Chemical and Pharmaceutical Bulletin

Selectivity of Group VIII Metals for the Catalytic Hydrogenation and Hydrogenolysis of Phenol

HARUHIKO YAMAMOTO, TAKAO KWAN

1969 Volume 17 Issue 6 Pages 1081-1089
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1081

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The hydrogenation of phenol has been investigated over group VIII metals by a gas chromatographic pulse technique. Major products were found to be cyclohexanone and cyclohexanol, but benzene, cyclohexane and other hydrocarbons were also formed. The relative amount of cyclohexanol over cyclohexanone formed during the hydrogenation varied by a factor of about 100 depending on both catalyst and reaction temperature. This result was interpreted in terms of the relative catalytic activity of metals for the consecutive reaction : [chemical formula] The initial product due to the breaking of the carbon-oxygen bond was benzene rather than cyclohexane even when cyclohexanol or cyclohexanone was injected in the presence of hydrogen. This unusual result was briefly discussed.

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Studies on the Proton Magnetic Resonance Spectra in Aromatic Systems. IX. Calculation of π-Electron Charge Density Distribution of the Substituted Benzene and Naphthalene Derivatives and ω-Technique

YOSHIO SASAKI, MIYOKO SUZUKI

1969 Volume 17 Issue 6 Pages 1090-1095
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1090

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ρNMR-π-electron charge density estimated from the revised shielding parameter-showed appreciable disagreement with that from HMO calculation using Streitwieser's parameter especially at meta position. The ω-technique has been applied to settle this problem and parameters for above treatment have been arranged so as to reconcile with ρNAR. Above treatments have also been applied to 1-substituted-3, 4-dimethoxybenzene, 2-substituted- and 2-substituted-6-methoxynaphthalene series, and favorable results have been acknowledged.

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Azamorphinan and Related Compounds. II. Synthesis of 3-Methoxy-9-azamorphinan Derivatives : Studies on the Syntheses of Heterocyclic Compounds. CCCXIX

TETSUJI KAMETANI, KAZUO KIGASAWA, KIKUO WAKISAKA, NAGATOSHI WAGATSUMA

1969 Volume 17 Issue 6 Pages 1096-1103
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1096

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In order to examine an analgesic activity of azamorphinan derivatives, 3-methoxy-9-azamorphinan (XII) was synthesized as follows. Reduction of octahydrocinnoline derivatives (VIIIa and VIIIb), which were obtained by condensation of 2-(3-methoxyphenyl)-cyclohexanone-2-acetic acid (VI) with hydrazine or benzylhydrazine, with lithium aluminum hydride afforded the corresponding decahydrocinnoline derivatives (IXa and IXb). Pictet-Spengler reaction of IXb gave N-benzyl-3-methoxy-9-azamorphinan (XIV), but cyclization of IXa failed. Therefore, ring-closure of Xa, which was obtained by catalytic hydrogenation of VIIIa, with HOCH₂SO₃Na, followed by lithium aluminum hydride reduction of XI, afforded the compound (XII). This compound (XII) was also obtained by debenzylation of XIV. Furthermore, N-alkylation of XII at the N₁₇-position with methyl, acetyl, allyl, β-phenethyl and cyclopropylmethyl halides gave the corresponding compounds (I, XIII, XVI, XV, and XVII), respectively.

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Studies on the Proton Magnetic Resonance Spectra in Aromatic Systems. XI. Heteroaromatic Series. III. Discussions on the Coupling Constants of Substituted Pyridines

YOSHIO SASAKI, MIYOKO SUZUKI

1969 Volume 17 Issue 6 Pages 1104-1108
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1104

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The coupling constants of substituted pyridines have been discussed with respect to substituent constant σ_i and σ_π. And, for the estimations of coupling constants, empirical equations : J≒(Jⁱ+J^π)_ref.+Σ△Jⁱ (1) and J≒(Jⁱ+J^π)_ref.+Σ△ (2) showed reliabilities in numerous substituted pyridines.

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Studies on Absorption of Drugs. IV. Effects of Surface Active Agents on Intestinal Absorption of Drugs

MASARU AOKI, AKIRA KAMADA, NOBORU YATA, KOICHI KISHIMOTO, CHIEKO MUGIN ...

