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Volume 77, Issue 10
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Catalytic Synthesis of C-AlkylpiperazinesTakeo Ishiguro, Eiichi Kitamura, Masaki Matsumura1957 Volume 77 Issue 10 Pages 1051-1054
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1) Various alkanolamines were heated under a high pressure, with Raney nickel as a catalyst, and piperazines were prepared; piperazine from ethanolamine, 1, 4-dimethylpiperazine from 2-methylaminoethanol, and trans- and cis-2, 5-dimethylpiperazine from 1-amino-2-propanol. 3-Amino-2-butanol failed to undergo the reaction under a pressure of 600 lb./in2.
2) Reaction of ethylenediamine and various glycols in an autoclave, with Raney nickel as a catalyst, affords various C-alkylpiperazines in a good yield. Reaction of ethylenediamine with ethyleneglycol, 1, 2-propanediol and 2, 3-butanediol respectively afforded piperazine, 2-methylpiperazine, and trans- and cis-2, 3-dimethylpiperazine. 2-Methyl-1, 2-propanediol and pinacol failed to undergo this reaction.
3) Piperazines were also prepared by the reaction of N-(2-hydroxyalkyl)ethylenediamine in vapor phase catalysis and in liquid phase under high pressure.View full abstractDownload PDF (545K) -
Synthesis of (+)-L-Histidyl-p-phenylenediamineSadasuke Okano, Yasuhiko Fukagawa1957 Volume 77 Issue 10 Pages 1055-1058
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt is very difficult to prepare histidyl-type derivatives in which the carboxyl in histidine is bonded to an amino group in other molecules. The amino group in histidine was first shielded by p-nitrobenzyl chloroformate to prepare Nα-p-nitrobenzyloxycarbonyl-L-histidine, reacted with p-nitroaniline to form N-(Nα-p-nitrobenzyloxycarbonyl-L-histidyl)-p-nitroaniline, and its catalytic reduction with palladium black aff orded(+)-N-L-histidyl-p-phenylenediamine. Besides this synthetic procedure, optical and paper chromatographic characteristics of the intermediates and the final product, and surface activity and optical density of the final product are also described.View full abstractDownload PDF (586K) -
Zinc-casein. (2)Akira Minato, Kentaro Tanaka1957 Volume 77 Issue 10 Pages 1058-1061
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPartial hydrolyzate of zinc-casein (Zn 1.5%) was submitted to pH-fractionation and paper chromatography. Zinc was found to be distributed as a chelate compound in the peptides precipitating out in the pH range of (I) 7.2-7.4 and (II) 8.6-8.8 (Fig. 1). Further complete hydrolysis and the same procedures showed that (I) consists of leucine, tyrosine, glutamic acid, lysine, and a zinc-chelated amino acid (Fig. 2), and (II) of glutamic acid, lysine, and a zinc-chelated amino acid (Fig. 4). The zinc-chelated amino acids from (I) and (II) were isolated and removal of zinc afforded only histidine. The ultraviolet spectrum of zinc-chelated amino acid exhibits a maximum absorption at 266mμ, which disappears on removing zinc (Figs. 5, 6). Paper electrophoresis of zinc-chelated amino acid in alkaline buffer solution revealed that the compound remains in the original point, showing that the dissociation of zinc and histidine in aqueous solution does not occur.View full abstractDownload PDF (518K) -
Syntheses of 2-Pyrroline Derivatives from 4-Aminobutyric Acid and L-Glutamic AcidIsamu Murakoshi1957 Volume 77 Issue 10 Pages 1062-1064
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDry distillation of 4-aminobutyric acid and its ethyl ester, as acetyl, benzoyl, or nicotinyl derivative, with equal volume of soda lime or calcium oxide, affords 2-methyl-, 2-phenyl-, or 2-(3-pyridyl)-2-pyrroline in respective yield of 25, 85, or 95%. The yield increases if the dry distillation is carried out on the esters. Similar cyclization of the acetyl and benzoyl derivatives of glutamic acid by dry distillation only afforded 2-phenyl-2-pyrroline in 15% yield and 2-methyl-2-pyrroline was not obtained. From the diethyl nicotinylglutamate, a picrate was obtained in 20% yield of the starting material as golden yellow needles, m. p. 201-202°, the structure of which is still unknown. Catalytic reduction of the 2-pyrroline derivatives with palladium-carbon as a catalyst affords pyrrolidine derivatives in quantitative yield. For example, myosmine affords dl-nornicotine.View full abstractDownload PDF (450K) -
Syntheses of Pyrido[3, 2, 1-k, l]phenothiazine Derivatives. (1)Kiichi Fujii1957 Volume 77 Issue 10 Pages 1065-1068
