Nous avons etudie que la nitrification de 4-lutidone a fourni 3, 5-dinitrolutidone-4 (I), dont nous avons pu synthetiser 4-chloro-3, 5-dinitrolutidine (III) en tres bon rendement. I1 faut noter que l'oxidation de (I) par permangnate de potasse ne se fournit que le derive monocarboxylique (II), mais, au-dessus, la decomposition du noyau pyridique. En partant de (III), nous avons obtenu huit substances nouvelles, 4-aryloxy-3, 5-dinitrolutidines (IV) a (XI).

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In the derivation of dl-1-phenyl-2-acylamino-1, 3-dibromopropanes to dl-phenyl-serinols, the stepwise displacement of bromine atoms by hydroxyl groups was examined in connection with earlier conclusions. It was found that the proximity of acyl group to the displacement centre favored the internal Sn₂ and that its distance from the neighborhood favored Sn₁ in the solvolytic condition.

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The synthesis of β-ionone starting from 2, 6, 6-trimethylcyclohexanone (I) was investigated. Oxidation of 2, 6, 6-trimethyl-1-vinylcyclohexanol (III) with chromium trioxide or ozone unexpectedly afforded (I). 1-(1'-Hydroxy-2', 6', 6'-trimethylcyclohexyl)-but-1-yn-3-ol (VI) was reduced with sodium in liquid ammonia and the product was oxidized with manganese dioxide to trans-1-(1'-hydroxy-2', 6', 6'-trimethylcyclohexyl) but-1-en-3-one (IX). An attempt to prepare β-ionone by the dehydration of (IX) was unsuccessful. Treatment of (IX) with zinc-acetic acid yielded a new isomer of dihydroionone, 1-(2', 6', 6'-trimethylcyclohexylidene) butan-3-one (XIII).

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By treatment with an excess of lithium aluminum hydride, 1-(1'-hydroxy-2', 6', 6'-trimethylcyclohexyl) but-1-yn-3-ol (I) was converted to 1-(2', 6', 6'-trimethylcyclohexylidene) but-1-en-3-ol (II), which was further oxidized to the corresponding allenone (III), a new isomer of ionone, by the action of activated manganese dioxide.

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By employing 4-aminoimidazole[4-¹⁴C]-5-carboxamide, formate-¹⁴C, and ³²P, the role of the carboxamide as a precursor of polynucleotide purines was examined. The in vitro incorporation of the labeled carboxamide into polynucleotide adenine and guanine was found by rat liver slices and by cell-free system. The specific activity was about 2∼5 times higher in adenine than in guanine. In the case of regenerating liver, generally higher specific activity was observed than in the case of normal liver. The stimulatory effect of the non-labeled carboxamide in the course of the incorporation of formate-¹⁴C and ³²P into polynucleotides was demonstrated.

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The effect of 4-aminotriazole-5-carboxamide and certain purine antimetabolites (e.g. 8-azaguanine, 6-mercaptopurine, and 2, 6-diaminopurine) as well as folic acid antimetabolites (e.g. aminopterin) on the incorporation of labeled 4-aminoimidazole[4-¹⁴C]-5-carboxamide, formate-¹⁴C, and ³²P into polynucleotides of rat or pigeon liver slices was demonstrated and certain aspects of their mode of action were discussed.

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During the course of studies on the incorporation of 4-aminoimidazole[4-¹⁴C]-5-carboxamide into polynucleotide purines with subcellular fractions of pigeon liver, a new diazotizable amine was obtained by the paper chromatography of the acid-soluble fraction of the incubation medium. The amine is a kind of arylamine associated with a ketose, which is neither ribose nor deoxyribose.

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Gracillin, a new diosgenin glycoside which was present together with dioscin in the water-insoluble saponins obtained from the rhizome of Dioscorea gracillima Miq., was proved to be composed of one mole each of diosgenin and of L-rhamnose and two of D-glucose. It afforded two prosapogenins C and A on partial hydrolysis, both of which were isolated and proved to be trillin (diosgenin monoglucoside) and glucosidoglucoside, respectively. Two possible formulae (I) and (II) were proposed for gracillin.

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d-5-Amino-α-santenic acid was prepared from d-isoketopinic acid as the starting material. The diaotization of this produced a dehydrosantenic acid, the dehydration product of the expected 5-hydroxy-α-santenic acid. The structure of the unsaturated acid was assumed as 5-dehydrosantenic acid.

