Chemical and Pharmaceutical Bulletin

Studies on Pilocereine and Related Compounds. II. Cleavage of O-Methylisopilocereine by Metallic Potassium in Liquid Ammonia.

Masao Tomita, Tohru Kikuchi, Kiyoshi Bessho, Yasuo Inubushi

1963 Volume 11 Issue 12 Pages 1477-1483
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1477

JOURNAL FREE ACCESS

Show abstractHide abstract

Potassium-liq. ammonia cleavage of O-methylisopilocereine yielded IIa and IIb as bisected bases. This suggested that the structure of isopilocereine is either Ia or XIa, although the previous assignment of Ia to pilocereine and piloceredine by Djerassi, et al. excluded structure (Ia). The synthesis of lophocerine (IIa) is also reported.

View full abstract

Download PDF (751K)
Studies on Pilocereine and Related Compounds. III. Synthesis of 2, 2', 3-Trimethoxydiphenyl Ether-4', 5- and -4', 6-dicarboxaldehyde.

Masao Tomita, Tohru Kikuchi, Kiyoshi Bessho, Toshio Hori, Yasuo Inubus ...

1963 Volume 11 Issue 12 Pages 1484-1490
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1484

JOURNAL FREE ACCESS

Show abstractHide abstract

As an important intermediate in the synthesis of Ib, several ways of preparing the dialdehyde (IX) were investigated and a considerable increase in total yield was achieved. Synthesis of XXXI, an intermediate in the synthesis of IIb, was also examined.

View full abstract

Download PDF (774K)
Studies on Pilocereine and Related Compounds. IV. Synthesis of O-Methylisopilocereine. (1).

Kiyoshi Bessho

1963 Volume 11 Issue 12 Pages 1491-1494
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1491

JOURNAL FREE ACCESS

Show abstractHide abstract

Base (I), which had been presumed to be O-methylisopilocereine, was synthesized and two racemic diastereomers were isolated. However, the fact that these bases are not O-methylisopilocereine suggested that the latter should be represented by formula (XII), which had been assigned to O-methylpilocereine and O-methylpiloceredine.

View full abstract

Download PDF (510K)
Studies on Pilocereine and Related Compounds. V. Synthesis of O-Methylisopilocereine. (2).

Kiyoshi Bessho

1963 Volume 11 Issue 12 Pages 1495-1499
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1495

JOURNAL FREE ACCESS

Show abstractHide abstract

Base (I), the structure of which had been considered to be that of O-methylpilocereine and O-methylpiloceredine, was synthesized from diphenyl ether dicarboxaldehyde (III). One of its racemic diastereomers was isolated in crystalline state. Both the crystalline base (I) and the mixture of its diastereomers had identical infrared spectra with O-methylisopilocereine in chloroform solution. The chromatographic behaviours also suggested that the formula (I) represents O-methylisopilocereine, not O-methylpilocereine.

View full abstract

Download PDF (593K)
Studies on Pilocereine and Related Compounds. VI. Synthesis of O-Methylisopilocereine. (3).

Kiyoshi Bessho

1963 Volume 11 Issue 12 Pages 1500-1503
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1500

JOURNAL FREE ACCESS

Show abstractHide abstract

Base (Ib) was synthesized by the Ullmann condensation between VII and VIII, and the two racemic diastereomers were obtained in crystalline states. One of them was proved to be O-methylisopilocereine, while the other was identified with the diastereomer obtained by another synthetic method. Non-identities of them with O-methylpilocereine, to which the formula (Ib) had been inadequately assigned, were also proved.

View full abstract

Download PDF (495K)
Studies on Pilocereine and Related Compounds. VII. Cleavage of O-Methylpilocereine by Metallic Potassium in Liquid Ammonia.

Kiyoshi Bessho

1963 Volume 11 Issue 12 Pages 1504-1507
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1504

JOURNAL FREE ACCESS

Show abstractHide abstract

The potassium-liq. ammonia cleavage of O-methylpilocereine was carried out in order to re-examine the structure (Ia) of pilocereine. In addition to the expected bases (II, IIIb, IVa, and IIIa), isopilocereine (Ia) and a phenolic base which is considered to be V were obtained. This result and new molecular formula C₄₅H₆₅O₆N₃ proposed lately by Djerassi, et al. pointed out the structure of pilccereine to be VIa. The formation of isopilocereine on treatment of pilocereine with potassium-liq. ammonia was illustrated as a normal cleavage reaction.