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDehydrative cyclization of 3-(10-phenothiazinyl) propionic acid (I) with phosphorus pentoxide or polyphosphoric acid afforded 1H-pyrido[3, 2, 1-k, l]phenothiazin-3(2H)-one (II), which was also obtained by the reaction of dialkylcadmium with the acid chloride of (I). This kind of cyclization reaction proceeded in two directions in 3-(2-chloro-10-phenothiazinyl) propionic acid, affording 10- and 4-chloro derivatives. Similar cyclization reactions were carried out on 3-diphenylaminopropionic acid, 3-(2-oxo-2, 3-dihydro-3-benzothiazolyl) propionic acid, 3-(9-carbazolyl) propionic acid, and corresponding cyclized products were isolated.View full abstractDownload PDF (604K) -
Syntheses of Pyrido[3, 2, 1-k, l]phenothiazine Derivatives. (2)Kiichi Fujii1957 Volume 77 Issue 10 Pages 1068-1070
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS3-Dimethylamino-2, 3-dihydro-1H-pyrido[3, 2, 1-k, l]phenothiazine, the compound resulting from ring-closure between the carbon in 1-or 9-position of Phenothiazine ring and the carbon in 3-position of the side chain of chlorpromazine, and allied compounds including the chloro derivatives were prepared by the reaction of 1H-pyrido[3, 2, 1-k, l]phenothiazin-3(2H)-one (III) with formamide and N- methylformamide, followed by hydrolysis or reduction. 2-Dialkylaminomethyl-1H-pyrido[3, 2, 1-k, l]phenothiazin-3(2H)-one, in which C=O links the carbon in 1-position of phenothiazine ring and the carbon in 2-position of the side chain of chlorpromazine was also synthesized by submitting (III) to Mannich reaction.View full abstractDownload PDF (386K) -
The Influence of Non-ionic Surfactants on the Activity of Sparingly Water-soluble FungicidesMasaru Aoki, Akira Kamada, Mitsuo Matsumoto, Kazuko Hasegawa, Yukio Is ...1957 Volume 77 Issue 10 Pages 1071-1075
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExaminations were made to see whether the decrease of antifungal effect of p-hydroxybenzoic acid esters when solubilized with the non-ionic surface active agents would also occur in other antifungal agents sparingly soluble in water, using phenylmercuric pentachlorophenoxide, Actamer, and G-11, against Aspergillus niger and Trichophyton rubrum. As indicated in Tables II to V, addition of non-ionic surfactant was found to decrease the potency of these antifungal agents. It was also recognized, as reported in the previous papers, that the concentration of the antifungal agent in the aqueous phase is more important than that in the micelle of the surface active agents. In aqueous solution, G-11 is more powerful than Actamer in antifungal activity but loses its effect with smaller amount of surfactant because it easily enters into the micelle. By using eight kinds of structurally different non-ionic surfactants it was observed that following five factors changed the effect of the surfactants on the potency of antifungal agents: balance of hydrophilic and lipophilic parts, additive polymerization degree of ethylene oxide, number of ester bond, difference in fatty acid, and the presence of a benzene ring.View full abstractDownload PDF (751K) -
Alkaloids of Berberis amurensis RUPR. var. japonica (REGEL) REHD. forma Bretschneideri (REND.) OHWI. (3). Structure of Berbamunine. (i)Masao Tomita, Takehiko Kugo1957 Volume 77 Issue 10 Pages 1075-1078
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA new phenolic base of m. p. 190-191° was isolated from Berberis amurensis RUPR. var. japonica (REGEL) REHD. forma Bretschneideri (REHD.) OHWI (Japanese name “Akajikuhebinoborazu”) and it was named berbamunine. Its molecular and rational formulae are indicated by C36H40O6N2=C32H25(OCH3)2 (OH)3 (-O-)(NCH3)2. Permanganate oxidation of the O-methyl ether of this base afforded 2-methoxydiphenyl ether-5, 4′-dicarboxylic acid (I) and the methine base obtained by the Hofmann degradation of the O-methyl ether methiodide was found to be identical with O-methyldauricine methyl ether. Consequently, it was clarified that this berbamunine is a phenolic base belonging to the dauricine type, of the biscoclaurine-type bases and that O-methylberbamunine, O-methyldauricine, and O-methylmagnoline are optical isomers indicated by the same structural formula (VI).View full abstractDownload PDF (618K) -
Alkaloids of Berberis amurensis RUPR. var. japonica (REGEL) REHD. forma Bretschneideri (REND.) OHWI. (4). Structure of Berbamunine. (ii)Masao Tomita, Takehiko Kugo1957 Volume 77 Issue 10 Pages 1079-1082
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCleavage reaction of O-ethylberbamunine (III) with metallic sodium in liquid ammonia was found to form quantitatively l-N-methyl-O, O-diethylcoclaurine (IV) and d-1-(4-hydroxybenzyl)-2-methyl-6-methoxy-7-ethoxyl-1, 2, 3, 4-tetrahydroisoquinoline (V). This has confirmed the positions of three phenolic hydroxyls in the berbamunine molecule.
