Chemical and Pharmaceutical Bulletin

Studies on Coenzyme Analogs. XVI. Synthesis of 9-D-Erythrityl-adenine and its Phosphates.

Morio Ikehara, Eiko Ohtsuka

1963 Volume 11 Issue 9 Pages 1095-1101
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1095

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9-D-Erythrityladenine was synthesized from 4, 6-dichloro-5-aminopyrimidine and 2, 4-O-ethylidene-erythritylamine, followed by the cyclization with acetic anhydride and ethyl orthoformate. The phosphorylation of erythrityladenine was achieved by the general method using P-diphenyl P'-morpholino pyrophosphorochloridate described in earlier report. 2', 3'-Di-O-acetylerythrityladenine 4'-triphosphate was obtained as decahydrate in a pure state.

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Studies on Coenzyme Analogs. XVII. A New Synthesis of Purine Nucleoside by the Condensation of Chloropyrimidine with Glucosylamine.

Morio Ikehara, Hiroshi Tada

1963 Volume 11 Issue 9 Pages 1102-1107
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1102

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The reaction between 4, 6-dichloro-5-nitropyrimidine or 4-amino-5-nitro-6-chloropyrimidine and 2, 3, 4, 6-tetra-O-acetyl-D-glucopyranosylamine was investigated. In the former case, in addition to 4-chloro-5-nitro-6-(2, 3, 4, 6-tetra-O-acetylglucosylamino) pyrimidine, 4, 6-bis-glucosylamino derivative was obtained. Ring-closure of 4-chloro-5-amino-6-(2, 3, 4, 6 tetra-O-acetylglucosylamino) pyrimidine was achieved by acetic anhyd. ethyl orthoformate and further two step reaction afforded 9-β-D-glucopyranosyladenine. By the carbon disulfide ring-closure of 4, 5-diamino-6-(2, 3, 4, 6-tetra-O-acetylglucosylamino) pyrimidine, 9-β-D-glucosyladenine and N⁶-glucosyladenine was obtained in the ratio of 2 : 9. After deacetylation of triaminopyrimidine derivative, however, the reaction occurred in the reversed ratio of 9 : 4.

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Studies on the Method of Thermal Analysis of Organic Medicinals. III. Relations between Methods of Sample Preparation and Obtained Phase Diagrams.

Keiji Sekiguchi, Yoshio Ueda, Yoshiko Nakamori

1963 Volume 11 Issue 9 Pages 1108-1122
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1108

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Three methods of sample preparation for the thermal analysis by the thaw-melt method were proposed. The heating procedure for solidification of the melt was proved to be very effective, especially for those samples that are apt to take vitreous states after fusion. Tests concerning both reliability and applicability the modified thaw-melt method were carried out on twelve kinds of organic binary system to which the application of the original method of Rheinboldt is thought to be difficult. The results indicate that the modified method is more accurate and reliable than the original one. The meaning and the use of the thaw point due to the metastable eutectic point in the system of compound formation were discussed.

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Studies on the Method of Thermal Analysis of Organic Medicinals. IV. Double Melting Point of Organic Binary Mixtures.

Keiji Sekiguchi, Keiji Ito, Yoshiko Nakamori

1963 Volume 11 Issue 9 Pages 1123-1133
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1123

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In order to improve the dependability of the thaw-melt method, the double melting point phenomenon which has hitherto been neglected or overlooked was investigated on five kinds of organic binary systems with one or two molecular compounds. The systems were those of aminopyrine and barbital, aminopyrine and sulfisoxazole, benzoic acid and isonicotinamide, nicotinamide and sulfamerazine, and urea and N-sulfanilyl-3, 4-xylamide. The metastable or the first melting point occurs either by the delayed peritectic reaction in a stable mixture or by the suspended compound formation in a metastable mixture. In the former case, the metastable melting points appear on the upper extension of the middle branch of the stable liquidus. In the latter, they are observed on either or both of the extensions of the right and the left branch of liquidus. The occurrence of this phenomenon depends not only on the nature of the system but also on the conditions of measurement, such as agitation and heating rate. The submerged maximum which was thought to be hypothetical was clearly observed with the system of aminopyrine and sulfisoxazole and that of urea and N-sulfanilyl-3, 4-xylamide. The isolated compound of the former was examined by the differential thermal analysis. Heat effect was noted only at the metastable melting point of this compound. If the sample contains no supercooled liquid, the occurrence of double melting point in the heating procedure is actually limited to those cases described above. It will therefore, be very useful for the detection of molecular compound. Also the knowledge of this phenomenon will help to construct a correct phase diagram.