1969 Volume 17 Issue 6 Pages 1109-1114
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1109

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Effects of surface active agents (ionic and nonionic) on intestinal absorption of drugs were studied on three method, i. e., (1) circulation with surfactants, (2) preperfusion with surfactant solutions, followed by circulation of drug solution free from surfactants, and (3) feeding experiments of surfactants solutions, followed by circulation of drug solution. Effects of surfactants were reviewed from two points. One is the effect due to interaction of drugs with surfactants and the other effect due to degeneration of the intestinal mucosa. It is concluded that the absorption of ionized species of drugs were more decreased than that of unionized species in degenerated intestinal mucosa, except for ionic interaction between drugs and surfactants.

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Organic Photochemistry. I. 3, 4-Dihydroisoquinolines from Tetrahydroisoquinoline N-Tosylates

BUNSUKE UMEZAWA, OSAMU HOSHINO, SHOHEI SAWAKI

1969 Volume 17 Issue 6 Pages 1115-1119
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1115

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Photolysis of 1-substituted 6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline N-tosylates (Va-d) with high pressure mercury lamps (100W and 400W) in neutral (EtOH) or basic [80% (v/v) EtOH containing Na₂CO₃] media was examined. Under these conditions, 3, 4-dihydro compounds (VIIa-d) were formed in moderate yields.

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Organic Photochemistry. II. Tetrahydroisoquinolines from Their N-Tosylates

BUNSUKE UMEZAWA, OSAMU HOSHINO, SHOHEI SAWAKI

1969 Volume 17 Issue 6 Pages 1120-1122
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1120

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Photolysis (high pressure mercury lamps, 100W and 400W) of 1-substituted 6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline N-tosylates (Ia-d) in a basic medium [80% (v/v) EtOH-Na₂CO₃] in the presence of NaBH₄ was carried out to give the corresponding amines (IIIa-d) in good yields.

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Synthesis of β-D-Galactofuranosides and Their Behavior toward β-Galactosidase

KAZUO YOSHIDA, NOBUKO IINO, TAKAKO KAMATA, KEITARO KATO

1969 Volume 17 Issue 6 Pages 1123-1127
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1123

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After ethanolysis of galactose with Dowex-50 as catalyst, ethyl β-D-galactofuranoside, ethyl β-D-galactopyranoside and ethyl α-D-galactopyranoside were isolated by cellulose column chromatography. m-Tolyl and guaiacol β-D-galactofuranoside were also prepared. Ethyl, phenyl, m-tolyl and guaiacol β-D-galactofuranoside were hydrolyzed by almond emulsin β-galactosidase, but not hydrolyzed by E. coli K 12 and bovine liver β-galactosidase. The kinetics of the hydrolysis of β-D-galactofuranoside by almond emulsin β-galactosidase were investigated. The pH optimum of the β-D-galactofuranoside is pH 5.0 in phosphate-citrate buffer. The Michaelis constant of phenyl β-D-galactofuranoside is 5.6×10^-2M. The kinetics of the hydrolysis of corresponding β-D-galactopyranoside were also investigated. The pH optimum is pH 4.5-5.0 for almond emulsin β-galactosidase, pH 5.5 for bovine liver β-galactosidase and pH 7.0-7.5 for E. coli K 12 β-galactosidase. The Michaelis constant of phenyl β-D-galactopyranoside for almond emulsin β-galactosidase is 3.2×10^-3M. The Michaelis constant of phenyl β-D-galactopyranoside is smaller than that of corresponding furanoside.