On the other hand, the phenolic base (VII), obtained from berbamine (VI) as an intermediate decomposition product in the first-step cleavage reaction with sodiumliquid ammonia, was methylated with diazomethane and the infrared absorption spectrum of the O-methyl ether (VIII) thereby obtained was compared with that of O-metllylberbamunine. As a result, the two substances were found to be entirely identical.
From the foregoing experimental results, it was proved that berbamunine would be represented by the structural formula (II) and that the configuration of the two asymmetric centers in its molecule would be (-, +).View full abstractDownload PDF (646K) -
Akira Ito, Osamu Amakasu1957 Volume 77 Issue 10 Pages 1083-1086
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSQuantitative determination of estradiol benzoate, progesterone, methyltestosterone, and ethisterone (in solution) and ethynylestradiol (in KBr disc) by infrared absorption spectral measurement was examined. The key band of the four kinds of steroid by solution method was the two absorptions originating in the functional groups at 3- and 17-(or 20)-positions, and for the key band of ethynylestradiol by the KBr disc method, the two absorptions at 1504 and 818cm-1, in the region from absorption of bulking agents. It was thereby found that using with authors' mefhod, small amount of steroid preparations were able to analyze in a short period of time. The accuracy was approximately 1.0-1.8% by standard deviation in the solution method and approx. 2.0% in the KBr disc method. In the case of ethinyl estradiol, it was found that the absorption (1-I/IB) and not the extinction log(1B/I) which was proportional to the quantity of substance dispersed in the KBr disc. Preparation of the sample was found to be satisfactory enough by trituration in a mortar.View full abstractDownload PDF (485K) -
Synthesis of 1-Methyl-5-semicarbazono-6-oxo-2, 3, 5, 6-tetrahydro-indole-2-sulfonateKoichi Tomino1957 Volume 77 Issue 10 Pages 1087-1089
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSWith the purpose of obtaining water-soluble derivatives of adrenochrome monosemicarbazone, epinephrine was reacted with sodium hydrogen sulfite with heating and white prismatic crystals, decomposing at 259°, were obtained, whose analytical values indicated C9H13O5NS. This substance was oxidized with potassium ferricyanide and semicarbazide was applied to the oxidized solution, from which yellowish orange crystals, m. p. 227-228°(decomp.), were obtained. This substance showed the same decomposition point and elemental analytical values as those of sodium 1-methyl-5-semicarbazono-6-oxo-2, 3, 5, 6-tetrahydroindole-3-sulfonate (tentatively designated as AC-17), but its infrared and ultraviolet spectra did not agree with those of the latter. This substance was extremely labile to alkali and immediately underwent decomposition. Its solubility in water was 5mg./cc. (0°), about 1/3 of that of AC-17 and about 15 times that of adrenochrome monosemicarbazone, clearly different from AC-17. Its clinical and pharmacological tests showed that it had about the same degree of styptic effect as AG 17.View full abstractDownload PDF (383K) -
Structure of Sodium 1-Methyl-5-semicarbazono-6-oxo-2, 3, 5, 6-tetrahydroindole-2-sulfonateKoichi Tomino1957 Volume 77 Issue 10 Pages 1090-1092
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn order to determine the structure of the new compound, having excellent hemostatic activity, tentatively designated as AC-44, the sulfonic acid compound (A), C9H13O5NS, prepared from epinephrine and sodium hydrogen sulfite, was studied. Methylation of (A) with dimethyl sulfate and sodium hydroxide afforded a nitrogenfree sulfonic acid (B), C10H12O3S, with generation of trimethylamine. Ozonic oxidation of (B) gave veratric acid and reaction of (B) with potassium cyanide gave 3, 4-dimethoxycinnamic acid via its nitrile. Therefore, (B) is 2-(3, 4-dimethoxyphenyl)ethanesulfonic acid and (A) would be 1-methylamino-2-(3, 4-dimethoxyphenyl)ethanesulfonic acid. These are all new reactions. These results have established the structure of AC-44 as sodium 1-methyl-5-semicarbazono-6-oxo-2, 3, 5, 6-tetrahydroindole-2-sulfonate.View full abstractDownload PDF (452K) -
