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MASATO MORI, HISANORI KANAYAMA, KOICHI TABATA, TANEZO TAGUCHI
1969 Volume 89 Issue 12 Pages
1631-1636
Published: December 25, 1969
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Bordwell, et al.
8) had reported that DL-trans-2-p-tolylthiocyclohexyl S-methyl xanthate (IX) suffered cis-elimination by the Chugaev reaction. However, the present study revealed that the analogue (Ia) carrying a methylthio group in place of the tolylthio group in IX underwent rearrangement to the corresponding dithiolcarbonate. The rearrangement of Ia was attributed to the anchimeric power of the methylthio group. A variety of 2-methylthioalkyl S-methyl xanthates and DL-trans-2-methylthiocyclohexyl N, N-dimethylthionocarbamate (Ib) were thermally treated and the results provided evidences for this rearrangement mechanism which was analogous to that proposed in the case of 2-dialkylaminoalkyl S-methyl xanthates.
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TETSUZO KATO, HIROSHI YAMANAKA, JUNSHI KAWAMATA
1969 Volume 89 Issue 12 Pages
1637-1640
Published: December 25, 1969
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Acetylation of ethyl 3-aminocrotonate (I) gives three kinds of monoacetate according to the kind of acetylation agent used. The product of mp 54° is a C-acetate (V) which is obtained in a good yield from I and ketene. The isomer (II) of mp 63° obtained by the treatment of I with acetic anhydride is an N-acetate of I, while the other isomer (III) of mp 108° obtained by the treatment of I with acetyl chloride in pyridine is also an N-acetate of I. II and III are considered to be cis-trans isomers with respect to the enamine carbon-carbon double bond. The structure of II, III, and V is not inconsistent with the result of their decomposition reaction and instrumental analyses.
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SHUZO TAKAGI, TOYOSHI KATAGI, KEIKO TAKEBAYASHI
1969 Volume 89 Issue 12 Pages
1641-1645
Published: December 25, 1969
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In a previous paper,
3) several alkaloids of Lycoris radiata HERB. were separated by gas chromatography using HI-EFF 8B as liquid phase, but lycorenine, one of the main bases, failed to be detected under various conditions. In this report, we give a description of conversion of lycorenine into various derivatives such as acetyl lycorenine, tetrahydrohomolycorine trimethylsilyl ether, diacetyl tetrahydrohomolycorine and deoxylycorenine ; these derivaties were chromatographed with OV-101, OV-17 and XE-60 column. An excellent separation of lycorenine was obtained by converting to tetrahydrohomolycorine TMS ether on 3% XE-60 column at 200°. We tried also to applicate this method to the extract of the alkaloids of Lycoris radiata HERB. Both lycorenine and homolycorine, in the extract, were converted to tetrahydrohomolycorine, which then was trimethylsilanized and chromatographed. The elution pattern is shown on Fig. 5. The quantitative determination of total tetrahydrohomolycorine was carried out using carbazole as internal standard. The amount of homolycorine was determined with a HI-EFF 8B column, while the approximate quantity of lycorenine was obtained by subtracting the amount of tetrahydrohomolycorine corresponding to homolycorine from the total tetrahydrohomolycorine.
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SUMI SUGIURA, SHOJI INOUE, YOSHITO KISHI, TOSHIO GOTO
1969 Volume 89 Issue 12 Pages
1646-1651
Published: December 25, 1969
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To confirm the sutructure of Cypridina luciferin, synthesis of 2-amino-5- (3-indolyl) -pyrazine (XXI) was carried out by condensation of 3-indolylglyoxal and α-aminoacetamidine. We confirmed that the indolyl group in XXI is substituted at 5 and not at 6 position of the pyrazine ring in comparing the nuclear magnetic resonance spectrum of XXI with that of authentic 2-amino-5-phenylpyrazine (IX) obtained by condensation of phenylglyoxal aldoxime and aminoacetonitrile followed by reduction. IX was also synthesized from phenylglyoxal and α-aminoacetamidine. Ultraviolet spectral behavior of the pyrazine (XXI) is nearly identical with that of etioluciferin obtained from natural luciferin, indicating that both XXI and etioluciferin have the same chromophore.