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Synthesis of 1-N-Oxides of Adenosine and 2-Alkyladenosine and Inosine 1-N-Oxide 5'-Phosphate

AKIHIRO YAMAZAKI, IZUMI KUMASHIRO, TADAO TAKENISHI

1969 Volume 17 Issue 6 Pages 1128-1133
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1128

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Reaction of 5-amino-4-cyano-1-(2', 3'-O-isopropylidene-β-D-ribofuranosyl) imidazole (I) with ethyl orthoformate followed by treatment with hydroxylamine afforded 2', 3'-O-isopropylideneadenosine 1-N-oxide (IVa), from which adenosine 1-N-oxide (Va) was obtained by removal of the isopropylidene group. Similarly, 2-methyladenosine 1-N-oxide (Vb) and 2-ethyladenosine 1-N-oxide (Vc) were prepared. When O-methylhydroxylamine was substituted for hydroxylamine in the ring closure reaction of IIa, 9-(2', 3'-O-isopropylidene-β-D-ribofuranosyl)-6-methoxyaminopurine (VIII) was obtained by ring opening and subsequent recyclization of the 1-methoxyadenosine derivative (VII). Deamination of IVa with nitrous acid resulted in the formation of inosine 1-N-oxide (X). Its isopropylidene derivative (XI) was phosphorylated with phosphoryl chloride to give, after acidic treatment, inosine 1-N-oxide 5'-phosphate (XII), whose flavoring activity was examined.

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Studies on Hard Gelatin Capsules. I. Water Vapor Transfer between Capsules and Powders

KOJI ITO, SHINICHIRO KAGA, YASUMITSU TAKEYA

1969 Volume 17 Issue 6 Pages 1134-1137
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1134

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The adsorption and desorption of water vapor on capsules, microcrystalline cellulose, corn and potato starches were observed and the water vapor transfer between capsules and the powders in the closed container was examined. Experimental equilibrium water contents and relative humidities after water vapor transfer and estimated values calculated from the sorption isotherms of these substances were in good agreement with each other.

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Studies on Hard Gelatin Capsules. II. The Capsule Filling on Powders and Effects of Glidant by Ring Filling Method-Machine

KOJI ITO, MASAHIRO HITOMI, SHINICHIRO KAGA, YASUMITSU TAKEYA

1969 Volume 17 Issue 6 Pages 1138-1145
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1138

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The filling characteristics of capsules were studied on cornstarch and lactose with and without Aerosil as glidant, using industrially semiautomatic-ring filling method-machine with the flat and the screw auger. On powders without Aerosil, the coefficient of variation of the dose showed that the filling by the screw auger was more accurate than that by the flat one. Deviations of the dose containing Aerosil became smaller and showed maximum effect between 0.1-2% Aerosil contents. The maximum filled weights were observed at 0.1-0.5% Aerosil contents but on lactose filling by the screw auger the filled weight decreased with Aerosil contents. The filled weight variation was compared with U. S. P. requirements. As the approach to reviewing the filling properties, two usual packing equations were applied for the relation between the filled weight and velocity of the ring.

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Reactivities of Radiation-protective Aminoalkylisothiuronium Salts. V. Calculation of the Extent of the Transguanylation from pH Drop in the Aqueous Solution of 2-Aminoethyl- and 3-Aminopropyl-isothiuronium Salts

AKIRA HANAKI

1969 Volume 17 Issue 6 Pages 1146-1152
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1146

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2-Aminoethylisothiuronium (AET) and 3-aminopropylisothiuronium (APT) salts undergo, in the presence of alkali, the rapid transguanylation accompanying with the continuous pH drop. Since the liberation of hydrogen ion was resulted undoubtedly from the transguanylation, the calculation of the extent of this transformation was attempted from the pH drop. The extent of the transguanylation, abbreviated as T, was expressed briefly as follows. p (1-T)=ΔpH This equation can be used in the case of APT, which undergoes the transguanylation alone. AET is cyclized along with the transguanylation, and the cyclization product, 2-aminothiazoline, is able to associate with free hydrogen ion. Therefore, the pH drop observed as a result of a certain extent of the transguanylation is decreased according to the increasing extents of the cyclization. The calculation in the case of AET was performed by using the following equation ; T=1-(1-a) K/a [H⁺]+(K-K")C/(K"+[H⁺])a where C, a, K and K"represent the extent of the cyclization determined experimentally, the equivalent of alkali added, the ionization constants of the transguanylation and the cyclization products, respectively.