The Influence of Enzymes on the Activity of Principle of Mainini ReactionMotosuke Kikutani1957 Volume 77 Issue 10 Pages 1092-1095
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe principle (MG) showing Mainini reaction, isolated from human placental chorionic membrane, is a sugar-rich protein. In order to find what part or group in the MG molecule is necessary for the appearance of biological activity of MG, it was submitted to the action of carbohydrase and proteolytic enzymes. It was thereby found that the componental sugar did not play any direct important role in the activity of MG but the protein portion was, and especially tyrosine among the componental amino acids, seemed to take part in this activity. Since the MG activity is markedly decreased when acetylated with ketene, it was concluded that tyrosine is essential for the manifestation of MG action.View full abstractDownload PDF (599K) -
Syntheses of α-Methyl-2-alkoxyphenethylamines and Nuclear Substituted DerivativesZen-ichi Horii, Takeshi Inoi1957 Volume 77 Issue 10 Pages 1095-1100
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAs a sympathomimetic amine, α-methyl-2-methoxyphenethylamines show various pharmacological activities. In order to obtain a more effective substance, ring-substituted derivatives of this amine were prepared. The ring substituted allyl phenyl ether, obtained from ring-substituted phenol and allyl bromide, was submitted to the Claisen rearrangement followed by alkylation, the ring-substituted 2-1-alkoxy-2-allylbenzene so obtained was reacted with hydrogen bromide to form ring-substituted 1-alkoxy-2-(2-bromopropyl) benzene, and this was reacted with ammonia or amines to form the corresponding ring-substituted α-methyl-2-alkoxyphenethyl-amines. The ring-substituted 1-alkoxy-2-propenylbenzene was substituted with a mixture of formic acid and hydrogen peroxide, the product was hydrolyzed with dilute acid, and the ring-substituted 1-alkoxyphenyl-2-propanone so obtained was submitted to reductive amination and Leuckart reaction to form the corresponding amines. These amines were further submitted to N-alkylation reaction and demethylation of the methoxyl group.View full abstractDownload PDF (749K) -
Synthesis of Haptenes. (2). L-Histidyl Derivatives of Phenylenediamines, Choline, Dialkylaminoethanols, and DL-AlaninolSadasuke Okano, Shoji Kojima, Yasuhiko Fukagawa1957 Volume 77 Issue 10 Pages 1100-1104
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSUsing Nα-p-nitrobenzyloxycarbonyl-L-histidine (I) as the starting material, N-L-histidyl-o(or m)-phenylenediamine, O-L-histidylcholine, L-histidine 2-dimethylaminoethyl ester, and L-histidine 2-diethylaminoethyl ester were prepared. N-L-Hi-stidyl-DL-alaninol was prepared from Nα-benzyloxycarbonyl-L-histidine. The phenylenediamine derivatives were obtained by the catalytic reduction of the corresponding N-(Nα-p-nitrobenzyloxycarbonyl-L-histidyl)-nitroanilines with palladium black catalyst, and were optically active. Diazotization of the aromatic amino group in the histidylphenylenediamine and coupling with 2-naphthol showed that the meta-derivatives undergo this coupling while the ortho derivatives do not, and this was assumed to be due to intramolecular condensation of the diazonium group in the ortho derivative to form an azimino type compound. Preparation of the esters of histidine with choline and dialkylaminoethanol effected through the anhydride of (I). This was especially facile in the reaction with choline and its hydrochloride was obtained in a high yield of 88%. This method of choline ester synthesis seems to be recommendable for the preparation of choline ester of amino acids in general. Action of three kinds of alkylaminoethanols against isolated intestine of a rabbit was tested by the Magnus method.View full abstractDownload PDF (663K) -
Synthesis of Haptenes (3). Nα-Aminobenzoyl-L-histidines and Nω-AminobenzoylhistaminesSadasuke Okano, Shoji Kojima, Hiroto Korenaga1957 Volume 77 Issue 10 Pages 1105-1107
