Chemical and Pharmaceutical Bulletin

Biochemical Studies on Quinone Derivatives. I. Effects of Naturally Occurring Benzoquinone Derivatives on Mitochondrial Preparations

Hikaru Ozawa, Shinsaku Natori, Kazutaka Momose

1965 Volume 13 Issue 9 Pages 1029-1035
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1029

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Effects of naturally occurring ρ-benzoquinone derivatives on mitochondrial respiration were studied. Plant quinones, such as rapanone and maesaquinone, stimulated succinate oxidase of intact mitochondria. These quinones and other derivatives reactivated succinate oxidase which was inhibited by acetone-treatment of mitochondria. However methylated quinones did not show reactivated efficiently. Reduced dihydroxy-maesaquinone dimethyl ether reacted with cytochrome c enzymatically, but the reaction was not inhibited by antimycin A addition. The other reduced quinones were reactive with cytochrome c nonenzymatically.

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Studies on Amino Sugars. I. Preparation of N-Acyl Derivatives of 2-Acetamido-2-deoxy-β-D-glucosylamine

Akira Yamamoto, Chieko Miyashita, Hisao Tsukamoto

1965 Volume 13 Issue 9 Pages 1036-1041
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1036

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2-Acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine (IV) was prepared by the hydrogenation of 2-acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosyl azide (III) which was obtained by the treatment of acetochloroglucosamine with NaN₃ in formamide at 85°.IV was characterized by the acetylation as N-acetyl-2-acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine (VI). IV in tetrahydrofuran or pyridine was condensed in the presence of dicyclohexylcarbodiimide with p-nitrobenzoic acid, isonicotinic acid, aceturic acid, hippuric acid and N-benzyloxycarbonyl glycine to yield the corresponding amides, followed by the removal of the protecting groups. N-(ρ-Aminobenzoyl)2-acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine was obtained by the hydrogenation of the corresponding p-nitrobenzamido derivative over Adams'catalyst.

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Studies on Amino Sugars. II. Preparation of N-[L-α(and β)-Aspartyl]-2-acetamido-2-deoxy-β-D-glucosylamine and N-(L-γ-Glutamyl)-2-acetamido-2-deoxy-β-D-glucosylamine

Akira Yamamoto, Chieko Miyashita, Hisao Tsukamoto

1965 Volume 13 Issue 9 Pages 1041-1046
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1041

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N-(L-β-Aspartyl)-2-acetamido-2-deoxy-β-D-glucosylamine has been prepared by the condensation of N-benzyloxycarbonyl-L-aspartic acid α-benzyl ester with 2-acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine in the presence of dicyclohexylcarbodiimide followed by hydrogenolysis and de-O-acetylation on the resulting 1-(α-benzyl N-benzyloxy-carbonyl-L-β-aspartamido)-2-acetamido-1, 2-dideoxy-3, 4, 6-tri-O-acetyl-β-D-glucose to remove the protecting groups. N-(L-β-Aspartyl)-2-acetamido-2-deoxy-β-D-glucosylamine and N-(L-γ-glutamyl)-2-acetamido-2-deoxy-β-D-glucosylamine have been prepared by the same method as for β-aspartylglycopeptide.

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Studies on Amino Sugars. III. Isolation and Identification of Crystalline N-Acetylglucosamine-asparagine Compound from Ovalbumin

Akira Yamamoto, Hisao Tsukamoto

1965 Volume 13 Issue 9 Pages 1046-1052
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1046

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Ovalbumin was hydrolysed with Pronase-P, and the carbohydrate-containing fragments were isolated as two glycopeptides. From partial hydrolysate of glycopeptides in 2N hydrochloric acid, N-acetylglucosamine-asparagine compound was isolated in pure, crystalline state, and its structure was established for N-(L-β-aspartyl)-2-acetamido-2-deoxy-β-D-glucosylamine.

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Camphane Derivatives. VII. Syntheses and Structure of 3-Methyl-3aβ, 7aβ-bornano[3, 2-d]oxazolidin-2-one and its Derivatives

Yoshio Hamashima, Kazuo Tori, Akira Takamizawa

1965 Volume 13 Issue 9 Pages 1052-1064
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1052

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In connection with the structure elucidation of two products, 3-methyl-7a-chloro-3aβ, 7aβ-bornano[3, 2-d]oxazolidin-2-one (III) and 3-methyl-3a-hydroxy-3aβ, 7aβ-bornano-[3, 2-d]oxazolidin-2-one (IV), obtained by the reaction of 3α-methylaminocamphor (I) with phosgene, 3-methyl-3aβ, 7aβ-bornano[3, 2-d]oxazolidin-2-one (V), 3-methyl-3aα, 7aα-bornano[3, 2-d]oxazolidin-2-one (VI) and their derivatives were synthesized and studied stereochemically. Their proton magnetic resonance spectra were also investigated.

