Chemical and Pharmaceutical Bulletin

Saponins of Timo ( ?? ?? : Anemarrhenae Rhizoma). II. Structure of Timosaponin A-III.

Toshio KAWASAKI, Tatsuo Yamauchi

1963 Volume 11 Issue 10 Pages 1221-1224
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1221

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Timosaponin A-III, the crystalline steroid saponin isolated from a commercial crude drug Timo (Anemarrhenae Rhizoma), has been shown to be sarsasapogenin O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside. The biose which forms the sugar moiety of timosaponin A-III was obtained as crystals from the partial hydrolyzate of the saponin and named timobiose.

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Terniflorin, a New Flavonoid Compound in Flowers of Clematis terniflora A. P. de CANDOLLE var. robusta TAMURA.

Masakazu Aritomi

1963 Volume 11 Issue 10 Pages 1225-1228
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1225

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The presence of a new flavonoid glycoside, terniflorin, C₃₀H₂₆O₁₂·H₂O, m. p. 266∼267°(decomp.), is demonstrated in flowers of Clematis terniflora A. P. de CANDOLLE var. robusta TAMURA (Ranunculaceae). On basis of composition, hydrolysis, and ultraviolet and infrared spectra, terniflorin is identified as apigenin-7-(p-coumaroyl)-β-D-glucoside.

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Usnic Acid. V. Some Decomposition Reaction of Methyl and Methyldihydrousnic Acids. The Revised Structure for Usnic Acid Isomethoxide.

Kotaro Takahashi, Yoshie Honda, Shuichi Miyashita

1963 Volume 11 Issue 10 Pages 1229-1235
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1229

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1) The ozonolysis of methyl- and methyldihydrousnic acid was discussed. 2) The structure of the formolysis product of methylusnic acid was elucidated as being II. 3) The structure of monoacetylusnic acid isomethoxide was reinvestigated and established as being V.

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Aldol-Condensation of Corticoids with Formaldehyde. Syntheses of 21-Hydroxy-methyl-corticoids and 21-Methyl-11β, 17α-dihydroxy-pregna-1, 4-diene-3, 20, 21-trione 17-Acetate.

Shunsaku Noguchi, Katsura Morita

1963 Volume 11 Issue 10 Pages 1235-1240
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1235

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21-Hydroxymethylprednisolone (II), 21-hydroxymethylhydrocortisone (VIII) and 21, 21-bis (hydroxymethyl) prednisolone (VI) were synthesized by the aldol condensation of the parent steroids with formaldehyde. When 21-hydroxymethylprednisolone diacetate (III) was passed through a column of aluminum oxide, a light yellow compound was obtained and the structure was assigned to 21-methyl-11β, 17α-dihydroxypregna-1, 4-diene-3, 20, 21-trione 17-acetate (X). The mechanism of the formation of X from III was also proposed.

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Kinetic Study of Hydrolysis of Thioacetazone and its Related Compounds.

Yutaka Asahi

1963 Volume 11 Issue 10 Pages 1241-1246
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1241

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The rate constant of hydrolysis (k₁) of thioacetazone and that of recombination (k₂) of its components, the aldehyde and the amine, were estimated by polarography and spectrophotometry. The relationships between the rate constant (k₁), acidity function and the concentration of buffer show that the reaction is a general acid and base catalysed reaction. The equilibrium constants K in strong and weak acid solutions are evaluated to be 8·10^-4 and 1·10^-5, respectively. Thermodynamic data are given as follows : &lrtri;H^* 15.4kcal. /mol., &lrtri;S^*-18.7 cal./deg. &lrtri;H 3.7 kcal./mol., &lrtri;S-2 cal./deg. for the hydrolysis, &lrtri;H^* 11.7kcal./mol., &lrtri;S^*-16.7 cal./deg. for the recombination. The sequence of stability for acid is S-methylthioacetazone > benzaldehyde thiosemicarbazone > thioacetazone > p-acetamidobenzaldehyde semicarbazone. The rate of deacetylation of p-acetamido-benzaldehyde is as small as one hundredth that of the hydrolysis of thioacetazone.

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Antiviral Effect and Syntheses of 4-Amino-6-alkylamino-s-triazine-2-carboxylic Acid Derivatives. Researches on Chemotherapeutic Drugs against Viruses. XXXVI.

Mitsuru Furukawa, Shigeshi Toyoshima, Takeo Ueda

1963 Volume 11 Issue 10 Pages 1247-1250
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1247

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New compounds of 4-amino-6-alkylamino-s-triazine-2-carboxylic acid and N-amidino-4-amino-6-alkylamino-s-triazine-2-carboxamide were synthesized from 1-alkyl-3-(4, 5-dioxo-2-imidazolidinylidene) guanidine prepared by condensation of 1-alkylbiguanide with diethyl oxalate and examined as to their antiviral effect. Among these compounds, N-amidino-4, 6-diamino-s-triazine-2-carboxamide was found to possess an inhibitory effect on polio virus.