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSNα-o(, m or p)-Aminobenzoyl-L-histidine and Nω-o(, m or p)-aminobenzoylhistamine were prepared by the catalytic reduction of the corresponding nitrobenzoyl derivatives. Reduction with tin or iron and hydrochloric acid was also carried out to compare the yield. Schotten-Baumann reaction for preparing nitrobenzoyl-histidine or -histamine differs according to the kind of the solvent used. In the case of Nω-o-nitrobenzoylhistamine, toluene is suitable and ether or ethanol is not, while toluene, benzene, or ether could be used in other cases. All the aminobenzoyl-L-histidines obtained were optically active. p-Nitro- and p-aminobenzoyl compounds and their hydrochloric acid hydrolyzates were examined by paper partition chromatography and satisfactory results were obtained. The ultraviolet absorption curves of six kinds of aminobenzoyl derivatives indicated that the maximum appeared in similar position in the histidine and histamine derivatives when they possessed amino groups on the benzene ring in corresponding positions. The surface tension of the aqueous solution of histidyl-o- and -m-phenylenediamines was measured and both were found to be surface active to a small degree.View full abstractDownload PDF (418K) -
Synthesis of Haptenes. (4). Stability of 1-Acyl- and 1-Arylsulfonylimidazole DerivativesSadasuke Okano, Yoshiko Nonaka, Yasuhiko Fukagawa1957 Volume 77 Issue 10 Pages 1108-1110
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt was found that the diazotization of the aromatic amino group in Nω-o(, m or p)-aminobenzoylhistamine, o(, m or p)-aminobenzoyl-L-histidine, and N-(L-histidyl)-o(, m or p)-phenylenediamine and basification of the reaction solution resulted in coloration, except in the case of histidyl-o-phenylenediamine. Absence of coloration in the latter was assumed to be due to intramolecular azimino-type condensation and the coloration in other compounds was thought to be the intramolecular coupling of the diazonium group into imidazole. Therefore, to prepare azoprotein by diazotization of such compounds and coupling with protein requires protection of imidazole from such intramolecular coupling. On the other hand, presence of a substituent in the imidazole ring is not desirable for immunological and pharmacological reasons. For this reason, attempt was made to introduce a labile substituent into 1-position of imidazole and liberating the said substituent under mild conditions after diazotization and coupling with protein. L-Histidine methyl ester derivatives in which the hydrogen in 1-position of the imidazole ring was substituted with benzoyl, acetyl, benzenesulfonyl, p-acetamidobenzenesulfonyl, or p-toluenesulfonyl group were prepared and their stability in acid and alkali solution and the time required for positivization of Pauli reaction were examined. The two acyl substituted derivatives were too labile for the present purpose but three kinds of arylsulfonyl derivatives were found to have suitable stability.View full abstractDownload PDF (477K) -
Masaichiro Masui, Yoichiro Ban1957 Volume 77 Issue 10 Pages 1111-1116
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn order to vary the distance of positive and negative charge centers, Δr, dicarboxylic acids were titrated with KOCH3 and R4NOH (R=CH3, C2H5, n-C4H9), as well as with LiOCH3 and NaOCH3. With tetramethylammonium hydroxide (TMAH), Dc value of numerous acids was obtained but less with tetraethylammonium hydroxide (TEAR), and not at all with tetrabutylammonium hydroxide (TBAH). As shown in Table I, values of Dc obtained with R4NOH are much smaller than those obtained with alkali. It is suggested from the data shown by equations (1) and (2), and in Table II, that the values of Δr TMAH and TEAH should be markedly large or small, and the values calculated from equation (3), based on the data in Table III, are 0.76 and 0.62 Å, respectively, being very small. This seems reasonable from the fact that, when titrated with two kinds of bases with different Δr, values of Dc found were in good agreement with the values calculated from equation (4) and Fig. 2. The reason for this seems to be the displacement of charge center of R4N+, or a large overall dissociation constants of R4N salts, rather than the solvation of alkali ions (Table V).