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Synthesis of Benzimidazoles and Its Related Compounds. Synthesis of Benzimidazoles and 7-Substituted 1 (3) H-Imidazo [4, 5-f] quinolines

SABURO ISHIWATA, YOUICHI SHIOKAWA

1969 Volume 17 Issue 6 Pages 1153-1157
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1153

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4 (7)- or 5 (6)-Substituted 2-methylbenzimidazole derivatives (III) were obtained by catalytic hydrogenation of the corresponding 2-chloro-2'-nitroacetanilide (II) in a good yield. Further, a mixture of 5 (6)-methoxy-2-methyl-6 (5)-nitrobenzimidazole (IVc) and its 4 (7)-nitro isomer was obtained by the reaction of 5 (6)-methoxy-2-methylbenzimidazole (IIIc) with fuming nitric acid. Similarly, nitration of 2, 4 (7)-dimethylbenzimidazole (IIId) gave 2, 4 (7)-dimethyl-5 (6)-nitrobenzimidazole (IVd). The title compounds were obtained by the reactions shown in Chart 1.

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Studies on Morphine Derivatives. II. The Stereochemistry of the By-products in the Synthesis of 3-Methoxy-N-methylmorphinan

KAZUHIKO KAWASAKI, HIROMU MATSUMURA

1969 Volume 17 Issue 6 Pages 1158-1174
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1158

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The absolute configuration of (+)-10-hydroxy-1, 2, 3, 3a, 11b, 11c-hexahydroaporphine A and B (IVa and IVb), which were obtained as by-products on the cyclization of (+)-1-(4-methoxybenzyl)-2-methyl-1, 2, 3, 4, 5, 6, 7, 8-octahydroisoquinoline (I) to (+)-3-hydroxy-N-methylmorphinan (II) was established by degradation reaction to 3-alkyl cyclohexane-1, 2-dicarboxylic acids.

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Biochemical Studies on the Metabolism of Penicillium islandicum Sopp. II. Acetyl-CoA Carboxylase and Related Enzymes

YOSHIO UENO, TAKASHI TATSUNO

1969 Volume 17 Issue 6 Pages 1175-1182
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1175

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In order to disclose the enzymatic mechanism of the biosynthesis of anthraquinoid pigment of P. islandicum Sopp. an investigation was made on acetyl-CoA carboxylase and related enzymes with the following results. 1) With the stationary culture of P. islandicum Sopp. on Czapek medium, luteoskyrin and other quinoid pigments were produced in the late stage of fungal growth ; 2) Sodium arsenate, monoiodoacetate, 2, 4-dinitrophenol and monofluoroacetate inhibited the fungal growth and the pigment formation, and malonate stimulated the latter. 3) With the crude and partially purified enzyme preparations of mechanically-disruptured mycelium, the formation of malonyl-CoA, the first intermediate of anthraquinoid pigments, was demonstrated. 4) With the crude extract of the mycelium, malonyl-CoA was decarboxylated to yield acetyl-CoA. 5) With the supernatant of the crude extract, the carboxyl group of pyruvate was exchanged with ¹⁴CO₂. 6) In the early phase of the fungal growth, activities of aldolase and citrate synthetase were relatively high, and in the later stage activities of malate dehydrogenase and glucose-6-phosphate dehydrogenase were remarkably high.

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Biochemical Studies on Glucuronides. IV. Cleavage of p-Nitrophenyl Glucuronide by Ultraviolet Light Irradiation at Alkaline Medium

YASUHIRO YAMANE, MOTOICHI MIYAZAKI, KAZUO SAKAI, CHIKATAKA AJIKI, LIMZ ...

1969 Volume 17 Issue 6 Pages 1183-1187
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1183

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Ultraviolet light irradiation was applied to the study of nonenzymatic dissociation of p-nitrophenyl glucuronide (PNG) at low temperature in acidic, neutral and alkaline conditions. The cleavage of PNG was negligible at acidic or neutral medium, but it was almost quantitative and the production of p-nitrophenol (PN) was over 90% at alkaline condition. Nevertheless, the recovery of sugar moiety of PNG was very low, and glucuronic and glucaric acids were formed only 5-8%, and under 1%, respectively.