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Metabolism of Drugs. XXXIX. Further Studies on Carbamate N-Glucuronide Formation in Animal Body.

Hisao Tsukamoto, Hidetoshi Yoshimura, Kiyoshi Tatsumi

1963 Volume 11 Issue 9 Pages 1134-1139
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1134

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Amorphous meprobamate N-glucuronide, a metabolite of meprobamate which was reported in the previous paper was converted to crystalline sodium salt and the structure was reconfirmed to be sodium meprobamate N-mono-β-D-glucopyranosiduronate. It was also proved that ethinamate (1-ethynylcyclohexylcarbamate) formed the corresponding N-glucuronide in rabbits after dosing the drug. Therefore it could be concluded that N-glucuronide formation might be one of the metabolic pathways in animal body for the drug possessing a carbamate group, although it was not the case for urethane which decomposed almost completely in animal body.

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Studies on Optically Active Amino Acids. IV. A New Synthetic Approach to Chloramphenicol Base from L-Phenylalanine.

Shunichi Yamada, Kenji Koga, Hisayuki Matsuo

1963 Volume 11 Issue 9 Pages 1140-1145
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1140

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A new synthetic approach to chloramphenicol base (XVII) was investigated starting with L-phenylalanine (II), making use of the same configuration of the α-carbon in (II) as that of the C-2 in XVII. Preliminary experiments starting with DL-phenylalanine was also described. The synthetic route is shown in Chart 2. threo-XVI and threo-XVII, the final product in this synthetic approach, were isolated from the mixture of threo- and erythro-XV by the application of the stereoselective acyl rearrangement reaction, which is shown in Chart 3.

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Potential Anticancer Agents. XIII. Reaction of 3, 6-Dimethylpyridazine 1-Oxide and Methylpyridazine 1-Oxides with Benzaldehyde.

Takanobu Itai, Shigeru Sako, Genzo Okusa

1963 Volume 11 Issue 9 Pages 1146-1150
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1146

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The nucleophilic activity of methyl group in 3, 6-dimethylpyridazine 1-oxide (I) and monomethylpyridazine 1-oxides (II) with benzaldehyde was studied. Their corresponding (β-hydroxyphenethyl) pyridazine 1-oxides and styryl compounds were gained. From the results, it may be deduced as follows. (i) The reactivity of 3-and 6-methyl groups in I were almost same, different from the cases of 3, 6-dichloropyridazine 1-oxide. (ii) 4- and 6-methyl groups in II were similarly reactive, but 5-methyl was more active, and 3-methyl less active than fore-mentioned two methyl groups. These styryl compounds that were produced respectively, were catalytically hydrogenated with Pd-C to corresponding phenethylpyridazine 1-oxides.

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On the Cardiolipin Analogues. Syntheses of Dipalmitoyl-D, L-α-glycerylphosphoryl-propanol Sodium Salt and Bis (dipalmitoyl-D, L-α-glyceryl-phosphoryl)-1, 3-propanediol Disodium Salt.

Keizo Inoue, Yasuji Suhara, Shoshichi Nojima

1963 Volume 11 Issue 9 Pages 1150-1156
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1150

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Dipalmitoyl-D, L-α-glycerylphosphorylpropanol sodium salt (I) and bis (dipalmitoyl-D, L-α-glycerylphosphoryl)-1, 3-propanediol disodium salt (II) were synthesized by the condensation of the silver salt of dipalmitoyl-D, L-α-glycerophosphoric acid benzyl ester (III) with alkyl iodide, followed by debenzylation with sodium iodide. It was found that II was converted to an acid form upon silicic acid column.

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Studies on Pyridazine Derivatives. V. Syntheses of 5-Substituted Derivatives of 3-Amino-6-alkoxypyridazine 2-Oxide.

Tatsuya Horie

1963 Volume 11 Issue 9 Pages 1157-1167
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1157

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In order to find antimicrobial agents, the substitution of 3-acetamido-6-alkoxypyridazine 2-oxide was investigated. As the results obtained, it was made clear that a number of 3-acetamido-6-alkoxypyridazine, 3-amino-6-alkoxypyridazine and their 2-oxides having such a substituent group as nitro, amino, hydroxyamino, azo, hydrazo, chloro, methoxy, methylthio, hydroxy, and mercapto at 5-position of the pyridazine rings, were synthesized. This finding is of use to develope the chemistry of pyridazine. Among these new compounds, 3-acetamido-and 3-amino-5-nitro-6-alkoxypyridazine 2-oxides were found to exert excellent in vitro effects on pathogenic bacteria.

