Treatment of dehydroabietic acid (Ia) with aluminum chloride in benzene affords two kinds of deisopropylated compound, (IIa) of m. p. 173°and (IIb) of m. p. 162°. The fact that the former possesses the same steric configuration as that of (Ia) was determined and some examinations were made on the chromium trioxide oxidation products of their methyl esters.

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It was established that deisopropylallodehydroabietic acid (Ib) had the methyl group between the two rings in α-configuration.

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(1) The decrease of procaine in the aqueous parenteral solution containing 0.5% of procaine hydrochloride and 5% of glucose (PGI) was satisfactorily explained by opposing reactions between formation and hydrolysis of procaine-N-glucoside (PNG). (2) The formation of PNG was proved to be an exothermic reaction, so that at epuilibrium state, higher the temperature, the less the amount of PNG formed, i. e. 66.5% of procaine was combined at 20°and 26.0% at 100°. The heat of reaction was found to be 4.77 Kcal. (3) It was found that the activation energies of formation and hydrolysis of PNG were approximately 14.0 and 18.8 Kcal., respectively. There was a tendency that the velocity constant increases with time, which is considered to be caused by the decrease of pH. (4) From the result obtained, it was concluded that storage of PGI in a refrigerator is not recommended and heat sterilization did not affect the amount of PNG at equilibrium.

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Seven alkylphenanthrenes of 1, 8-dialkyl and 1, 6, 7-trialkyl substituted were synthesized. One of these, 1, 8-dimethylphenanthrene, was identical with an alkylphenanthrene derived from hypognavinol, an aconite alkaloid.

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Ultraviolet and infrared spectra of alkylphenanthrenes were analyzed. In ultraviolet spectra, the absorption maxima were classified into three groups and the first maximum of the group-II (phenanthrene : 291 mμ, log ε 4.17) was the most sensitive to the wave length shift by introduction of substituents. In infrared spectra the bands between 11∼15μ were analyzed as out-of-plane bending vibrations of the aromatic CH groups.

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Barium salts of glycerol 1, 2-cyclic phosphate (GCP), 1, 2-propanediol cyclic phosphate (PCP), ethyleneglycol cyclic phosphate (ECP), and 2, 3-butanediol cyclic phosphate (BCP) were synthesized and Rf values of the pure products on paper chromatograms were given.

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Synthesized glycerol 1, 2-cyclic phosphate (GCP) was hydrolysed to glycerol-1 and -2 phosphate under both acid and alkaline conditions and from the quantitative estimation of the resulting glycerol-1 phosphate, the mode of hydrolytic reaction of glycerophos-phorylcholine was discussed. Synthetic 1, 2-propanediol cyclic phosphate (PCP) was found to give only 1, 2-propanediol-1 phosphate after hydrolysis under tested acid and alkaline conditions. GCP, PCP, synthetic ethyleneglycol cyclic phosphate (ECP), and 2, 3-butanediol cyclic phosphate (BCP) were tested for their stabilities to hydrolysis at various pHs.

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The Leuckart reaction of carbonyl compounds with a mixture of 1, 3-dialkylurea and formic acid gave the corresponding N-alkylamino compounds (Table I). However, the same reaction of a mixture of 1, 3-diphenylurea and formic acid with benzophenone did not proceed similarly, giving a mixture of o- and p-aminotriphenylmethane. The mechanism shown in Chart 1 was proposed for this reaction.

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It was ascertained by paper partition chromatography, ultraviolet spectrum, and bioassay with L. casei that the green fluorescent substance, G compound, isolated from the mycelium of Er. ashbyii readily reacts with diacetyl or with acetoin to form riboflavin. These results established the structure 8-ribityl-6, 7-dimethyllumazine, formerly proposed by the author for the G compound. On the other hand, a large quantity of acetoin was detected in the mycelium and the culture filtrate, and comparing the amount with those of riboflavin and G compound in these materials, the assumption was made that the biosynthesis of riboflavin by Er. ashbyii might be effected by condensation of acetoin with G compound at the position of the methyl groups.

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The hydrogen bonding power of antipyrine and aminopyrine was examined by the measurement of infrared absorption spectra of various ternary solutions and it was concluded that the molecular complexes C₆H₅OH····OC (C₁₀H₁₂N₂) and C₆H₅OH····OC (C₁₂H₁₇N₃) formed in the solution by intermolecular hydrogen bonding. The order of the strengths of these hydrogen bond was considerably large.

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The hydrogen bonding power of santonin was examined by the measurement of infrared absorption spectra in various ternary solutions and it was concluded that the molecular complexes R-OH····OC (C₁₄H₁₈O₂) were formed in the solution by intermolecular hydrogen bond. The order of the strengths of these hydrogen bond were considerably large.

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An infrared method has been developed for the simultaneous determination of santonin, thymol, tetrachloroethylene, and ascaridol (main component of chenopodium oil) in a mixture. The manipulations are simple and rapid to perform, and accuracy and precision of analyses are good.