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SUMI SUGIURA, SHOJI INOUE, YOSHITO KISHI, TOSHIO GOTO
1969 Volume 89 Issue 12 Pages
1652-1656
Published: December 25, 1969
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2-Amino-5-benzamidovaleramidine dihydrobromide (X) was synthesized from 4-benzamidobutyraldehyde diethyl acetal. Using the similar procedure reported in the previous paper for the preparation of 2-amino-5- (3-indolyl) pyrazine, X and 3-indolylglyoxal were condensed to afford benzoyletioluciferamine (XII), which in turn was hydrolyzed with methanolic KOH to give etioluciferamine (I). Synthetic I was proved to be identical with I obtained from natural luciferin.
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YOSHITO KISHI, SUMI SUGIURA, SHOJI INOUE, TOSHIO GOTO
1969 Volume 89 Issue 12 Pages
1657-1660
Published: December 25, 1969
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Synthetic Cypridina etioluciferamine (I) described in the previous paper, was transformed in a good yield to Cypridina etioluciferin (II) by condensation with S-ethylisothiourea. II was identical with the natural Cypridina etioluciferin in every respects. II was successfully converted to Cypridina luciferin (III) by using the following procedures ; the etioluciferin (II) was treated with D-2-oxo-3-methylvaleric acid (IV) in ethanol, reduced by aluminum amalgam or by catalytic hydrogenation, and finally treated with DCC in ethanol under argon at 4°. The product, Cypridina luciferin (III), was purified through an alumina column and isolated as its hydrobromide. The synthesized luciferin (III) hydrobromide was found to be identical with the natural luciferin hydrobromide in every respects (biological activity, UV spectrum, IR spectrum, mp, mixed mp, paper chromatography).
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ISAMU MURAKOSHI, KUNIO TAKADA, JOJU HAGINIWA
1969 Volume 89 Issue 12 Pages
1661-1663
Published: December 25, 1969
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Dry distillation of ethyl 3-oxoindolizidine-5-propionate (I) with the same amount of soda lime as reported previously affords 1, 2, 4, 4a, 5, 6, 7, 7a-octahydropyrrolo [2, 1, 5-cd] -indolizine (II) in 48% yield. In order to confirm the α, β-enamine structure of II, conc. potassium cyanide solution was added dropwise with stirring to a solution of the perchlorate (III) of II. In this case, the cyano compound (IV) was also obtained in a quantitative yield. Attempted recrystallization of the picrate of IV from hot ethanol yielded the picrate of II by elimination of hydrocyanic acid as shown in Chart 1.
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YOSHIO AIZAWA, MORIO IWASAKI
1969 Volume 89 Issue 12 Pages
1664-1668
Published: December 25, 1969
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Influence of inflammation on the phospholipid metabolism in skeletal muscle and action of anti-inflammatory drugs on that were examined. Phospholipid content in skeletal muscle increased by inflammation and reached a maxium on the sixth day of inflammation. Incorporation of orthophosphate-
32P into phospholipid of skeletal muscle was also increased by inflammation and reached a maxium on the fourth day of inflammation. The increase of incorporation of orthophosphate-
32P into phospholipid by inflammation was inhibited by subcutaneous injection of cortisone or prednisolone. The incorporation of orthophosphate-
32P into phospholipid in inflammatory skeletal muscle was inhibited by the addition in vitro of cortisone, prednisolone, or dexamethazone but that of intact muscle was not affected.
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ITSUHIKO MORI, NORIKO TSUNEMATSU, MASAKI SHINOGI
1969 Volume 89 Issue 12 Pages
1669-1672
Published: December 25, 1969
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Some 34 common metallic ions were separated rapidly and identified by thin-layer electrophoresis on one piece (6.5×2 cm) of thin-layer Chromatosheet (Eastman Kodak Co., silicagel). Fundamental experiments were carried out at first using citric acid as the electrolytic solution. The relationship between the migration distance and migration time as well as the electric potential gradient, the concentration of citric acid, and pH of the electrolytic solution were examined. The electrophoresis was carried out for 5 min with 300 V/6.5 cm, using 0.1 M citric acid as the electrolytic solution. The samples were spotted at 1.5 cm from the chromatostrip end (anode side). Electrophoresis of
140Ba-
140La was also carried out for 5, 7, and 10 min, and about 90% separation of
140La was obtained by electrophoresis for 10 min.
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SHUICHI SETO, TOSHIKATSU HIRATSUKA, HIROKO TODA
1969 Volume 89 Issue 12 Pages
1673-1677
Published: December 25, 1969
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It has been clarified that tropone
4) (Ia) is stabilized by the resonance effect of the structure Ib, from some experimental data, for example, dipole moment,
5) electron diffraction,
6) and IR spectrum.