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Studies on Nucleosides and Nucleotides. XII. Syntheses of 3'-Amino-3'-deoxypentofuranosylcytosines

MIYOSHI HIRATA, TOSHIHIKO KOBAYASHI, TAKEO NAITO

1969 Volume 17 Issue 6 Pages 1188-1193
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1188

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1-(3'-Amino-3'-deoxy-β-D-arabinofuranosyl) cytosine derivatives (IX), (X), and (XI) were prepared from 1-(3'-azido-3'-deoxy-β-D-arabinofuranosyl) uracil (III) via 4-thiouracil derivative (VII). Attempts to prepare 2', 3'-epoxide (XVII) of down-configuration from di-O-mesyl derivative (XVI) with sodium hydroxide was failed and instead 2, 2'-anhydronucleoside (XVIII) was obtained.

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On the Interaction of Oxygen with Cobalt Phthalocyanine in Solution as investigated by ESR

YUZURU OGATA, KUNIOMI MARUMO, TAKAO KWAN

1969 Volume 17 Issue 6 Pages 1194-1199
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1194

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The interaction of oxygen with cobalt phthalocyanine in solution has been investigated by an ESR method. When the solution was exposed to oxygen, g∼2.3 singal due to the complex decreased while new resonance line developed at g-value very close to that of a fre spin. The change of the two ESR signals was reversible with respect to ambient oxygen pressure. Moreover, when ascorbic acid was present initially in the solution, the uptake of oxygen took place in a catalytic way. Prolonged contact of the cobalt complex with oxygen in the absence of ascorbic acid gave rise to another narrower signal irreversibly again very close to that of a free spin, resulting in very poor catalytic ability. The behavior of the ESR signals was discussed in association with weak or destructive oxidation of the complex.

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Studies on Metabolism of 3-Desoxyestrone. II. Isolation and Characterization of Urinary Metabolites of 3-Desoxyestrone in Rabbit

TOSHIO NAMBARA, MITSUTERU NUMAZAWA

1969 Volume 17 Issue 6 Pages 1200-1205
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1200

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The metabolic fate of 3-desoxyestrone, which is used as a lipid-shifting drug, has been investigated with rabbit. Five phenolic and three neutral metabolites were separated from the urine after oral administration of 3-desoxyestrone. The structures of these metabolites were characterized by direct comparison with the authentic samples, respectively (see Chart 1). The biochemical significance of the transformations observed has been discussed.

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Steroid Series. XX. Reaction of α, β-Epoxyketone with Dimethyl Sulfoxide

YASUHIRO MORISAWA, KATSUMI TANABE

1969 Volume 17 Issue 6 Pages 1206-1211
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1206

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The oxidation of 17β-hydroxy-4β, 5-epoxy-5α-androstan-3-one (I) and its 4α, 5α-isomer (II) with dimethyl sulfoxide gave 4, 17β-dihydroxyandrost-4-en-3-one (IV), 17β-hydroxyandrosta-1, 4-dien-3-one (V), 2, 17β-dihydroxyandrosta-1, 4-dien-3-one (VI) and 2α, 17β-dihydroxyandrost-4-en-3-one (VII). The same reaction of 17β-acetoxy-4β, 5-epoxy-19-nor-5β-androstan-3-one (IIIa) afforded 4, 17β-dihydroxy-19-norandrost-4-en-3-one 17-acetate (VIIIa), estra-1, 3, 5 (10)-triene-3, 17β-diol 17-acetate (IX) and estra-1, 3, 5 (10)-triene-2, 3, 17β-triol 17-acetate (X). The corresponding 19-oxosteroid (IIIb) yielded the estrane derivatives (IX and X), while 19-hydroxymethyl steroid (IIIc) gave, in addition to the estrane derivatives (IX and X), 4, 17β, 19-trihydroxyandrost-4-en-3-one 17-acetate (VIIIc) and 17β-acetoxy-2β, 19-oxidoandrost-4-en-3-one (XI).