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Polyphosphate Esters as a Synthetic Agent. III. Amide and Peptide Syntheses

Yuichi Kanaoka, Minoru Machida, Osamu Yonemitsu, Yoshio Ban

1965 Volume 13 Issue 9 Pages 1065-1072
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1065

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PPE(polyphosphate esters) was shown to be a good agent for amide synthesis from a variety of carboxylic acids and primary amines. It also effected imide cyclization. Though in the presence of PPE peptide derivatives were obtained by coupling aminoacids or peptides, full racemization took place. The structure of PPE was discussed with brief review of literatures.

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Studies on the Structures of Some Cholestanoindoles

Yoshio Ban, Yasuhiko Sato

1965 Volume 13 Issue 9 Pages 1073-1077
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1073

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The structures of indolocholestanes derived from 5α-(I) and 5β-cholestan-3-ones (IV) have been established as V and III, respectively, by chemical degradations.

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Studies on Conformation and Reactivity. III. The Polyphosphoric Acid-catalyzed Ring Opening of 4, 5-Epoxy-3-oxo Steroids. 3. The Synthesis of 16α, 17-Epoxy-4-ethyl-thiopregn-4-ene-3, 20-dione and its Analogs

Munemitsu Tomoeda, Tetsuya Furuta, Toshitaka Koga

1965 Volume 13 Issue 9 Pages 1078-1084
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1078

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An example of the mild and selective catalytic action of PPA for the ring opening reaction of α, β-epoxy ketone systems under different steric environment in the steroid nucleus was described. A remarkably inert character of the 16α, 17-epoxy-20-oxo system in the pregnane series for the ring opening under PPA catalysis with such nucleophile as alkylmercaptans was observed. The effcient catalytic action of PPA for normal ring opening at C-4 of 4β, 5 : 16α, 17-diepoxy-5β-pregnane-3, 20-dione (IIb) was reported. Ethanethiol reacted with the diepoxide (IIb) in PPA-dioxane affording 16α, 17-epoxy-4-ethylthiopregn-4-ene-3, 20-dione (IV) and a further product, 3, 4-bis (ethylthio)-16α, 17-epoxypregna-3, 5-dien-20-one (V). Ethanedithiol and 2-mercaptoethanol reacted with IIb, as expected, affording 16α, 17-epoxy-20-oxopregna-3, 5-dieno[3, 4-b]dithiane (VI) and its oxathiane derivative (VII) respectively.

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The Schmidt Reaction with Some Tetralone and Indanone Derivatives

Shinsaku Minami, Masatsugu Tomita, Hideji Takamatsu, Shojiro Uyeo

1965 Volume 13 Issue 9 Pages 1084-1091
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1084

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While the Schmidt reaction on indanones or tetralones containing no substituents on the benzene moiety of the respective molecules are reported to yield carbostyrils or homocarbostyrils as the sole isolable product, it has been shown that when these compounds contain an electron releasing substituent (e.g. methoxyl group) in the benzene ring, the Schmidt reaction gives both isocarbostyrils and carbostyrils or homoisocarbosyrils and homocarbostyrils in a variable ratio depending upon the structure of the starting materials.

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Studies on Morphine Alkaloids. II. Indolinocodeine. I. A New Skeletal Rearrangement of 14-Bromocodeine

Shigenobu Okuda, Sadao Yamaguchi, Kyosuke Tsuda

1965 Volume 13 Issue 9 Pages 1092-1103
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1092

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Neopine (III), isoneopine (XXII) and indolinocodeine (XVII) were isolated from the sodium borohydride reduction mixture of 14-bromocodeinone (I) or 14-bromocodeine (II). The structures of new compounds, XVII and XXII, were elucidated. Hydroindole structure is comprised in XVII instead of hydroisoquinoline skeleton in codeine. The reaction mechanisms for production of the above three compounds were also discussed.

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Studies on Chemical Carcinogens. I. Reduction of 4-Substituted Quinoline N-Oxide with Sodium Borohydride

Yutaka Kawazoe, Misako Tachibana

1965 Volume 13 Issue 9 Pages 1103-1107
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1103

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4-Substituted quinoline N-oxides were reduced by sodium borohydride and the reaction mechanism was discussed. It was revealed, for example, that 4-nitroquinoline N-oxide underwent competitive nucleophilic reactions to produced denitrated quinoline N-oxide, deoxygenated 4-nitroquinoline and 4-hydroxylaminoquinoline N-oxide which is a reduction product of nitro group, respectively.