For the estimation of r, Δr values of 2.35, 2.73, and 0.76 should respectively be adopted for NaOCH3, KOCH3 and TMAH, TMAH is especially useful since its salts are all soluble.View full abstractDownload PDF (810K) -
Color Reaction and its Mechanism of Diaryl Disulfides in Sulfuric AcidKiyoshi Kawahara1957 Volume 77 Issue 10 Pages 1116-1120
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSColoration of diaryl disulfide by sulfuric acid was first pointed out by Stenhouse. Coloration of dialkyl, diaryl, diaralkyl, and diheterocylic disulfides with sulfuric acid was examined and it was found that these disulfides in general colored yellow or blue with sulfuric acid, with the exception of a few insoluble in sulfuric acid. Fries suggested the formation of a thianthrene-type compounds as the reaction mechanism for this coloration. However, since the diaryl disulfides possessing substituents in the two ortho positions undergo coloration with sulfuric acid in spite of the fact that they would hardly form the thianthrene-type compounds, this reaction mechanism seemed to be somewhat doubtful and Fries' experiments were reëxamined. It was thereby clarified that the compound reported to have been obtained by Fries from diphenyl disulfide as “structurally unknown substance not possessing a sulfonic acid group and sparingly soluble in water” was a diphenyl disulfide with the sulfonic acid groups substituted in each ring and that dimesityl disulfide, possessing substitutents in the two ortho positions afforded dimesityl disulfide with one sulfonic acid group in the ring (V). Some discussions were made on the value of this coloration reaction as determination of -S-S-type compounds and such feasibility within a limited range was pointed out.View full abstractDownload PDF (633K) -
Antioxidative Effect of Phenolic Compounds containing Sulfur for Fats and OilsMasuo Akagi, Isamu Aoki1957 Volume 77 Issue 10 Pages 1121-1123
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAntioxidative effect of 16 kinds of sulfur-containing compounds of hydroquinone system, 3 kinds of the benzoquinone system, and 6 kinds of benzoquinone derivatives was tested with methyl oleate as the substrate. The compounds formed by the introduction of thiols, possessing active methylene or phenolic hydroxyl, into hydroquinone had the strongest effect. With alkylthiohydroquinones, those with alkyls of lower member were more effective than those of higher member. In monothio and dithio derivatives of hydroquinone, monothio derivatives had better effect. Benzoquinone derivatives were practically ineffective but the addition of phosphoric acid or ascorbic acid stearate as synergist increased the effect, although the synergist itself was entirely ineffective. These hydroquinone and benzoquinone derivatives all tended to be colored easily and were sparingly soluble in methyl oleate.View full abstractDownload PDF (355K) -
N-(1-Methyl-2-thiocyano-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)-methyl]formamide (Cyanothiamine) and its Derivatives. (1)Haruo Yonemoto1957 Volume 77 Issue 10 Pages 1124-1127
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSApplication of cyanogen bromide to the sodium salt of thiol-type thiamine afforded N-(1-methyl-2-thiocyano-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)-methyl]formamide (cyanothiamine). The structure of cyanothiamine is proved by the formation of 2-methyl-4-amino-5-aminomethylpyrimidine, formic acid, and 2-imino-3-[(2-methyl-4-amino-5-pyrimidinyl)methyl]-4-methyl-5-hydroxyethylthiazole by its decomposition with hydrochloric acid.View full abstractDownload PDF (671K) -
N-(1-Methyl-2-thiocyano-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]-formamide (Cyanothiamine) and its Derivatives. (2)Haruo Yonemoto1957 Volume 77 Issue 10 Pages 1128-1132
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSApplication of alkali to cyanothiamine affords a substance (A) of m. p. 136° and its structure was examined. The oxidation of (A) gives a sulfone derivative and decomposition of (A) with hydrochloric acid affords 2-methyl-4-amino-5-aminomethyl-pyrimidine, formic acid, and 2-acetylthiacyclobutane. The structure of the cyclobutane compound was established by the synthesis of 2-(1-hydroxyethyl)thiacyclo-butane, its reduction product.View full abstractDownload PDF (699K) -
Action of Cyanogen Bromide on Thiol Form of Thiamine. (1)Shizuka Kasahara1957 Volume 77 Issue 10 Pages 1133-1136
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1). Addition of 3 moles of sodium hydroxide to the aqueous solution of thiamine hydrochloride to form the sodium salt of thiol-type thiamine, followed by the addition of aqueous solution of cyanogen bromide, and immediate basification with 30% sodium hydroxide afford colorless hydrate crystals of m. p. 109.5°, which give a dehydrated compound of m. p. 134-136° by drying over phosphorus pentoxide.