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Steroid Series. XXI. Reaction of 4-Halo-Δ⁴-3-oxosteroides with Dimethyl Sulfoxide

YASUHIRO MORISAWA, KATSUMI TANABE

1969 Volume 17 Issue 6 Pages 1212-1217
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1212

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The reaction of 4-chloro-Δ⁴-3-oxosteroids (Ia, c, e) with dimethyl sulfoxide were shown to yield Δ^{4, 6}-3-oxosteroids (IIg, h, i). These were accompanied by the 3, 6-dione (III) and Δ⁴-3, 6-dione (IV) in the case of 19-methylsteroid, by estra-1, 3, 5 (10)-triene-3, 17β-diol 17-acetate (VII) from 19-norsteroid, and by Δ⁴-3-oxo-6β, 19-oxide (VI) from 19-hydroxymethylsteroid. With dimethylsulfoxide 4-bromo-Δ⁴-3-oxosteroids (Ib, d, f) gave the 4-bromo-Δ^{4, 6}-3-oxosteroids (IIb, d, V) under the same reaction conditions. Bromination of 17β-acetoxyandrosta-4, 6-dien-3-one (IIg) in dimethylsulfoxide afforded the bromotrienone (X), the 2α-bromo (VIII) and 2, 2-dibromo (IX)-derivatives of IIg being intermediates in the conversion.

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Drug Absorption, Metabolism, and Excretion. V. Pharmacokinetic Studies on Renal Transport. (2). Analysis of p-Aminohippurate Run Out from the Kidney Slices by using Simultaneous Chemical Reaction and Diffusion Model

TAMOTSU KOIZUMI, JUICHIRO SHIBASAKI

1969 Volume 17 Issue 6 Pages 1218-1224
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1218

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Experimental data reported on PAH run out from the kidney slices were analyzed by applying the simultaneous chemical reaction and diffusion (SCRD) model. Various characteristic features of the experimental data were clearly explained by the proposed model.

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The Structure of Futoamide : A Constituent of Piper futokadzura SIEB. et ZUCC.

SHUJI TAKAHASHI, MASAAKI KURABAYASHI, AKIRA OGISO, HIROSHI MISHIMA

1969 Volume 17 Issue 6 Pages 1225-1228
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1225

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Structure of futoamide, isolated from Piper futokadzura SIEB. et ZUCC., was determined as N-isobutyl-7-(3, 4-methylenedioxyphenyl) hepta-2, 6-dienoic amide, which was synthesized by an unambiguous route.

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Studies on Peptides. XXII. Synthesis of the partially Protected Pentadecapeptide related to Monkey and Human β-Melanocyte-stimulating Hormones

HARUAKI YAJIMA, YOSHIO OKADA, HIROKI KAWATANI, NARIAKIRA MIZOKAMI

1969 Volume 17 Issue 6 Pages 1229-1236
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1229

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Synthesis of the partially protected pentadecapeptide related to monkey and human β-melanocyte-stimulating hormone, H-Pro-Tyr-Arg-Met-Glu-His-Phe-Arg-Trp-Gly-Ser-Pro-Pro-Lys (N^ε-formyl)-Asp-OH (III), was described. Condensation of Z-Glu (γ-OBzl)-OH with H-His-Phe-Arg-Trp-Gly-Ser-Pro-Pro-Lys (N^ε-formyl)-Asp-OH (IV) by the p-nitrophenyl ester method and subsequent hydrogenation gave H-Glu-IV, which was condensed with Boc-Met-OH by the same procedure. Treatment of the product with trifluoroacetic acid gave H-Met-Glu-IV. Boc-Arg (N^G-nitro)-OH was condensed with this dodecapeptide by the mixed anhydride procedure and the product was treated with hydrogen fluoride to give H-Arg-Met-Glu-IV, to which Boc-Pro-Tyr-OH was added by the azide procedure to afford the protected III. Treatment of which with trifluoroacetic acid gave III. The MSH activity of the synthetic peptides was as follows ; H-Glu-IV, 6.0×10⁶ : H-Met-Glu-IV, 1.9×10⁶, 2.3×10⁷ : H-Arg-Met-Glu-IV, 1.8×10⁸ and III, 2.2×10¹²units/g.