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Oxidation of 3-Enol Derivatives of 4-En-3-oxo-steroids by tert-Butyl Chromate.

Kikuo Yasuda

1963 Volume 11 Issue 9 Pages 1167-1174
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1167

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3-Enol acetates of some 4-en-3-oxo-steroids were oxidized to the corresponding 7-ones with t-butyl chromate and 3-enol methyl ethers were to the corresponding 4-ene-3, 6-diones, 6β-hydroxy-4-en-3-ones or 4, 6-dien-3-ones according to the reaction conditions. 3-Enol methyl ethers were prepared with methyl orthoformate in dioxane by catalysis of p-toluenesulfonic acid. 17α-Acetoxy-5α, 6β-dichloropregnane-3, 20-dione was converted into 3-methoxy-6-chloro-17α-acetoxypregna-3, 5-dien-20-one in one step.

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Metabolic Products of Fungi. XXI. On Ustilaginoidins. (1). The Reactions of Ustilaginoidin A.

Shoji Shibata, Akihiro Ohta, Yukio Ogihara

1963 Volume 11 Issue 9 Pages 1174-1178
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1174

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An orange red pigment, ustilaginoidin A, C₂₈H₁₈O₁₀, m.p. >300°, [α]_D -384° (dioxane), was isolated from false the smutted ball growing on rice spike. It has been shown that ustilaginoidin A possesses two hindered and four unhindered hydroxyls giving tetraacetate, tetrabenzoate, and hexamethyl ether. On alkaline degradation, ustilaginoidin A gave unstable product A and acetone. The product A afforded peracetate, C₃₆H₃₀O₁₆, and permethyl ether, C₂₈H₃₀O_8· Ustilaginoidin A hexamethyl ether yielded product B, C₃₀H₃₀O₁₀, on alkaline degradation, which gave diacetate and dimethyl ether. The ultraviolet spectral study has suggested a close structural correlation between the product A and 1, 1'-binaphthalene or 1-phenylnaphthalene.

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Metabolic Products of Fungi. XXII. On Ustilaginoidins. (2). The Structure of Ustilaginoidin A.

Shoji Shibata, Yukio Ogihara, Akihiro Ohta

1963 Volume 11 Issue 9 Pages 1179-1182
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1179

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Ustilaginoidin A has been formulated as 2, 2'-dimethyl-5, 5', 6, 6', 8, 8'-hexahydroxy-9, 9'-bis (4H-naphtho [2, 3-b] pyran-4-one) on the basis of the infrared and nuclear magnetic resonance spectral analyses of ustilaginoidin A and its degradation products, product A and product B and their derivatives.

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Systematic Analysis of Steroids. I. Systematic Analysis of Steroid Hormones by Thin Layer Chromatography.

Michiko Takeuchi

1963 Volume 11 Issue 9 Pages 1183-1188
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1183

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Systematic and simultaneous analysis of twenty-six steroid hormones was carried out by thin layer chromatography. Twenty-eight solvent systems consisting of various organic solvents in various proportions were used as the mobile phase. The interrelationship among chemical structure and adsorptivity onto silica gel of steroid hormones is discussed. Characteristic color reaction of steroid hormones and four coloring reagents was examined.

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Systematic Analysis of Steroids. II. Analysis of Steroid Sapogenins by Thin Layer Chromatography.

Nobue Matsumoto

1963 Volume 11 Issue 9 Pages 1189-1192
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1189

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Thin layer chromatography was applied to systematic, simultaneous analysis of twenty kinds of steroid sapogenins. Examining into twenty-two solvent systems and four coloring reagents, simultaneous, sensitive analysis was successfully carried out.

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The Synthesis of β-Carboline Derivatives. III. A Synthesis of 10-Methoxy-6, 7-dihydro-12H-indolo [2, 3-a] quinolizinium Salts.