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The infrared spectra of 10 monosubstituted and 23 disubstituted anthraquinones were determined in the region of 650∼900 cm^-1, and the strong characteristic absorption bands obtained were found to be correlated to their structures.

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In monosubstituted naphthalene compounds, the charateristic absorption bands in the region of 1650∼2000cm^-1 could be correlated with their structure.

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It was found that various glycosides are present in the seeds of Digitalis purpurea and these were found to be separatory identifiable by paper partition chromatography using filter paper soaked in water and methyl ethyl ketone saturated with water as the developing solution. By the use of three kinds of coloring agents, a total of 17 spots were found, assumed to be those of unknown glycosides. This confirmed that a fairly large amount of water-soluble glycosides was present. The use of the foregoing solvent system for column partition chromatography resulted in extremely easy purification of digitalinum verum which was obtained finally as crystals. A presence of a small amount of cardioglycoside, extremely similar to digitalinum verum and very difficult to be separated from it, was detected and it was assumed to be glucogitofucoside, separated as the acetate from the leaves of Digitalis lanata, by paper partition chromatography of the sugar portion of the acid hydrolyzate.

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Of the unknown cardioglycosides contained in the seeds of Digitalis purpurea reported in the preceding paper, substance A-VIII was isolated in crystalline state. This substance occurs as a very bitter needle crystals, m. p. 252∼254° (Kofler, uncorr.) ; [α]²1_D-3.1°, C₄₂H₆₆O₁₉·2H₂O ; negative to the Keller-Kiliani reaction, sulfuric acid layer in carmine red, and positive to Legal and Raymond reactions ; U. V. λ^EtOH_max 218mμ (log ε 4.21). Its hydrolysis with 3.5% hydrochloric acid afforded dianhydrogitoxigenin and the sugar portion was found to be digitalose and glucose by paper partition chromatography. Determination of glucose by the Borel-Hostetteler-Devel method showed the presence of two moles. This substance was found to be a new glycoside, a triglycoside, of gitoxigenin series, and was named gitostin. A structure of gitoxigenin-glucosido-glucosido-digitaloside forgitostin as the gitoxigenin-series glycoside corresponding to odoroside-G was forwarded.

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Gitostin, a new cardiotonic glycoside isolated from the seeds of Digitalis purpurea, was hydrolyzed with digestive enzyme from the intestine of a snail (Euhadra quaesita DESHAYES) and strospeside was obtained, confirming the structure of gitostin as gitoxigenin-glucosido-glucosido-digitaloside. Partial decomposition of gitostin with the same enzyme afforded digitalinum verum, indicating that this enzyme effected stepwise hydrolysis, liberating one mole each of glucose. From the fact that only digitalinum verum is obtained from gitostin, the extra glucose was found to be bonded to the glucose in digitalinum verum, and by the comparison of molecular rotation of gitostin and digitalinum verum, the bonding of this glucosylglucoside was confirmed to be in β-position to the terminal glucose.

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Stoll has recently succeeded in crystallizing purpurea glycoside-A and -B, the true glycosides of Digitalis purpurea, but crystallization of these glycosides is generally difficult. Therefore, attempts were made to derive these glycosides to crystalline acetates and feasibility of their identification through these acetates was examined. As a result, the foregoing two glycosides and gitoxin were obtained as crystalline acetates and their melting points, optical rotation, coloration reaction, and paper partition chromatography have been described, together with those of the acetates of known digitalis glycosides and various aglycone acetates. Oral administration of gitoxin acetate and purpurea glycoside-B acetate showed them to be more toxic than their respective glycosides and their lethal dose in rats was found to have been much lowered.

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1) From the infrared absorption spectral examination of normal- and iso-dihydrothiamine and related compounds (VII), it was confirmed that the structure of normal- and iso-dihydrothiamine should not be represented by the hitherto used structural formula (I) but by (II) from the fact that these compounds show absorption of an amino group but not of hydroxyl group and absorptions at 1030 and 840 cm^-1 of characteristic ring vibration. 2) 3-Benzyl-3a-methyl-perhydrofuro[2, 3-d]thiazole compounds (VII) were synthesized by the reduction of benzylthiazolium compounds (VIII) with lithium aluminum hydride or sodium borohydride, or by the condensation of benzylamine, formaldehyde, and 3-acetyl-3-mercaptopropanol.

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Ethyl esters of N-isopropylidene-, N-benzylidene-, and N-p-nitrobenzylidene-D-methionine (II, I, and III) were prepared. The relative velocities of racemization of the Schiff bases were measured resulting in the order of (II)«(I)«(III). It has been postulated by Holland that prototropy in Schiff bases derived from α-amino acid esters occurs through tautomerism in the >C^*H-N=C< structure. The relative velocities found experimentally were in reverse of the theoretical assumption that they would be (II) > (I) > (III) by the electronic effect of the N-substituent, if the said postulation were correct. The findings support the view that the prototropic change occurs originally in the >C^*H-C=O structure and is additionally helped by the azomethine structure in the molecule.

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