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Studies on Peptides. XXIII. Total Synthesis of Monkey β-Melanocyte-stimulating Hormone

HARUAKI YAJIMA, YOSHIO OKADA, YASUHIKO KINOMURA, NARIAKIRA MIZOKAMI, H ...

1969 Volume 17 Issue 6 Pages 1237-1245
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1237

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Total synthesis of monkey β-melanocyte-stimulating hormone was described. The synthesis involved in the coupling reaction of N^a-t-butoxycarbonyl-β-t-butylaspartyl-γ-t-butylglutamylglycine with prolyltyrosylarginylmethionylglutamylhistidylphenylalanylarginyltryptophylglycylserylprolylprolyl-N^ε-formyllysylaspartic acid by the N-hydroxysuccinimide ester method and subsequent removal of all of the protecting groups from the product, i. e., t-butyl and t-butoxycarbonyl groups by trifluoroacetic acid and the formyl group by hydrazine acetate. Synthetic monkey β-MSH exhibited 6×10⁹ and 2.5×10¹⁰MSH U/g.

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Bufadienolides. III. Reduction of Resibufogenin with Sodium Borohydride

YOSHIAKI KAMANO, HIROSHI YAMAMOTO, MANKI KOMATSU

1969 Volume 17 Issue 6 Pages 1246-1250
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1246

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Partial reduction of resibufogenin (III) having 14β, 15β-epoxide with sodium borohydride under various conditions was examined. No bufalin (IV) corresponding 14β-hydroxy compound was obtained in any case, but instead there was produced 14β, 15β-epoxy-5β-chol-20 (22)-ene-3β, 21, 24-triol (V) by the cleavage of an α-pyrone ring. Then V was converted into the corresponding triacetate (VI), bromide (VII) and saturated compound (VIII). The result of this reaction differed that of the reaction of Marinobufagin (I), which was reported to yield Telocinobufagin (II) corresponding 14β-hydroxy compound. In our case, it is interesting that 14β, 15β-epoxy ring is intact by the treatment with sodium borohydride whereas the α-pyrone ring cleavages smoothly to afford Δ^{20 (22)}-compound. This reaction mechanism was considered to be as depicted in Chart 3.

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Bufadienolides. IV. A New Route to Pregnane Series from Resibufogenin

YOSHIAKI KAMANO, HIROSHI YAMAMOTO, MANKI KOMATSU

1969 Volume 17 Issue 6 Pages 1251-1254
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1251

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In the previous paper, it was reported that the treatment of resibufogenin (I) with sodium borohydride gave 14β, 15β-epoxy-5β-chol-20 (22)-en-3β, 21, 24-triol (III) in a good yield. Therefore, it is considered that the cleavage reaction of a side chain double bond of III might be led to pregnane derivatives. After III was acetylated, the triacetate (IV) obtained was ozonized at -60° to give 14β, 15β-epoxy-20-oxo-5β-pregnane-3β, 21-diyl diacetate (V). This was confirmed by the elemental analyses and spectral data. Then, partial hydrolysis of V with potassium bicarbonate yielded 3-monoacetate (VI). The treatment of VI with periodic acid, followed by usual methylation gave the known methyl 3β-acetoxy-14β, 15β-epoxy-5β-androstane-17-carboxylate (VII). The identity was established by comparison with the authentic sample, which was prepared independently from acetyl-resibufogenin (II) by the method of Linde and Meyer. The success of the three-step conversion of resibufogenin to a pregnane derivatives (V), which proceeded in a 50% overall yield, opened a new route to pregnane derivatives having A/B- and C/D-cis ring system.