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Biological Photochemistry. I. The Correlation between the Photodynamical Behaviors and the Chemical Structures of Nucleic Acid-bases, Nucleosides, and Related Compounds in the Presence of Methylene-blue

Kazuko Zenda, Mineo Saneyoshi, Goro Chihara

1965 Volume 13 Issue 9 Pages 1108-1113
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1108

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As a study on mechanism of photodynamic action with methylene-blue, the authors examined structural correlation of 40 kinds of nucleic acid-bases, nucleosides and related compounds with their photodynamic degradation by visible light-irradiation in the presence of methylene-bule. As a result, it became established that : 1) Above-mentioned compounds, in order to be easily photodynamically degradated, need to have the lactim structure with respect to N 1 and 3-position in pyrimidine moiety of purine ring. 2) Imidazol ring seems to be essential for photodegradation. 3) Existence of substituent in 8, 9-position in purine didn't affect on photochemical reaction.

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Prediction of Stability in Pharmaceutical Preparations. XIV. The Complete pH Dependent Solvolytic Degradations of an Iodinated Nucleoside, the Antiviral 5-Iodo-2'-deoxyuridine

Edward R. Garrett, Pramod B. Chemburkar, Tokuji Suzuki

1965 Volume 13 Issue 9 Pages 1113-1130
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1113

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a) The solvolysis of the antiviral, 5-iodo-2'-deoxyuridine (IDU) is catalyzed by hydrogen ions and solvent, in the acetate and low pH phosphate buffer regions, and by hydroxyl ions and solvent, in the borate buffer and high pH alkaline region. b) The solvolysis of IDU is first-order with respect to IDU over the pH range of 3.9 to 12.0. c) The Arrhenius parameters at different pH values varied. These parameters have been evaluated at specific pH values. d) The general procedure for the prediction of stability of IDU at any pH value has been discussed. e) In the alkaline region the proposed mechanism involves two routes : (1) the production of uracil through the formation of the intermediate deoxyuridine as the minor route and (2) the formation of 5-hydroxy-2'-deoxyuridine which degrades further as the major route.

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Preparation of α-Benzyl N-Benzyloxycarbonyl-DL-aspartate and its Resolution by 2-Acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine

Akira Yamamoto, Hisao Tsukamoto

1965 Volume 13 Issue 9 Pages 1131-1134
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1131

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N-Benzyloxycarbonyl-DL-aspartic acid α-benzyl ester was prepared from N-benzyl-oxycarbonyl-L-aspartic anhydride on racemisation in the prersence of dicyclohexylamine and condensed with 2-acetamido-2-deoxy-3, 4, 6-tri-O-acetyl-β-D-glucosylamine to give diastereomeric two glycopeptide acetates, 1-(α-benzyl N-benzyloxycarbonyl-L-β-aspart-amido)-2-acetamido-1, 2-dideoxy-3, 4, 6-tri-O-acetyl-β-D-glucose and 1-(α-benzyl N-benzyloxycarbonyl-D-β-aspartamido)-2-acetamido-1, 2-dideoxy-3, 4, 6-tri-O-acetyl-β-D-glucose. Both compounds were subjected to hydrogenolysis and de-O-acetylation to give the resulting two glycopeptide, N-(L-β-aspartyl)-2-acetamido-2-deoxy-β-D-glucosylamine and N-(D-β-aspartyl)-2-acetamido-2-deoxy-β-D-glucosylamine.

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Syntheses of N-(2-Pyridylmethyl)aniline and its Derivatives

Seiji Miyano

1965 Volume 13 Issue 9 Pages 1135-1137
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1135

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Synthesis of 8-Hydroxypurine Nucleosides

Morio Ikehara, Hiroshi Tada, Kei Muneyama

1965 Volume 13 Issue 9 Pages 1140-1142
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1140

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A Total Synthesis of Coenzyme A via Thiazoline Intermediate

Masao Shimizu, Osamu Nagase, Seizaburo Okada, Yasuhiro Hosokawa, Hiroa ...

1965 Volume 13 Issue 9 Pages 1142-1144
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1142

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B-Homoprogesterone

Jyun'ichi Himizu, Toshihiko Shichita

1965 Volume 13 Issue 9 Pages 1145-1147
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1145

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Semisynthetic Penicillins. I. a-Methylthio-2-chlorocinnamylpenicillin

Teiichiro Ito, Tadao Ishii, Motohiro Nishio

1965 Volume 13 Issue 9 Pages 1148-1150
Published: September 25, 1965
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.13.1148

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