Chemical and Pharmaceutical Bulletin

Studies on the sulfur-containing Chelating Agents. I.. Syntheses of β-Mercaptoketones and their Copper Chelates. (1)

Hisashi Tanaka, Akira Yokoyama

1960 Volume 8 Issue 4 Pages 275-279
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.275

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β-Mercaptoketones were prepared as a new type of chelating agent in which the mercapto and keto groups take part in chelate formation. β-Mercapto-β-phenylpropio-phenone was prepared by the addition of hydrogen sulfide to α-benzylideneacetophenone under pressure. This method was applied to the syntheses of β-mercapto-β-(p-methoxyphenyl)-, α-methyl-β-mercapto-β-phenyl-, and α, β-diphenyl-β-mercaptopropiophenones. In most cases, corresponding disulfides were also obtained as a result of the addition of hydrogen sulfide. These mercaptoketones formed orange-yellow chelates with copper and the ratio of ligand to copper was found to be 1 : 1.

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Studies on the Sulfur-containing Chelating Agents. II. Syntheses of β-Mercaptoketones and their Copper Chelates. (2).

Hisashi Tanaka, Akira Yokoyama

1960 Volume 8 Issue 4 Pages 280-283
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.280

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β-Mercaptoketones, β-mercapto-β-(m-tolyl)-and β-mercapto-β-(p-chlorophenyl)-propiophenone, β-mercapto-β-phenyl-p-chloropropiophenone, β-mercapto-β-phenyl-p-methoxypropiophenone, and β-mercapto-β-(1-naphthyl)propiophenone, were prepared by the addition of hydrogen sulfide to the corresponding α-benzylideneacetophenones and α-1-naphthylideneacetophenone. These mercaptoketones formed chelate compounds with copper and the ratio of ligand to copper was found to be 1 : 1.

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Uber eine neue Nitrierung des Chinolin-1-oxides. (4).

Eiji Ochiai, Chikara Kaneko

1960 Volume 8 Issue 4 Pages 284-286
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.284

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4-Chlor-und 4-Bromchinolin-1-oxid ergaben bei der Nitrierung mit Benzoylchlorid und Silbernitrat in einer Chloroform-Losung das entsprechende 3-Halogenderivat des 4-Hydroxy-1-benzoyloxychinolinbetains(IV bzw. V). 2-Athoxychinolin-1-oxid ergab bei der Einwirkung von Benzoylnitrat 1-Benzoyloxycarbostyril (VI). Die Entstehung von (IV), (V) und (VI) bestatigt den von den Verfassern kurzlich vorgeschlagenen Reaktionsmechanismus fur die Nitrierung von Chinolin-1-oxid mittels Acylnitrates.

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Uber eine modifizierte Reissert'sche Reaktion in der Chinolin-1-oxid-Reihe.

chikara Kaneko

1960 Volume 8 Issue 4 Pages 286-289
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.286

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Eine modifizierte Reissert'sche Reaktion auf Chinolin-1-oxid bzw. seine Derivate durch Einwirkung von Benzoylchlorid und Silbercyanid in einer Chloroform-Losung wurde ausgefuhrt und die in der Tabelle I gezeigten Ergebnisse erhalten. Der Mechanismus fur diese Reaktion wurde beigebracht.

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Synthesis in the Erythrinane Group of Compounds. I. A Synthesis

Shigehiko Sugasawa, Hiroshi Yoshikawa

1960 Volume 8 Issue 4 Pages 290-293
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.290

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A new synthesis of 15, 16-dimethoxyerythrinane was described. 3, 4-Dimethoxyphenethylamine was condensed with cyclohexane-1, 2-dione in the presence of phoshoric acid to yield the basic spiroketone (II), which was converted into N-ethoxycarbonylacetyl derivative(IV') by the conventional method. The latter was cyclyzed by means of sodium hydride in boilng ethanol to give the dehydrated tatracyclic compound (VII) in a good yield. The decarboxylation product (VIII) of (VII) was reduced catalytically to furnish (IX), which on being reduced with lithium aluminum hydride gave rise to 15, 16-dimethoxyery-thrinane (X).