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Studies on Decomposition and Stabilization of Drugs in Solution. XIV. Stabilization of Methantheline Bromide and Choline Derivatives in Aqueous Solution by Surface-active Agents.

Hisashi Nogami, Shoji Awazu, Motoharu Iwatsuru

1963 Volume 11 Issue 10 Pages 1251-1255
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1251

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1) The decomposition of methantheline bromide was repressed by the addition of alkyl sulfate (anionic surfactant). The longer the alkyl chain length of alkyl sulfate, the greater the effect was. 2) The addition of surfactant enhanced the stability of cholinesters, and the effect increased with the acyl chain length.

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Studies on polyamines. II. Metabolism of Spermidine and spermine by Amine Oxidase in Beef Serum.

Tsutomu Unemoto

1963 Volume 11 Issue 10 Pages 1255-1264
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1255

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The oxidation of spermidine and spermine by the partially purified amine oxidase of beef serum was examined. Under the present conditions, when spermidine was used as substrate, 1 mole each of ammonia and hydrogen peroxide were formed consuming 1 mole of oxygen. By contrast, in the case of spermine 2 moles each of ammonia and hydrogen peroxide were formed consuming 2 moles of oxygen. At the end of reaction, amino groups assayed in the reaction products of the two polyamines were found to be 2 moles equivalent of primary amino groups per 1 mole of the substrates. Another finding was that putrescine was identified and determined in the end products. The presence of an unidentified amino aldehyde in the end products was suggested using the resorcinol reagent which yield a fluorescent compound with the amino aldehyde. From these observations, possible pathways of the oxidative degradation of spermidine and spermine by the said enzyme were discussed.

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Steroid Studies. XLIII. An Aromatization Reaction of a Cross Conjugated Dienone System with Zinc. (8).

Kyosuke Tsuda, Shigeo Nozoe, Kazuhiko Ohata

1963 Volume 11 Issue 10 Pages 1265-1270
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1265

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Using Methyl 2, 4-Dibromo-3, 12-dioxocholanate (III) as a starting material Methyl 3, 12-dioxochola-1, 4-dienate (IV) and methyl 3, 12-dioxochola-4, 6-dienate (VI) were prepared. Methyl 3, 12-dioxochola-1, 4, 9 (11)-trienate (IX) was obtained by bromination and dehydrobromination of methyl 3, 12-dioxocholanate (II) or dehydrogenation with selenium dioxide in tert-amyl alcohol of methyl 3, 12-dioxochol-9 (11)-enate (VIII). Aromatization of IX with zinc in pyridine, dimethylformamide, or ethanol afforded 3-hydroxy-12-oxo-19-norchola-1, 3, 5 (10), 9 (11)-tetraenic acid methyl ester (X). Hydrogenation, followed by chromium-trioxide-oxidation and Huang-Minlon reduction or Huang-Minlon reduction and then hydrogenation of X afforded 3-hydroxy-19-norchola-1, 3, 5 (10)-trienic acid methyl ester (XVIII).

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Stereo-chemistry of Steroids Containing Aromatic A-Ring. III. Hydrogenation of 11β-Hydroxy-&lrtri;⁸-dehydroestrone.

Kyosuke Tsuda, Shigeo Nozoe, Yutaka Okada

1963 Volume 11 Issue 10 Pages 1271-1275
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1271

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Reduction of the &lrtri;⁸-double bond in 3, 11β-dihydroxyestra-1, 3, 5 (10), 8-tetraen-17-one (II) was carried out. Catalytic hydrogenation of II occurred from rear side and afforded the compound having 8α, 9α-configuration, which was assigned in consideration of its resistance to acetylation and by leading to 9 (11)-dehydro-8-isoestrone methyl ether, whereas reduction of II with lithium in liquid ammonia afforded estradiol.

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Untersuchungen uber Steroide. XLVI. Uber die vier Isomere des zum Progesteron gehorigen 14, 15-Diols.

Hiroko Hasegawa, Yoshihiro Sato, Kyosuke Tsuda

1963 Volume 11 Issue 10 Pages 1275-1282
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1275

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Es wird uber die Synthese sowie die Konfigurationsbestimmung der vier Isomeren des zum Progesteron gehorigen 14, 15-Diols geschrieben.

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Studies on the Drugs for Peptic Ulcer. Pharmacological Studies on the Effects of Synthetic Antispasmodics mixed with Antacid.