2). Addition of 3 moles of sodium hydroxide to the aqueous solution of thiamine hydrochloride to form the sodium salt of thiol-type thiamine and application of 1 mole of cyanogen bromide to it affords colorless hydrate crystals of m. p. 78-80°. Recrystallization from dehydrated ethanol gives N-(1-methyl-2-thiocyanato-4-hydroxy-l-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide (III) as crystals melting with decomposition at 150.5-151.5°. This substance is decomposed by hydrochloric acid into 2-methyl-4-amino-5-aminomethylpyrimidine and formic acid, by sodium hydroxide into thiamine, thiamine disulfide, and a substance of m. p. 134-136°, and reduced by sodium sulfide or cysteine hydrochloride into thiamine. The substance of m. p. 134-136° is identical with the unknown substance obtained by Yurugi by the pyrolysis of thiamine disulfide.View full abstractDownload PDF (561K) -
Hydrolysis of the Nonionic Surfactant by Pancreatic LipaseMorie Nishida1957 Volume 77 Issue 10 Pages 1137-1141
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDecomposition of nonionic surface active agents by pancreatic lipase was examined. Surfactants possessing ester bonding with fatty acid are easily decomposed by pancreatic lipase and the degree of such decomposition seems to be dependent on the kinds of fatty acid rather than the structure of surfactants when fairly soluble in water. Such lipophilic surfactants are liable to form an emulsion and are hardly decomposed and increase of the concentration of surfactants decreases the decomposition. Effect of solubilization of solutes was also examined. Solubilization of a non-polar solute, toluene, was found to decrease the decomposition of the surfactants with increasing amount of toluene. Solubilization of hexanol, possessing a polar group, was also found to decrease decomposition of Tween-type surfactants, such as polyoxyethylene sorbitan monolaurate and oleate, with increasing amount of hexanol. With Myrj-type, like polyoxyethylene oleate and stearate, the situation was somewhat different from the case of toluene and the decomposition of the surfactants increased with the increasing amount of hexanol up to a certain limit, after which decomposition of the surfactants decreased with increasing solubilization of hexanol. These experimental results indicated that there is a difference in the decomposition of surface active agents according to their structure.View full abstractDownload PDF (729K) -
Hydrolysis of Solubilized Esters by Pancreatic LipaseMorie Nishida1957 Volume 77 Issue 10 Pages 1141-1145
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExamination was made on the decomposition of esters, solubilized by nonionic surface active agents, by pancreatic lipase. The surfactants used were ether-type agents that are not decomposed by lipase, with polyoxyethylene lauryl ether as the chief agent. Comparative examinations were made on the solubilization and emulsification systems with ester-type surfactants. The presence of a surfactant activated the hydrolysis of comparatively water-soluble ethyl acetate and triacetin by the lipase, either in solubilization or emulsification system. Decomposition of triacetin was accelerated the most by the ether-type surfactants which are not decomposed by lipase. Ester-type surfactants, either of Tween-type or Myrj-type, accelerated the decomposition of esters the most when the agents themselves are inert to lipase decomposition. With ethyl butyrate, which is slightly less hydrophilic than ethyl acetate, decomposition is accelerated by lipase in the solubilization system and suppressed in emulsification system. Decomposition of all lipophilic esters by lipase is suppressed in the presence of surfactants, either in solubilization or emulsification system.View full abstractDownload PDF (674K) -
Syntheses and Antispasmodic Actions of Alkamine Esters of 9-Xanthenylacetic AcidToshio Matsuno, Ichizo Okabayashi1957 Volume 77 Issue 10 Pages 1145-1148
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeven kinds of alkamine esters of 9-xanthenylacetic acid, obtained by the condensation of 9-xantheriol with malonic acid in pyridine, and an alkamine ester of 9-xanthenylcyanoacetic acid, were prepared. 2, 7-Dinitro-9-xanthenol does not undergo condensation with malonic acid and forms 9-acetoxyxanthene compound on heating with acetic anhydride. Comparative examinations were made on the toxicity, antiacetylcholine, antihistamine, and anti-barium chloride activities of these alkamine esters. In general, these compounds had stronger antiacetylcholine activity than other activities and this action was the strongest in 2-diisopropylaminoethyl 9-xanthenylacetate hydrochloride.View full abstractDownload PDF (488K) -