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i) Dianhydrorugulosin, C₃₀H₁₈O₈, which was derived from rugulosin, C₃₀H₂₂O₁₀, a pigment of P.rugulosum Thom, by a dehydrationreaction, was converted into bisnordianhydrorugulosin which was synthetically proved to be identical with 4, 5, 4', 5'-tetrahydroxybianthraquinone-(1, 1'). ii) Iridoskyrin, C₃₀H₁₈O₁₀, a pigment of P.islandicum Sopp, yielded islandicin (1, 4, 5-trihydroxy-2-methylanthraquinone) by reductive cleavage with alkaline Na₂S₂O₄. Dianhydrorugulosin gave chrysophanol by the same reaction. iii) Dianhydrorugulosin was derived from iridoskyrin by the action of HI and red phosphorus, then with CrO₃, losing two hydroxyls. iv) By the above reactions, the structure of dianhydrorugulosin was established as being 4, 5, 4', 5'-tetrahydroxy-7, 7'-dimethylbianthraquinone-(1, 1'), while iridoskyrin was proved conversely to be 4, 5, 8, 4', 5', 8'-hexahydroxy-7, 7'-dimethylbianthraquinone-(1, 1'). v) A fundamental skeleton of rugulosin has been forwarded.

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1) The main product of m.p. 204°, which was previously obtained by the nitration of phenazine N-oxide, was converted into 3-methoxyphenazine 5-oxide by refluxing with methanolic solution of potassium hydroxide. 2) 1-and 2-Chlorophenazine were not nitrated with conc. sulfuric acid and potassium nitrate, even when the temperature was raised to 80°. 3) 1-, 2-, and 3-Chlorophenazine 5-oxides were substituted at the same 7-position by the nitro group.

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A quaternary alkaloid magnoflorine (I) has been identified from the stem and root of Berberis amurensis Rupr. var. japonica (Regel) Rehd. forma Bretschneideri (Rehd.) Ohwi (Berberidaceae). The wide distribution of magnoflorine (I) throughout the families Magnoliaceae (M.grandiflora L.), Menispermaceae (Cocculus trilobus DC.), and Berberidaceae (B.amurensis) is of significance in biogenesis of alkaloids.

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Epistephanine (I : R=CH₃), an alkaloid of Stephania japonica Miers and its dimethiodide (IV), on hydrogenation, did not yield racemic compounds but optically active ones in either case. Epistephanine (I : R=CH₃), on hydrogenation with zinc and sulfuric acid, afforded only hydroepistephanine-A (II) as the dihydro derivative. Treatment of (II) with methyl iodide gave N-methylhydroepistephanine-A dimethiodide (III), which was shown by direct comparison of their specific rotations and infrared spectra to be identical with O-methyloxyacanthine dimethiodide (III)(asymmetric centers, +, -). Epistephanine dimethiodide (IV), when reduced with either sodium borohydride or zinc-sulfuric acid, afforded N-methylhydroepisephanine monomethiodide, from which N-methylhydroepistephanine-B dimethiodide (VI) was derived. It was found that (VI) is identical with O-methylrepandine dimethiodide (IX)(asymmetric centers, +, +) by infrared spectral determinations, and that since the values of their specific rotations have the opposite sign to each other, (VI) is an antipode of (IX) and hence its asymmetric centers are (-, -).

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4-Aminoimidazole[4-¹⁴C]-5-carboxamide hydrochloride (AICA-¹⁴C) was synthesized in order to use it as the radioactive biological tracer to follow the biosynthetic mechanism of polynucleotide purines and the behavior of antimetabolites expected to act during the course of such biosysnthesis. The synthetic route started with barium carbonate-¹⁴C and went through 7 steps including sodium cyanide-¹⁴C, malon-amamidine[3-¹⁴C]hydrochloride, and formamidomalonamamidine[3-¹⁴C]hydrochloride hemihydrate, with a final yield of 23% of AICA-¹⁴C.

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1) The application of Kitamura's reaction to ethyl 3-nitropyridyl-4-thiocarbamate resulted in the formation of ethyl 3-nitropyridyl-4-carbamate, which was identical with the product obtained by the reaction of 3-nitro-4-aminopyridine with ClCO₂C₂H₅. 2) The reaction mechanism of the thiocyano compound with alcohols was reconsidered.

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The report made by Sugasawa and Ban that the oily oxidation product, produced in 66% yield, of 1-methyl-3-ethylpyridinium methosulfate consisted of 1-methyl-3-ethyl-2-pyridone only, was in error, which was caused by a cursory examination of the distillation product. The present study revealed that the oily oxidation product was really a mixture of 1-methyl-3-ethyl-2-and-6-pyridone in proportion of approximately 8 : 1. Their separation was made possible through picrates, of which the one from the 2-pyridone is freely soluble in ether, whereas the other is practically insoluble in cold ether. By using the oxidation agent in a certain excess, the yield of the product attained as high as 84% of the theoretical.

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