View full abstract

Download PDF (506K)
Studies on Pilocereine and Related Compounds. VIII. Structures of Isopilocereine and Desmethylisopilocereine.

Kiyoshi Bessho

1963 Volume 11 Issue 12 Pages 1507-1510
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1507

JOURNAL FREE ACCESS

Show abstractHide abstract

The structure of isopilocereine (Ib) and desmethylisopilocereine (Ic) were established by potassium-liq. ammonia cleavage reactions of their O-ethyl ethers, Id and Ie.

View full abstract

Download PDF (487K)
Pyridazines. V. The Reaction of Methyl Substituted 4-Nitropyridazine 1-Oxides with Acetyl Chloride.

Masaru Ogata

1963 Volume 11 Issue 12 Pages 1511-1516
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1511

JOURNAL FREE ACCESS

Show abstractHide abstract

Reaction of excess acetyl chloride on a 3-substituted 4-nitro-6-methylpyridazine 1-oxide (Ia, b, c and XIII) result in the formation of 3-substituted 4-chloro-6-formylpyridazine 1-oxide oximes (IIa, b, c and XVIII), together with 3-substituted 4-chloro-6-methylpyridazine 1-oxides (IIa, b, c and XVII). Reaction of 3-methyl-4-nitropyridazine 1-oxide (XII) and 4-nitro-5-methylpyridazine 1-oxide (XIV) with acetyl chloride gave only 3-methyl-4-chloropyridazine 1-oxide (XIII) and 4-chloro-5-methylpyridazine 1-oxide (XV) respectively.

View full abstract

Download PDF (685K)
Pyridazines. VI. Reaction of Methylpyridazine N-Oxides with Amyl Nitrite.

Masaru Ogata

1963 Volume 11 Issue 12 Pages 1517-1522
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1517

JOURNAL FREE ACCESS

Show abstractHide abstract

The reaction of methylpyridazine N-oxides with amyl nitrite in the presence of sodium amide in liquid ammonia afforded the corresponding syn-aldoximes. These syn-aldoximes were isomerized to anti-aldoximes with hydrochloric acid or heating alone except the case of some aldoximes. The configuration of the aldoximes was confirmed by the infrared and nuclear magnetic resonance spectra.

View full abstract

Download PDF (645K)
Pyridazines. VII. Synthesis of Cyanopyridazines.

Masaru Ogata

1963 Volume 11 Issue 12 Pages 1522-1527
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1522

JOURNAL FREE ACCESS

Show abstractHide abstract

3-Chloro, 3-methyl, 3-methoxy, 3-benzyloxy, and 3-phenyl-6-cyanopyridazine (III, VI, X, XII, XIV) was synthesized from 3-chloro, 3-methyl, 3-methoxy, 3-benzyloxy, and 3-phenylpyridazine 1-oxide (II, V, IX, XI, XIII).

View full abstract

Download PDF (692K)
Pyridazines. VIII. Syntheses and Nuclear Magnetic Resonance Spectra of Cinnoline N-Oxides.

Masaru Ogata, Hideo Kano, Kazuo Tori

1963 Volume 11 Issue 12 Pages 1527-1539
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1527

JOURNAL FREE ACCESS

Show abstractHide abstract

Cinnoline 1-oxide (II), cinnoline 2-oxide (III), 4-methylcinnoline 1-oxide (V), 4-methylcinnoline 2-oxide (VI), 3-chlorocinnoline 1-oxide (VIII), and 3-methoxycinnoline 1-oxide (XXI) were synthesized. For confirmation of the structure of these compounds, cinnoline 1-oxide (II) and 3-chlorocinnoline 1-oxide (VIII) were prepared from their corresponding 5, 6, 7, 8-tetrahydro derivatives (XI and XIII) by bromination with N-bromosuccimide followed by dehydrobromination with sodium methoxide. The structures of isomeric 4-methylcinnoline N-oxides were determined by the application of ultraviolet and nuclear magnetic resonance spectroscopies. The nuclear magnetic resonance spectra of the cinnoline N-oxides synthesized were examined. The interpretation of the spectra was made in connection with those of pyridazine N-oxides and of quinoline N-oxides. The proton H₈ shows its signal peak at a lower field than do the other protons, owing to the magnetic anisotropy effect of the N-O group.