7) In aminotropone and aminotropolone derivatives, contribution of the structure Ib should result in the decrease of basicity of the amino group. The pK
a values of aminotropones and aminotropolones
11-18) (III to XIII) were measured by the spectroscopic method
8) in order to investigate the contribution of the structure of Ib type for stabilization of the compounds III to XIII. It was found that the basicity of aminotropones and aminotropolones (Table II) tends to rise as the distance between the amino group and the carbonyl group increases, and is comparable to those of cyanoaniline,
19) chloroaniline,
20) and bromoaniline.
21) Tautomerism of asymmetric aminotropolones was also discussed. By comparison of the UV spectra of aminotropolones with those of aminotropones, it was concluded that 3-aminotropolone (XI) and 4-aminotropolone (XII) exist predominantly as the tautomeric structure of 2-aminotropone type (XIa) and 3-aminotropone type (XIIa), respectively, in water.
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MASAO TOMITA, TOKUNOSUKE SAWADA, MUTSUO KOZUKA, MITSUKO TAKEUCHI, MICH ...
1969 Volume 89 Issue 12 Pages
1678-1681
Published: December 25, 1969
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From the root tuber of Stephania cepharantha HAYATA (Japanese name "Tamasaki-tsuzurafuji") cultivated in Japan, cepharanthine (I), isotetrandrine (II), cycleanine (III), and berbamine (IV) were isolated together with a new crypto-phenolic base of bisbenzylisoquinoline type, cepharanoline (decomp. 270°, [α]
35D +319° (CHCl
3), C
36H
36O
6N
2). The O-methylcepharanoline (mp 103°, [α]
30D +287° (CHCl
3), C
37H
38O
6N
2) was identified by comparison with cepharanthine (I). The mass spectrum of cepharanoline revealed that the phenolic hydroxyl in cepharanoline is present in 4'-position. These experiments revealed that cepharanoline is represented by formula VII.
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TAICHI OHMOTO
1969 Volume 89 Issue 12 Pages
1682-1687
Published: December 25, 1969
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Distribution of triterpenoids and related compounds was examined for six species of Gramineous plants, with special reference to the chemotaxonomical point of view. The triterpenoids thus identified are shown in Table I. Arborinol methyl ether (Vd), a new triterpene methyl ether, was isolated from the culms and leaves of Imperata cylindrica BEAUV. var. koenigii, DURAND et SCHINZ and identified with the synthetic specimen.
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TAKAJI KOYAMA, MUTSUKO TODA, TAKASHI HIROTA, MAKI HASHIMOTO, MASATOSHI ...
1969 Volume 89 Issue 12 Pages
1688-1690
Published: December 25, 1969
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Heating of α-acyl-3, 4-methylenedioxyphenylacetonitriles (I) with H
2NCHO and POCl
3 afforded pyrimidines (II) and enamines (III), the intermediate of pyrimidines, but isoquinolines were not isolated. Thus α-formyl derivative (Ia) gave 4-amino-5- (3', 4'-methylenedioxyphenyl) pyrimidine (IIa), α-acetyl derivative (Ib) gave β-amino-α- (3, 4-methylenedioxyphenyl) crotononitrile (IIIb), but under more drastic conditions Ib or IIIb gave 4-amino-6-methyl-5- (3', 4'-methylenedioxyphenyl) pyrimidine (IIb), and α-benzoyl derivative (Ic) gave 4-amino-5- (3', 4'-methylenedioxyphenyl) -6-phenyl-pyrimidine (IIc), and β-amino-α- (3', 4'-methylenedioxyphenyl) cinnamonitrile (IIIc), but under more drastic conditions Ic or IIIc gave only IIc. 3, 4-Methylenedioxyphenylacetonitrile (IV) gave IIa and 3, 4-methylenedioxyphenylacetamide (V) under the same reaction conditions.
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JUN-ICHI KUNITOMO, YASUKO OKAMOTO, ETSUKO YUGE, YOSHIKO NAGAI
1969 Volume 89 Issue 12 Pages
1691-1695
Published: December 25, 1969
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Examinations were made on tertiary bases contained in Formosan Stephania sasakii HAYATA, and pronuciferine (VII), roemerine (IX), nuciferine (VIII) (a non-phenolic base), and tuduranine (X) (a phenolic base) were isolated and identified besides the known cepharanthine (I), crebanine (II), phanostenine (IV), and berbamine (III). Three new bases, aknadinine, base VI, and base XIII were also isolated.