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Infrared Spectra of Some Indole and Pyrrole Compounds

Yuichi Kanaoka, Yoshio Ban, Takeshi Oishi, Osamu Yonemitsu, Masanao Te ...

1960 Volume 8 Issue 4 Pages 294-301
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.294

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Infrared Spectra of a number of indole compounds have been examined and the characteristic frequencies of indole group are given. The CH out-of plane bending vibration of the pyrrole moiety of the indole ring and related methylpyrroles are discussed.

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Studies on the Components of Fritillaria Thunbergii MIQ. I. Isolation of Peimine and its new Glycoside.

Hiroshi Morimoto, Seiichi Kimata

1960 Volume 8 Issue 4 Pages 302-307
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.302

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Peimine (I) and Peiminoside (II), a new glycoside (C₃₃H₅₅O₈N), were isolated from bulbs of Fritillaria Thunbergii MIQ. (Bai-mo, ?? ?? )produced in Japan, and the latter was found to be a glycoside consisting of peimine and D-glucose.

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Studies on Coenzyme Analogs. I. Synthesis of 3-β-D-Ribofuranosyl-2-oxo-2, 3-dihydropyrimidine (6-Deoxyuridine) and its 5'-Phosphate.

Morio Ikehara

1960 Volume 8 Issue 4 Pages 308-313
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.308

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A new nucleoside, 3-(β-D-ribofuranosyl)-2-oxo-2, 3-dihydropyrimidine (6-deoxyruidine), was synthesized from 2-hydroxypyrimidin-1-ylmercury chloride and 2, 3, 5-tri-O-benzoyl-ribofuranosyl chloride, followed by removal of protecting groups. 6-Deoxyruidine 5'-monophosphate and 2'(or 3'), 5'-diphosphate were obtained by phosphorylation of 6-deoxyuridine.

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Studies on the Constituents of Asclepiadaceae Plants. I. On the Components of Cynanchum caudatum Max.

Hiroshi Mitsuhashi, Yuzuru Shimizu

1960 Volume 8 Issue 4 Pages 313-317
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.313

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The root of Cynanchum caudatum Max. was proved to contain a glycoside mixture, β-sitosterol and lupeol acetate. The glycosides showed a strong Keller-Killiani reaction, suggesting the presence of 2-deoxy-sugar. The sugar portion of the glycosides was found to be D-cymarose by paper partition chromatography comparing with an authentic specimen and by preparation of cymaronic acid phenylhydrazide, m.p. 152∼154°. One of the aglycone, cynanchogenin, m.p. 167°, was isolated by chromatography using alumina.

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Studies on the Constituents of Asclepiadaceae Plants. II. On the Struture of Cynanchogenin from Cynanchum caudatum Max.

Hiroshi Mitsuhashi, Yuzuru Shimizu

1960 Volume 8 Issue 4 Pages 318-323
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.318

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Hydrogenation of cynanchogenin (I), m.p. 167°, C₂₈H₄₂O₆, gave a dihydro compound (II). Alkaline hydrolysis of (I) gave an unsaturated acid (VIII) and deacylcynanchogenin (VII), C₂₁H₃₂O₅. The same treatment of (II) gave (VII) and a saturated acid (IX). The satruated acid was proved to be 3, 4-dimethylpentanoic acid by synthesis . By the permanganate oxidation, the unsaturated acid was shown to be 3, 4-dimethyl-2-pentenoic acid. Deacylcynanchogenin has one ketone group, one double bond, and four hydroxyl groups, two of which easily undergo acetylation. Reduction of cynanchogenin with lithium aluminum hydride gave a polyol compound (XIV), which was also obtained by the reduction of deacylcynanchogenin with sodium borohydride.

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Synthesis in the Morphinan Group. III. A Synthesis of 2, 3-and 3, 4-Ethylenedioxy-N-methylmorphinan and their Optical Resolution

Mitsuo Sasamoto

1960 Volume 8 Issue 4 Pages 324-329
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.324

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For phamacological evaluation, 2, 3-and 3, 4-ethylenedioxy-N-methylmorphinans were prepared. 3, 4-Ethylenedioxyphenylacetic acid was prepared through two different ways; 6-formylbenzodioxane was converted to the amide, from which two N-methylmorphinan were obtained according to the method of Schnider. The Structrues of the two isomeric N-methylmorphinans were cofirmed by infrared spectral data. 3, 4-Ethylenedioxy-N-methylmorphinan was resolved into the optical antipodes, using bibenzoyl-d-tartaric acid.