Keijiro Takagi, Yutaka Kasuya, Kazuo Watanabe

1963 Volume 11 Issue 10 Pages 1282-1290
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1282

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The stability of some antispasmodics mixed with antacid was examined, and the effect of combined administration of these two drugs was studied by experimental peptic ulcer. The antispasmodics used seemed not to be decomposed when they were mixed with synthetic aluminum silicate. From the resuls of the assay with mydriasis of mice eyes, is was shown that the antispasmodics by the antacid reduced the abesorption of these drugs from gastroin-tetinal tract, but practically this will not affect their pharmacological activity seriously, because gastric juice will facilitate the dissociation of the drug from antacid. To examine the effects of the drugs on peptic ulcer, Shay rats were used. Ulcer formation on Shay rat's stomach was treated as the duantal response, and ED 50 of some drugs was calculated. By this method it was shown that synergism of antispasmodics with antacid was of the type of potentiation.

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Infrared Spectra of Thiourea and its Inclusion Compounds. IV. Investigations on Aggregational States of Some Cyclohexane Derivatives.

Masao Nishikawa

1963 Volume 11 Issue 10 Pages 1290-1298
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1290

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Aggregational states of cyclohexanecarboxylic acid, cyclohexanol, cyclohexanemethanol and trans-2-chlorocyclohexanol, when they were enclosed in thiourea channels were investigated by the method described in the previous papers of this series. In the case of cyclohexanecarboxylic acid, the dimer structure similar to that found in the liquid states or in solution in less polar solvents was detected. The conformation of this acid could not be determined by this technique but the equatorial form, expected from stereochemical consideration, was ascertained by some other experimental evidences. Two OH stretching bands were found in cyclohexanol-thiourea adduct, one arising from the free hydroxyl group and the other from the dimer. The dimer formation seemed to stabilize the equatorial conformation so that the tendency of increasing the axial conformation in thiourea channels was not observed in this case. The intramolecular hydrogen bond of trans-2-chlorocyclohexanol was found to persist even in the thiourea adduct.

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Cularine and Related Compounds. V. Investigation of the Ullmann Reaction Products of Methyl (2-Bromo-4, 5-dimethoxyphenyl) acetate with Phenolic Compounds, and an Approach to the Total Synthesis of Cularine.

Tetsuji Kametani, Keiichiro Fukumoto, Shiroshi Shibuya, Takuo Nakano

1963 Volume 11 Issue 10 Pages 1299-1305
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1299

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Preparation of the cyclic amide (II) as the key intermediate for the synthesis of cularine was elaborated. Bischler-Napieralski cyclization of this amide appeared to proceed as expected to give the desired isoquinoline derivative, didehydronorcularine, in a crude state, which, however, was readily oxidized and turned during purification into the corresponding ketone derivative, which was characterized as its picrate.

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Untersuchung uber Alkaloide von Papaveraceen. VI. Alkaloide von Corydalis incisa. (5). Uber die Struktur des Corynolins. (1).

Narao Takao

1963 Volume 11 Issue 10 Pages 1306-1312
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1306

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Es wird die Struktur des Corynolins, C₂₁H₂₁O₅N, das Hauptalkaloid von Corydalis incisa beschrieben. Bei der KMnO₄-Oxydation liefert es ein Produkt mit 6-gliedrigem Laktam. Das des-N-Produkt, C₂₀H₂₀O₄, wurde durch zweimaligen Emde-Abbau aus Desoxydihydrocorynolin, sowie Desoxycorynolin abgeleitet. Durch Destillation des Corynolins mit Zinkstaub entsteht Benzo [c] phenanthridin. Diese Tatsachen zeigen, dass das Corynolin zu der Benzo [c] phenanthridin-Gruppe gehort. Ausserdem wird Hydrastsaure bei der KMnO₄-Oxydation des Desoxycorynolins erhalten. Die Infrarot Spektren und Protonresonanz Spektren von einigen Derivaten weisen auf die Vermutete Struktur des Corynolins.

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Untersuchung uber Alkaloide von Papaveraceen. VII. Alkaloide von Corydalis incisa. (6). Uber die Struktur des Corynolins. (2).

Narao Takao

1963 Volume 11 Issue 10 Pages 1312-1316
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1312

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Die Stellungen ber beiden Methylendioxygruppe des Corynolins werden dadurch bestimmt, dass Dihydrosanguinarin aus Desoxycorynolin abgeleitet wurde. Ausserdem wurde die Stellung der quartaren Methylgruppe dadurch bestimmt, dass 2-Methyl-6, 7-methylendioxynaphthalin aus dem Des-N-Produkt von Desoxycorynolin, sowie Desoxy-dihydrocorynolin durch Pyrolyse-Reaktion erhalten wurde. Die Stellung der alkoholischen Hydroxygruppe und die Konstellation des Corynolins werden aus den herangezogenen Infrarot Spektren diskutiert.