View full abstract

Download PDF (1230K)
Studies on the Metabolic N-Demethylation. III. Acceleration of Drug Metabolizing Enzyme in Rat Liver.

Yukio Kuroiwa, Kenichiro Minegishi, Seiichi Okui

1963 Volume 11 Issue 12 Pages 1540-1545
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1540

JOURNAL FREE ACCESS

Show abstractHide abstract

The demethylation activity for the N-methylbarbiturates was localized in the microsomal fraction and required NADPH and oxygen. This activity was increased markedly with pretreatment of some barbiturates but not with carcinogenic substances such as DAB, 3-MC and benzpyrene. The activity of the demethylation or hydroxylation of barbiturates was generally decreased by the pretreatment of carcinogenic substances. In accord with the increase of enzyme activity, in the time course of induction after the pretreatment of phenobarbital, two maximum peaks were appeared around 24∼40 hours and 60∼70 hours when cyclobarbital, methylbarbital, and 3-methyl-MAB were employed as the substrates. By the pretreatment of 3-MC the demethylation of 3-methyl-MAB was stimulated, but the demethylation of methylbarbital was not.

View full abstract

Download PDF (645K)
Thin Layer Chromatography of Steroid Saponins and their Derivatives.

Toshio Kawasaki, Kazumoto Miyahara

1963 Volume 11 Issue 12 Pages 1546-1550
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1546

JOURNAL FREE ACCESS

Show abstractHide abstract

Thin layer chromatography on silica gel-gypsum was applied to steroid saponins and their derivatives such as peracetates and permethylates. The method has many advantages over paper chromatography in speed, sensitivity, and, above all, in resolving power of the closely related high molecular weight saponins and of the slightly polar derivatives.

View full abstract

Download PDF (582K)
Syntheses and Antiviral Activity of 3-Thioxo-6-aryl-3, 4-dihydro-as-triazin-5 (2H)-one and 6-Aryl-as-triazine-3, 5 (2H, 4H)-dione.

Sumiko Watanabe, Takeo Ueda

1963 Volume 11 Issue 12 Pages 1551-1556
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1551

JOURNAL FREE ACCESS

Show abstractHide abstract

Twelve compounds of phenylpyruvic acid thiosemicarbazone derivatives substituted with alkyl group, hydroxy group, alkoxy group or halogen atom at 2, 3-and/or 4-position in benzene ring, nine compounds of 3-thioxo-6-aryl-3, 4-dihydro-as-triazin-5 (2H)-one, five compounds of 3-methylthio-6-aryl-as-triazin-5 (4H)-one, and five compounds of 6-aryl-as-triazine-3, 5 (2H, 4H)-dione were newly synthesized. Among these compounds, 3, 4-dimethoxyphenylpyruvic acid thiosemicarbazone showed remarkable activity on the multiplication of the Mahoney strain of polio virus type 1, while 6-phenyl-, and 6-(p-propoxybenzyl)-3, 4-dihydro-as-triazin-5 (2H)-one, and 6-(p-chlorobenzyl)-as-triazine-3, 5(2H, 4H)-dione were slightly effective on the virus by using 100×TCID₅₀ of the virus.

View full abstract

Download PDF (590K)
Studies on Acetylenic Compounds. XXXIV. Rearrangement of Propargylammonium Halide Derivatives.

Issei Iwai, Tetsuo Hiraoka

1963 Volume 11 Issue 12 Pages 1556-1563
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1556

JOURNAL FREE ACCESS

Show abstractHide abstract

The Stevens type rearrangement of phenylpropargylammonium halide derivatives was carried out. This rearrangement usually consists of 1, 2-shift of migratory group, however, it was found that bis phenylpropargylammonium halide derivative underwent the 1, 4-shift to give an allenic compound. The rearrangement was extended to a ring expansion reaction.

View full abstract

Download PDF (890K)
Studies on Acetylenic Compounds. XXXV. The Cyclization Reaction of some Propargylammonium Derivatives. (1).