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TOSHIO ANMO, MASAHARU NARITOMI, MASAMICHI ASANO, HAJIME SUZUKI, NOBUKO ...
1969 Volume 89 Issue 12 Pages
1696-1699
Published: December 25, 1969
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Ethoxybenzamide is commonly used as an antipyretic and analgesic agent. Capping occurs to pure ethoxybenzamide tablets when compressed with high pressure. This phenomenon was examined by measuring the variation in the "stress relaxation rate constant" of compressed powder and that of the "momentary rate of recovery in resiliency of the tablet" in relation to the increased pressure. As a consequence, it was considered that the tendency of the tablet to recover resilience with increased pressure was a potential factor in the phenomenon of capping, which is considered to be caused directly by the destruction, at the second "packing state, " of combination of the powder particles completed at the first "structure fixed state."
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HIROYUKI SHINKAI, ICHIRO TANAKA
1969 Volume 89 Issue 12 Pages
1700-1703
Published: December 25, 1969
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Accumulation of hydrocortisone [4-
14C] acetate into the epidermis and its release from the corium into saline were examined by the in vitro method described previously. The skin used was epidermis separated from a full-thickness of the skin excised from human or guinea pig abdomen. The results of examination showed that the rate of release of hydrocortisone [4-
14C] acetate from the liquid vehicles to the epidermis was equal to the rate of its release to the full-thickness skin, and radioactivity was not detected in the saline, as reported ealier. However, when the corium, removed of epidermis, was used, release of labeled hydrocortisone acetate from liquid paraffin into saline through the corium was remarkably increased, and the amount of labeled hydrocortisone acetate in saline increased with lapse of time. When other vehicles were used, such as propylene glycol-water (30 : 70) or HS-12-P (Iauricdiethanolamide) -water (10 : 90), the release of labeled hydrocortisone acetate into saline was not detected. Therefore, release of hydrocortisone [4-
14C] acetate from liquid vehicle into saline through the corium dose not always increased with removal of the epidermis.
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SADAO BABA, SHOZABURO OGIYA
1969 Volume 89 Issue 12 Pages
1704-1711
Published: December 25, 1969
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The following investigations were carried out on : 1. The yield of dinitrophenyl derivatives of aliphatic amines in human urine and their extraction rate from the reaction mixture using various solvents. 2. The thin-layer chromatographic identification of aliphatic amines in urine of patients after dinitrophenylation. 3. The separatory estimation of ethanolamine, methylamine and dimethylamine in urine of patients by isolating their dinitrophenyl derivatives by ion exchange chromatography and reversed phase chromatography. 4. The gas chromatography of dinitrophenyl derivatives of aliphatic amines in human urine with SE-30 or OV-17 as liquid phase.
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SADAO BABA
1969 Volume 89 Issue 12 Pages
1712-1714
Published: December 25, 1969
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The occurrence of three new aliphatic amines in human urine was definitely proved. A satisfactory analytical procedure was established by extracting the amine distillate derived from a large quantity of urine (100-200 ml) with chloroform and by removing a great part of ammonia and methylamine. Isobutylamine and n-butylamine were identified by analyzing the extract in the amino acid analyzer. Each fraction containing isobutylamine or n-butylamine was collected, dinitrophenylated and then submitted to gas chromatography to provide further identification of isobutylamine and n-butylamine as their DNP-derivatives. Moreover, n-hexylamine was evidently identified by thin-layer and gas chromatography.
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TETSUZO KATO, YUKIO KUBOTA
1969 Volume 89 Issue 12 Pages
1715-1718
Published: December 25, 1969
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Reaction of diketene with urethan and acid amide was examined. Heating of urethan with excess of diketene results in the formation of N-acetoacetylurethan (III) and N-ethoxycarbonyl-2, 6-dimethyl-4-oxo-4H-pyran-3-carboxamide (IV). IV is also obtained by refluxing III and diketene in benzene, in the presence of triethylamine. Acetamide and benzamide react with diketene in acetic acid to form respectively N-acetoacetyl-acetamide (VI : R=CH
3) and N-acetoacetylbenzamide (VI : R=C
6H
5). Under the same condition, formamide and diketene form 3-acetyl-6-methyl-2, 4-pyridinedione (V) but the corresponding products were not isolated in the reaction with other acid amides.