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Studies on the Constituents of Umbelliferae Plants. VIII. Distribution of Alkylphthalides in Umbelliferae Plants.

Hiroshi Mitsuhashi, Toshio Muramatsu, Ukon Nagai, Toshio Nakano, Koji ...

1963 Volume 11 Issue 10 Pages 1317-1319
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1317

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The distribution of alkylphthalides in the roots of Ligusticum acutilobum SIEB. et Zucc., Ligusticum acutiloba var. sugiyamae HIKINO, Cnidium officinale MAKINO, Apium graveolens L., Levisticum officinale KOCH, and Angelica anomale LALIEMENT have been surveyed. From the roots of Angelica anomale no alkylphthalides could be found. The results are summarized in Table II.

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Untersuchung uber die Bestandteile von Gleditschia horrida MAKINO. Isolierung von Triacanthin.

Hiroshi Morimoto, Haruji Oshio

1963 Volume 11 Issue 10 Pages 1320-1322
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1320

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In Gleditschia horrida MAKINO (〓 ?? ) wurde ein Alkaloid, das Triacanthin (I), gefunden. Die Ausbeute betrug, bezogen auf die getrockneten Ausgangsmaterialien : 0.01% aus Blattern, 0.0001% aus der Rinde und 0.0005% aus luftgetrockneten Fruchten (der auf dem Markt verkauften Drogen).

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Cularine and Related Compounds. IV. The Oximination and Reduction of 2, 3, 6-Trimethoxydibenzo [b, f] oxepin-10 (11H) -one.

Tetsuji Kametani, Keiichiro Fukumoto

1963 Volume 11 Issue 10 Pages 1322-1325
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1322

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Oximination of 2, 3, 6-trimethoxydibenzo [b, f] oxepin-10 (11H)-one (II) yielded three compounds, among which mono- and di-oximes were elucidated. Catalytic hydrogenation of the ketone (II) in the presence of Adams catalyst in acetic acid gave the carbinol (VII), m. p. 167°, accompanied by a small amount of the starting material. When the carbinol (VII) was heated with p-toluenesulfonic acid at 120∼140° for 10 minutes, VII was dehydrated and yielded yellow needles (VIII), m. p. 115∼116.5°.

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New Inter-relationship of Abietic Acid and Agathic Acid

Akira Tahara, Osamu Hoshino, Yasuhiko Hamazaki

1963 Volume 11 Issue 10 Pages 1328-1331
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1328

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Reactions of Quinoline 1-Oxide with Enamines of Cyclohexanone

Masatomo Hamana, Hiroshi Noda

1963 Volume 11 Issue 10 Pages 1331-1333
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1331

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On the Structure of Metaplexigenin and Benzoylramanone

Hiroshi Mitsuhashi, Taro Nomura

1963 Volume 11 Issue 10 Pages 1333-1336
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1333

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On the Alkaloid of Fritillaria verticillate WILD. var. Thunbergii BAKER. II. The Structure of Verticine.

Sho Ito, Michiharu Kato, Koichi Shibata, Tetsuo Nozoe

1963 Volume 11 Issue 10 Pages 1337-1340
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1337

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Hydroxylation of Digitoxigenin Derivatives by Absidia orchidis

Tamotsu Okumura, Yoshio Nozaki, Daisuke Satoh

1963 Volume 11 Issue 10 Pages 1340-1342
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1340

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Choline in Panax ginseng C. A. MEYER

Kichitaro Takatori, Terushige Kato, Shingo Asano, Masawaka Ozaki, Tosh ...

1963 Volume 11 Issue 10 Pages 1342-1343
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1342

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Structure of Helicobasidin, a Novel Benzoquinone from Helicobasidium mompa TANAKA

Shinsaku Natori, Hideko Ogawa, Kazutaka Yamaguchi, Hidejiro Nishikawa

1963 Volume 11 Issue 10 Pages 1343-1345
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1343

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Relative Configuration of Sciadin, Dimethylsciadinonate. and Sciadinone, and Substitution of Oxygen in the Lactone Ring of Sciadin with Nitrogen

Chikara Kaneko, Takashi Tsuchiya, Masayuki Ishikawa

1963 Volume 11 Issue 10 Pages 1346-1349
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1346

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Syntheses of (+)-Isosophoramine and (-)-13-Alkylsubstituted Sophoramine from (+)-Matrine

Shigenobu Okuda, Hiromitsu Kamata, Kyosuke Tsuda

1963 Volume 11 Issue 10 Pages 1349-1351
Published: October 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1349

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