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Synthesis in the Morphinan Group. IV. Structural Proof of 2, 3-and 3, 4-Ethylenedioxy-N-methylmorphinan.

Mitsuo Sasamoto

1960 Volume 8 Issue 4 Pages 329-335
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.329

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2, 3-Ethylenedioxy-N-methylmorphinan and 3, 4-ethylenedioxy-N-methylmorphinan, synthesized earlier, were submitted to the Hofmann degradations and by syntheses of their degradation products their structrues were confirmed as 2, 3- and 3, 4-ethylene-dioxyphenanthrene.

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Studies on Streptomyces Antibiotic, Cycloheximide. VII. On the Configuration of Naramycin-B and Isocycloheximide.

Tomoharu Okuda, Makoto Suzuki, Yoshiyuki Egawa

1960 Volume 8 Issue 4 Pages 335-340
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.335

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Physicochemical Comparisons were made on Naramycin-B and isocycloheximide, which are stereoisomers of cycloheximide, and it was confirmed that the two antibiotics are similar but not quite equal to each other, and that, mainly from the interpretations of their rotatory dispersion curves, the absolute configurations of Naramycin-B and isocycloheximide respectively belong to(2S : 4S : 6R : αS)-and (2R : 4S : 6R : αS)-series.

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Action of Cyanogen Bromide on Thiamine. III. Synthesis of 2-Methyl-6-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-5, 6-dihydropyrimido[4, 5-d]pyrimidine (Neocyanothiamine).

Shizuka Kasahara

1960 Volume 8 Issue 4 Pages 340-347
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.340

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From the measurement of absorption spectrum of thiamine dissolved in sodium ethoxide, it is considered that thiamine is converted into the cyclic thiol-form(III) as a result of intramolecular addition of 4-amino group in the pyrimidine ring and the thiazolium ring, losing hydrochloric acid and opening the thiazole ring. The reaction of 0.1 mole of cyanogen bromide with the cyclic thiol-type thiamine, produced from 0.1 mole of thiamine hydrochloride in ethanol suspension by the action of 0.3 mole of sodium ethoxide, gives 2-methyl-6-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-5, 6-dihydropyrimido[4, 5-d]pyrimidine (V). This substance is hydrolyzed into N-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide (IV) by dilute acid and converted into thiochrome through thiolcarbamic ester derivative (XIX) on heating with alcohols and also ecomposed into N-[1-(2-thiacyclobutylidene)ethyl]-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide(VI) and thiamine by the action of sodium hydroxide. On the basis of these experimental results, the mechanism of the formation of thiochrome from thiamine is discussed with that suggested by Sykes, et al. and by Matsukawa, et al.

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Action of Cyanogen Bromide on Thiamine. IV. Studies on 2-Methyl-6-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-5, 6-dihydropyrimido[4, 5-d]pyrimidine (Neocyanothiamine).

Shizuka Kasahara

1960 Volume 8 Issue 4 Pages 348-356
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.348

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2-Methyl-6-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-5, 6-dihydropyrimido[4, 5-d]-pyrimidine(V) is decomposed into thiamine (III), N-(1-methyl-2-thiocyanato-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide (IV), thiamine anhydride (VI), thiochrome (VIII), and HCNO by the action of water. The yield decreases in the order of (III), (IV), (VI), and (VIII), while in hot water, the yield of (VIII) is increased. The action of hydrous acid on (V) gives (IV). On the other hand, the reaction of (V) with acid under anhydrous condition gives its salt (XV), which is converted into 2-imino-3-(2-methyl-4-formamido-5-pyrimidinyl)methyl-3a-methyl-3a, 5, 6, 6a-tetrahydrofuro[2, 3-d]-thiazole (XIII) by the action of sodium hydrogencarbonate and water. (XIII) changes to 2-imino-3-(2-methyl-4-amino-5-pyrimidinyl)methyl-3a-methyl-3a, 5, 6, 6a-tetrahydrofuro[2, 3-d]thiazole (XII) with a loss of formic acid by the action of mineral and acetic acid or sodium hydroxide. When heated with water, (XIII) also changes to 2, 8a-dimethyl-5a, 6, 7, 8a-tetrahydrofuro-[2, 3-h]thiochromine (VII) through (XII) produced by hydrolysis liberating ammonia.