Yoshio Ban, Masako Seo

1963 Volume 11 Issue 9 Pages 1193-1195
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1193

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10-Methoxy-6, 7-dihydro-12H-indolo [2, 3-a] quinolizinium salts were prepared in ca. 90% yield through condensation of 6-methoxytryptophol tosylate with 2-bromopyridine, which is the best record so far described for this type of condensations. The above salt was hydrogenated to the octahydroindolo [2, 3-a] quinolizine derivative.

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The Synthesis of 3-Spirooxindole Derivatives. IV. The Conversion of 3-Spirooxindole to Indole Derivative.

Takeshi Oishi, Shizuo Maeno, Yoshio Ban

1963 Volume 11 Issue 9 Pages 1195-1197
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1195

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The conversion of 1-methylspiro (indoline-3, 1'-indolizine)-2-one to 12-methyl-1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo [2, 3-a] quinolizine is described as a preliminary for the chemical correlation of N-methylrhynchophyllane with N-methyldihydrocorynantheane.

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Studies on the Constituents of Asclepiadaceae Plants. XI. Separation of New Aglycones from Cynanchum caudatum MAXIM.

Hiroshi Mitsuhashi, Yuzuru Shimizu, Taro Nomura, Tazu Yamada, Emiko Ya ...

1963 Volume 11 Issue 9 Pages 1198-1200
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1198

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The alkaline hydrolysate of the crude aglycones of Cynanchum caudatum MAXIM. showed the existence of two new aglycones, besides deacylcynanchogenin and sarcostin, by paper chromatography. The one (A₃) was shown to be deacetylmetaplexigenin, and the other (A₄) as isodeacylcynanchogenin. A₄ appears to be an isomer of deacylcynan-chogenin formed under the conditions of alkaline hydrolysis.

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Determination of Threonine in Lipid of Animal Brain.

Makoto Hayashi, Yoshinori Nakajima, Keizo Inoue, Komei Miyaki

1963 Volume 11 Issue 9 Pages 1200-1202
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1200

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Quantitative analysis of threonine in brain lipid of various animals was performed and it was found that brain lipid of mouse and rat containes 0.04μmole of threonine per 10μmoles of lipid-P, while that of guinea-pig and rabbit does not contain threonine at all.

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Formation of a Micelle-like Structure in Aqueous Solution of 1, 4-Hexanediol.

Yuriko Kato

1963 Volume 11 Issue 9 Pages 1202-1204
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1202

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Structure of Valeranone

Hiroshi Hikino, Yasuko Hikino, Yasuyoshi Takeshita, Kanji Meguro, Tsun ...

1963 Volume 11 Issue 9 Pages 1207-1210
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1207

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Structure of Kanokonol

Hiroshi Hikino, Yasuko Hikino, Tsunematsu Takemoto

1963 Volume 11 Issue 9 Pages 1210-1212
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1210

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Isolation of cis-and trans-2-Methoxymethylene-3-ethoxypropionitrile

Akira Takamizawa, Kentaro Hirai, Kazuo Tori

1963 Volume 11 Issue 9 Pages 1212-1213
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1212

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Structure of p-Ethoxyphenylurea-N-glucuronide

Masuo Akagi, Takayoshi Uematsu, Isamu Aoki, Masanobu Haga, Masakatsu S ...

1963 Volume 11 Issue 9 Pages 1214-1215
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1214

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2-Methyl-3-o-hydroxymethylphenyl-4 (3H)-quinazolinone, a Metabolite of 2-Methyl-3-o-tolyl-4 (3H)-quinazolinone in Rabbit

Masuo Akagi, Yoneshiro Oketani, Sumitaka Yamane

1963 Volume 11 Issue 9 Pages 1216-1217
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1216

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Isolation of 2-Phenylacetamide, Indole-3-acetamide, and Indole-3-carboxaldehyde from Etiolated Seedling of Phaseolus

Yo Isogai, Toshihiko Okamoto, Toru Koizumi

1963 Volume 11 Issue 9 Pages 1217-1218
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1217

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Carcinostatic Methanesulfonic Acid Esters of Nitrogen Mustard Analogs

Morizo Ishidate, Yoshio Sakurai, Zenzo Tamura, Toshio Nambara, M.M.El. ...

1963 Volume 11 Issue 9 Pages 1218-1219
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1218

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Partial Synthesis of Securinine

Seiichi Saito, Noboru Shigematsu, Hiroshi Yoshikawa, Zen-ichi Horii, Y ...

1963 Volume 11 Issue 9 Pages 1219-1220
Published: September 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1219

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