Koku Matsumoto, Setsuko Sone1957 Volume 77 Issue 10 Pages 1149-1150
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMutual solubility of a pyridine-water-carbontetrachloride system was measured at 15° and 30° in order to examine whether carbontetrachloride is best suited for the extraction of pyridine from aqueous solution of pyridine and to find out the extraction effect. Selective power of carbontetrachloride to pyridine was also examined. It was thereby found that the selective power P was 2.5 (15°) and 2.2 (30°) at the upper end of the solutrope and 4.2 (15°) and 3.5 (30°) at its lower end. For the sake of comparison, the selective power of benzene to pyridine was calculated from Smith's data and the value was found to be smaller than that of carbontetrachloride. This indicates that carbontetrachloride is better than benzene as the extraction solvent for pyridine and that its extraction effect is greater at the lower end of the solutrope at a low temperature.View full abstractDownload PDF (252K) -
Koku Matsumoto, Setsuko Sone1957 Volume 77 Issue 10 Pages 1151-1152
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMutual solubility of a glycerol-water-butanol system was measured at 20° and 40° and the solubility was found to be greater at higher temperature. Distribution curve of glycerol in the water-rich and butanol-rich phases was calculated and glycerol was found to be distributed in larger amount in the former phase. It would not be suitable to determine the amount of water in glycerol from the mutual solubility of a three-componental system, with butanol as an entrainer and butanol is not a good extraction solvent for extracting glycerol from its aqueous solution since the selective power of butanol as a solvent is 0.449 (20°) and -0.128 (40°). The tie-line data was linear in Bachman's equation but was only partially linear by Hand's and Major's equations.View full abstractDownload PDF (253K) -
Koku Matsumoto, Setsuko Sone1957 Volume 77 Issue 10 Pages 1153-1155
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMutual solubility of an alcohol-water-carbontetrachloride system was measured at 15° and 30° and selective power of carbontetrachloride for alcohols was calculated. It was thereby found that the selective power of cabontetrachloride was 1.03 (15°) and 0.98 (30°) for the ethanol system, 9.35 (15°) and 7.65 (30°) at the upper end and 2.27 (15°) and 2.26 (30°) at the lower end of the solutrope for the propanol system, and 4.21 (15° and 30°) at the upper end and 2.37 (15°) and 2.28 (30°) at the lower end of the solutrope for the isopropanol system. It follows that the extraction effect of carbontetrachloride is rather low for ethanol but greater for propanol and is an excellent extraction solvent.View full abstractDownload PDF (448K) -
Saburo Muraoka, Atsushi Takada1957 Volume 77 Issue 10 Pages 1155-1156
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFor the purpose of preparing arginine hydrazine, hydrazine hydrate was applied to arginine methyl ester hydrochloride but the objective substance was not obtained and in its stead, triaminoguanidine (I) was obtained as colorless needles, m. p. 227°. (I) is also obtained by the reaction of arginine with hydrazine hydrate but the reaction was accompanied by the formation of ornithine.
Biological activity of triaminoguanidine was also examined and it was found to inhibit the growth of Escherichia coli No. 1 and the concentration necessary for complete inhibition was 100γ/cc., indicating about the same degree of inhibitory activity as that of hydrazine hydrate or semicarbazide.View full abstractDownload PDF (302K) -
On the Structure of Aritasone. (2)Tsunematsu Takemoto, Tadashi Nakajima1957 Volume 77 Issue 10 Pages 1157-1158
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSInfrared spectra of structurally known pinocamphone (II), 2-methylenecyclohexanone dimere (III), 2-methylcyclohexanone (IV), and 2-ethylcyclohexanone (V) and that of aritasone were compared at νc=o, and it was concluded that the structure of aritasone, considered to be a dimer of pinocarvone, would be more appropriately represented by (Ib) than (Ia). In this case, the ring with the carbonyl in (Ib) would be in chair form and the bond of the carbonyl and ether is assumed to be in coplanar direction.View full abstractDownload PDF (250K) -
Tomoji Suzuki, Fumihiko Tanaka1957 Volume 77 Issue 10 Pages 1159-1160
Published: October 25, 1957
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (501K)
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