with the increasing concentration of the acid. It seemed to require three moles of anthrone to one mole of glucose in the reaction. The soluble part of coloring matter of the reaction in benzene was separated on alumina and was shown to consist of several dyes which gave different coloration with sulfuric acid. One of the main dyes was isolated in crystalline form, and its probable structure might be 1, 2, 5-or 1, 3, 5-trianthronylidenepentane from its analytical data and infrared spectrum, and its reaction mechanism was considered. The same dye was also isolated from anthronated xylose and the reaction mechanism with the pentose was discussed.

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Tsuchiya and Kaneko¹⁾ had isolated a substance exhibiting ultraviolet absorption maxima (in heptane) at 231, 290, and 315mμ from rice bran oil and named it oryzanol. Utilizing the fact that oryzanol is a phenolic substance, the rice bran oil removed of free fatty acids by sodium carbonate in dichloroethane solution was passed through an alumina column and the adsorbed phenolic substance was eluted. This phenolic substance, as an ether solution, was purified by transiting to potassium hydroxide solution and further recrystallized to crystalline oryzanol. This was acetylated and fractionally recrystallized from ethyl acetate, separating into three kinds of substances. The most sparingly soluble portion was in a minute amount but the other two liberated phenolic substances on deacetylation. These were designated as oryzanol-A and -B.

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The methyl ether obtained from oryzanol-A and dimethyl sulfate is saponified with ethanolic potassium hydroxide to form 3, 4-dimethoxycinnamic acid and a neutral substance. Under a more drastic conditions, oryzanol-A itself is saponified to form the same neutral substance and ferulic acid. The neutral substance is a kind of triterpenoid alcohol and was determined as cycloartenol by the comparison of the constants of various derivatives and a mixed fusion of its acetate and benzoate. Therefore, oryzanol-A is cycloartenyl ferulate and the absorption in the ultraviolet range is due to the ferulic acid moiety. Oryzanol-B was also found to be the ferulate of a triterpenoid alcohol but the nature of this alcohol was not established. Its properties were similar to cycloartenol but its infrared spectrum revealed the presence of a vinylidene group, while cyclo-artenol possesses anisopropy lidene group. As shown in Table II, the constants of various derivatives were clearly different from those of cyclolaudenol, which possesses a vinylidene group.

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2-Substituted oxazolo [b] quinoxaline with a new skeleton was synthesized by heating 2-amino-3-quinoxalinol with excess of acyl chlorides at 180∼210°, by boiling with three volumes of acyl chlorides in nitrobenzene, or by heating 2-acylamino-3-quinoxalinol with phosphoryl chloride. When the 2-substituted radical of oxazolo [b] quinoxaline is aliphatic, 2-substituted oxazolo [b] quinoxaline was not obtained but the compounds formed when the substituents were aromatic radicals. This problem is now under investigation.

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Di-and trialkylphenanthrenes were synthesized. 1-Ethyl-6-isopropyl-, m. p. 65.0∼65.5°(picrate : m. p. 118∼120°, trinitrobenzene complex : m. p. 147∼148°). 6-Ethyl-1-isopropyl-, m. p. 61∼63°(trinitrobenzene complex : m. p. 151∼152°). 1, 2-Dimethyl-6-isopropyl-, m. p. 109∼110°(picrate : m. p. 140∼141°, trinitrobenzene complex : m. p. 157°). 2, 6-Diethyl-1-methyl-, m. p. 57∼63°(trinitrobenzene complex : m. p. 137∼145°). 1, 2-Diethyl-6-methyl-, m. p. 47∼49°(trinitrobenzene complex : m. p. 169∼170°). 1-Isopropyl-6, 9-dimethyl-, m. p. 41∼43°(picrate : m. p. 159∼161°, trinitrobenzene complex : m. p. 186∼188°). 2-Ethyl-5-methyl-, oil, (trinitrobenzene complex : m. p. 112∼113°).

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Three alkylphenanthrenes were derived by the selenium dehydrogenation of resinic acid derivatives. 7-Isopropyl-1, 6-dimethylphenanthrene, m. p. 102∼103°(trinitrobenzene complex : m. p. 184∼185°, picrate : m. p. 169.5∼170.5°). 6-Isopropyl-1, 7-dimethyl-, oil, (trinitrobenzene complex : m. p. 188°, picrate : m. p. 178∼179°). 6-Ethyl-1, 7-dimethyl-, m. p. 70∼71°(trinitrobenzene complex : m. p. 170.5∼171.5 ; picrate : m. p. 160∼161°).

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Durch Nitrierung von Chinolin-N-oxyd mit Benzoylnitrat in Chloroform-bzw. Dioxan-Losung wurde das 3-Nitrochinolin-N-oxyd mit befriedigender Ausbeute erhalten. Pyridin-N-oxyd gibt bei ganz analoger Reaktion das 3-Nitropyridin-N-oxyd trotz sehr schlechter Ausbeute. UV-Absorptionsspektren der isomeren Mononitroderivate des Chinolin-N-oxydes wurden verglichen.

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Synthesis of a morphinan analog in which the ring nitrogen was transposed to 6-position has been described. A benzyl group was introduced into 5-position of 5, 6, 7, 8-tetrahydroisoquinoline, whose methohalide was reduced to the octahydroisoquinoline, and the objective compound was obtained by heating the latter in hydrobromic acid to effect rearrangement-cyclization.

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The position of nitrogen in the morphinan skeleton corresponds to the 17-position of D-ring, or 7-position of the C-ring. A synthesis of the morphinan with the nitrogen in this 7-position has been described.

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By the ¹⁴C-tracer experiment it was proved that methionine takes part as a source of N-methyl group of l-ephedrine in Ephedra plant.

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The analysis of aldehydes which are available for perfume preparation was successfully carried out by paper chromatography. A method of converting aldehydes into hydrogen sulfite compounds, which makes it possible to treat them by the usual paritition chromatography with aqueous stationary phase, was studied. Studies were also made on developing aldehydes by a reversed phase chromatography on paper previously treated with an organic silicone resin. These two methods are considered to be helpful in the microanalysis of perfumes containig several aldehyde components. Quantitative results were also described by double-beam, automatic recording densitometer.

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3-Picoline 1-oxide was derived to 4-chloro-3-picoline by heating with phosphoryl chloride, and the chlorine at 4-position was substituted with nitrile, which was further converted to the carboxyl, ethoxycarbonyl, or benzoyl group.

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m-Anisidine and m-nitroanisole were condensed by Wohl-Aue method and 1, 8-dimethoxyphenazine and its 5-N-oxide were obtained.

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Menadione was prepared from itaconic acid according to the reaction scheme described in the text. The direct oxidation of 2-methyl-1-tetralone to menadione (method A) appeared to be more convenient than that described by Sah³⁾ in view of avoiding the processes of the tetralone derivative to 2-methylnaphthalene. Method B was a little tedious but gave a good yield in each process. From these experiments, it could be concluded that itaconic acid is valuable as the staring material for the preparation of menadione.

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