Issei Iwai, Tetsuo Hiraoka

1963 Volume 11 Issue 12 Pages 1564-1568
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1564

JOURNAL FREE ACCESS

Show abstractHide abstract

The intramolecular cyclization reaction of propargylammonium halide derivatives was carried out and it was found that dimethyl (2-propynyl) (3-phenyl-2-propynyl)-ammonium bromide (II) gave 2-methylbenz [f] isoindoline (III) on treatment with sodium ethoxide in alcohol and 2-methyl-1-(2-propynyl) pyridinium bromide gave 2-methyl-indolizine (XII) on heating in sodium bicarbonate solution. Analogously, 2-amino-1-(2-propynyl) pyridinium bromide (XV) afforded 2-methylimidazo [1, 2-α] pyridine (XVI).

View full abstract

Download PDF (581K)
Studies on Acetylenic Compounds. XXXVI. Total Synthesis of Ethyl 3-Amino-3-deoxy-β-DL-arabinofuranoside.

Tadahiro Iwashige, Motoji Asai, Issei Iwai

1963 Volume 11 Issue 12 Pages 1569-1575
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1569

JOURNAL FREE ACCESS

Show abstractHide abstract

Ethyl 5-O-(2'-tetrahydropyranyl)-2, 3-anhydro-β-DL-lyxofuranoside (VIDL) was predominantly formed by the action of alkali on a chlorohydrin derivative, which was prepared by hypochlorous acid addition of 2'-ethoxy-5-(2'-tetrahydropyranyloxy) methyl-2, 5-dihydrofuran (I). Then, ethyl 3-amino-3-deoxy-β-DL-arabinofuranoside (IXDL) was synthesized from VIDL.

View full abstract

Download PDF (720K)
Metabolic Products of Fungi. XXIII. On Ustilaginoidins. (3). The Structures of Ustilaginoidins B and C.

Shoji Shibata, Yukio Ogihara

1963 Volume 11 Issue 12 Pages 1576-1578
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1576

JOURNAL FREE ACCESS

Show abstractHide abstract

The structures of ustilaginoidin B, C₂₈H₁₈O₁₁, m.p. >300°, [α]²⁵_D-360°(dioxan) and ustilaginoidin C, C₂₈H₁₈O₁₂, m.p. >300°, [α]²⁵_D-260°(dioxan) which were isolated as the pigments of Ustilaginoidea virens (COOKE) TAKAHASHI, were studied mostly by the NMR spectral analyses of their peracetates to conclude as being formulated as II (R=H) and III (R=H), respectively.

View full abstract

Download PDF (366K)
Untersuchungen auf dem Gebiet der mikrobiologischen Umsetzung. XX. Hydroxylierung von Progesteron mittels Syncepharastrum racemosum COHN (5).

Yoshihiro Sato, Tokuji Tanaka, Mitsugi Kato, Kyosuke Tsuda

1963 Volume 11 Issue 12 Pages 1579-1585
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1579

JOURNAL FREE ACCESS

Show abstractHide abstract

Inkubation von Progesteron (I) mit Kulturen von Syncephalastrum racemosum COHN ergab neben den bekannten Produkten, namlich 15β-Hydroxyprogesteron (II), 6β, 11α-Dihydroxyprogesteron (VI), 7β, 15β-Dihydroxyprogesteron (IV) und 7β, 14α, 15β-Trihydroxyprogesteron (VII), noch unbekannte Produkte, namlich 6β, 15β-Dihydroxyprogesteron (V) und 15β-Hydroxy-5α-pregnan-3, 6-20-trion (III).

View full abstract

Download PDF (888K)
Uber eine Reaktion der N-Oxyde der Chinolin-Reihe mit Bleitetraacetat (II).

Akihiro Ohta

1963 Volume 11 Issue 12 Pages 1586-1587
Published: December 25, 1963
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.11.1586

JOURNAL FREE ACCESS

Show abstractHide abstract

Bei der Einwirkung von Bleitetrabenzoat auf Chinolin-N-oxyd (I) und bei der Oxydation von 2-Benzoyloxychinolin (IV) mit Permaleinsaure wurde N-Benzoyloxycarbostyril (II) erhalten. Dabei wurde der Mechanismus der Bleitetraacetat-Oxydation von Chinolin-N-oxyd (I) vorgeschlagen.

View full abstract

Download PDF (360K)

Register with J-STAGE for free!