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On the Absolute Configuration of Natural 24-Alkylsterols.

Yukichi Kishida

1960 Volume 8 Issue 4 Pages 357-364
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.357

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(+)-Limonene (I) was converted to (+)-trans-p-methane-1, 2-diol (III) via dihydrolimonene (II) by known methods. (III) was converted to (+)-3-isopropyl-6-oxoheptanoic acid (VI), either by direct oxidation of (III) with Lemieux reagent or by two-step oxidation via keto-aldehyde, 3-isopropyl-6-oxoheptanal (V). (VI) was, in turn, converted to its (+)-ester (VIII), (+)-ketal-alcohol (X), ketal-alcohol tosylate (XI) and finally to a levorotatory ketone, 5-isopropyl-2-heptanone (XII). Since the (-)-ketone (XII) has the same absolute configuration around its asymmetric carbon as (+)-limonene (I), (XII) must be (-)-(S)-5-isopropyl-2-heptanone, corresponding to the 24β-ethyl in the steroid-chain. The antipode of (XII), (+)-(R)-ketone (XII'), has already been obtained directly from β-sito-sterol by Dirscherl and Nahm. Hence the ethyl group of the stigmasterol series must have α-configuration in the extended Plattner's convention proposed by Fieser and Fieser. This result confirmed the recent conclusion which contradicted the deduction Bergmann and others. The author proposes the revision of the older representation of C₂₉-natural sterols in regard to the C-24 configurations.

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Studies on the Periodic Acid Oxidation of N-Glycosides. XV. Studies on the Periodic Acid Oxidation of Anilines. (8). A Consideration on the Mechanism of Periodic Acid Oxidation of α-Glycols.

Hiroya Tanabe

1960 Volume 8 Issue 4 Pages 365-366
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.365

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The hypothesis suggested by Waters on the mechanism of the decomposition of α-glycol with periodic acid was examined and from the fact that in the periodic acid oxidation solutions of α-glycol the formation of a free radical was not observed, this hypothesis was proved not to be reasonable and consequently it was shown that the periodic acid oxidation mechanisms of aniline and of α-glycol were different from each other.

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Studies on Coenzyme Analoges. II. A convenient Synthesis of "Thioinosine."

Morio Ikehara

1960 Volume 8 Issue 4 Pages 367-368
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.367

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Syntheses of Pyridazine Derivatives. IV. Reaction of 3, 6-Dimethoxypyridazine 1-Oxide with Phosphoryl Chloride.

Hiroshi Igeta

1960 Volume 8 Issue 4 Pages 368-369
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.368

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Treatment of 3, 6-dimethoxypyridazine 1-oxide (I) with phosphoryl chloride at room temperatrue gave a chloro-dimethoxyl compound (II), m.p. 86°, and reaction of (II) with sodium methoxide yielded a trimethoxyl compound (III), which was proved to be identical with 3, 4, 6-trimethoxypyridazine. This shows that, when ortho position of the N-oxide group in pyridazine N-oxides is substituted, the reaction with phoshoryl chloride seems to give a chloro compound which has chlorine atom at a position para to the N-oxide group.

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Occurrence of Nucleotides in the Culture Fluid of a Microorganism

Tadashi Okabayashi, Eitaro Masuo

1960 Volume 8 Issue 4 Pages 370-372
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.370

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Uber Taxinin

Torizo Takahashi, Kan-ichi Ueda, Yoshifumi Maki, Katsumaro Minamoto

1960 Volume 8 Issue 4 Pages 372-373
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.372

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Characterization of Hydroxyl Groups and the Result of Dehydrogenation of Pseudokobusine

Mitsutaka Natsume

1960 Volume 8 Issue 4 Pages 374-375
Published: April 25, 1960
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.8.374

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