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KATSUAKI MORISAKA, YASUO NAKAMOTO
1969 Volume 89 Issue 12 Pages
1718-1723
Published: December 25, 1969
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It was clarified through animal experiments with rats that absorption of salicylic acid series compounds, such as aspirin, through the digestive tract was accelerated by the presence of an additive of taurine-like or related compounds such as glycine, glycine ethyl ester, sarcosine, and l-, d-, and β-typg alanines. Distribution coefficient of aspirin and such compounds was found to remain unchanged by the presence of these additives, and it was assumed that the action of these additives was specific to the membraneous surface of the digestive tract. Such effect of the additives was also indicated in the measurement of urinary excretion of salicylic acid series compounds after their oral administration in rats, and approximate correlation between was confirmed.
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ISAMU MURAKOSHI, YING MEI YUE, MASASI GOO, JOJU HAGINIWA
1969 Volume 89 Issue 12 Pages
1723-1725
Published: December 25, 1969
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It was found that (-)-trans-4-hydroxypipecolic acid (I) is present in young leaves of acacia species in a high concentration (as shown in Table I) and that the young leaves of Acacia mollissima before flowering time are useful as a natural source of I. The structure of I was determined by chemical reactions shown in Chart I.
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ITSUHIKO MORI, MASAKI SHINOGI, NORIKO TSUNEMATSU
1969 Volume 89 Issue 12 Pages
1726-1728
Published: December 25, 1969
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Rapid separation of some 20 inorganic anions was examined using a small-scale electrophoretic apparatus (16×10×5 cm) with different supporting substances carriers such as thin-layer Chromatosheet (Eastman Kodak Co., silicagel, 6.5×2 cm) and filter paper (Toyo Roshi No. 51, 6.5×2 cm). The electrophoresis was carried out for 5 min with 300 V/6.5 cm, using 0.05N sodium carbonate as the electrolytic solution and the sample was spotted at 1 cm from the strip end (cathode side). These results were shown as relative mobility of inorganic anions against IO
3-. Electropherograms on the Chromatosheet were compact and clear, except for I
-, IO
3-, and IO
4-, which separated only on the filter paper.
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SEIGO FUKUSHIMA, YUKIO AKAHORI, TOMOYUKI TSUNEYA
1969 Volume 89 Issue 12 Pages
1729-1731
Published: December 25, 1969
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Numerous compounds have been identified in the essential oil of green tea but in the present series of experiments, several unknown components were isolated from the high-boiling fraction of the essential oil of green tea by the use of gas, column, and thin-layer chromatography. Two of these components were identified as dihydroactinidiolide and p-vinylphenol, obtained earlier from the Actinidia polygama and black tea. The identification was based on infrared, ultraviolet, mass, and nuclear magnetic resonance spectral data.
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HIROSHI ISAKA
1969 Volume 89 Issue 12 Pages
1732-1735
Published: December 25, 1969
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Ninety-eight strains of soil microorganisms were isolated from the soil of the field cultivating poppy (Papaverium somniferium L). One of these soil microorgnisms, Cladosporium cladosporioides (Fres) de Vries, decomposed 70% of morphine contained in the potato medium, at 25° for eight days. Two products were isolated and identified to be normorphine and pseudomorphine. The degradation mechanism of morphine by this microorganism is also discussed.
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MASAITI YASUE, YOSISIGE KATO, MAMORU SUGIMOTO, JINSAKU SAKAKIBARA
1969 Volume 89 Issue 12 Pages
1736-1739
Published: December 25, 1969
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The benzene-soluble part of the methanol extract of the red shoots of Lyonia ovalifolia var. elliptica was treated by alumina column chromatography and following substances were isolated : Nonacosane, 2-nonacosanone, 1-tetracosanol, β-sitosterol, taraxerol, betulin 3-acetate, oleanolic acid, and ursolic acid. The crude nonacosane was examined through gas chromatography and it was found to be contaminated with a small amount of pentacosane, hexacosane, heptacosane, octacosane, triacontane, and hentriacontane. Betulin 3-acetate, mp 263°, was newly found as one of the natural products, and identified with the partially hydrolized product of betulin diacetate. The isomeric substance, betulin 28-acetate, mp 218.5°, a new compound, was synthesized by partial acetylation of betulin, which was obtained from the bark of Betula platyphylla var. japonica.
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MARI SAKUMA, YOSHISHIGE SATO
1969 Volume 89 Issue 12 Pages
1740-1742
Published: December 25, 1969
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MAMORU SUGIURA, KUNIO KANO, KAZUAKI KIMURA, SEIZI HIRAKU, HIROYUKI ONO ...
1969 Volume 89 Issue 12 Pages
1741-1742
Published: December 25, 1969
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