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Polyphosphoric Acid-catalyzed Beckmann Rearrangement of 3-Keto-steroid Oximes

MASARU KOBAYASHI, YUZURU SHIMIZU, HIROSHI MITSUHASHI

1969 Volume 17 Issue 6 Pages 1255-1260
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1255

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Synthesis of the Furan Derivatives. XLIV. Oxidation of Dimethyl Sulfonium Bromides in Dimethyl Sulfoxide Solution

HARUO SAIKACHI, JUNRO MATSUO

1969 Volume 17 Issue 6 Pages 1260-1263
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1260

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Benzodiazepines. III. A Novel Synthesis of a 1-Cyclopropylmethyl-1, 4-benzodiazepine Derivative

SHIGEHO INABA, TOSHIYUKI HIROHASHI, HISAO YAMAMOTO

1969 Volume 17 Issue 6 Pages 1263-1265
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1263

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A Simpler Synthesis of D-Pantothenic Acid 4'-Phosphate

MASANORI YOSHIOKA, KEIJIRO SAMEJIMA, ZENZO TAMURA

1969 Volume 17 Issue 6 Pages 1265-1267
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1265

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Synthesis of 9-(4'-Hydroxybutyl)-2-amino-6-hydroxypurine 4'-Phosphate

AKIHIRO YAMAZAKI

1969 Volume 17 Issue 6 Pages 1268-1270
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1268

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Bis (guanidinoethyl) amine Derivatives

TAKEO UEDA, SACHIKO KOBAYASHI

1969 Volume 17 Issue 6 Pages 1270-1276
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1270

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Quantitative Analysis of Primary Amines by Ion-exchange Chromatography

MASASHICHI YOSHIOKA, AKIRA OHARA, HIKARU KONDO, HARUO KANAZAWA

1969 Volume 17 Issue 6 Pages 1276-1279
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1276

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The Reimer-Tiemann Reaction of m-Halophenols. III. Formation of Dialdehydes

SHIGERU KOBAYASHI, MASARU AZEKAWA, MANABU TAOKA

1969 Volume 17 Issue 6 Pages 1279-1283
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1279

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A New Phytochemical Survey of Malaya. II. Chemical Screening

K.C. CHAN, L.E. TEO

1969 Volume 17 Issue 6 Pages 1284-1286
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1284

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The Boron Content of Brown Palladium Catalyst

CHAUYANG CHEN, HARUHIKO YAMAMOTO, TAKAO KWAN

1969 Volume 17 Issue 6 Pages 1287-1289
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1287

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Photochemistry of Heterocyclic Compounds. (5). The Photolysis of 9-Cyanoacridine 10-Oxides : The Synthesis of Benzo [c]-2-aza-1, 6-oxido [10] annulenes, Oxepino [2, 3-b] quinolines, and 11-Cyano-6-oxo-6H-azepino [a] indoles

CHIKARA KANEKO, SACHIKO YAMADA, MASAYUKI ISHIKAWA

1969 Volume 17 Issue 6 Pages 1294-1297
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1294

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Deamination of 8-Amino-1, 2, 3, 4-tetrahydro-6, 7-dimethoxy-1-(4-methoxybenzyl)-2-methylisoquinoline

SABURO ISHIWATA, KEIICHI ITAKURA

1969 Volume 17 Issue 6 Pages 1298-1299
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1298

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Structures of New Flavonoids, Sophoradin and Sophoranone, from Sophora subprostrata

MANKI KOMATSU, TSUYOSHI TOMIMORI, KATSUO HATAYAMA, YUKIKO MAKIGUCHI, N ...

1969 Volume 17 Issue 6 Pages 1299-1301
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1299

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Structures of New Flavonoids, Sophoradochromene and Sophoranochromene, from Sophora subprostrata

MANKI KOMATSU, TSUYOSHI TOMIMORI, KATSUO HATAYAMA, YUKIKO MAKIGUCHI, N ...

1969 Volume 17 Issue 6 Pages 1302-1304
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1302

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Microdetermination of Glucose using 3-Methyl-2-benzothiazolone Hydrazone Hydrochloride and Glucose Oxidase-Catalase Enzyme System

AKIO TSUJI, TOSHIO KINOSHITA, AKIKO SAKAI, MASANORI HOSHINO

1969 Volume 17 Issue 6 Pages 1304-1305
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1304

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Formation of Lichen Substances by Mycobionts of Lichens. Isolation of (+) Usnic Acid and Salazinic Acid from Mycobionts of Ramalina spp.

TAKEYA KOMIYA, SHOJI SHIBATA

1969 Volume 17 Issue 6 Pages 1305-1306
Published: June 25, 1969
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.17.1305

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