Chemical and Pharmaceutical Bulletin

Titration in Nonaqueous Solutions. XV. Direct Differential Potentiometric Titration by Glass-Glass Retarded Electrodes. (1). Titration in Anhydrous Acetic Acid.

Tetsu Kashima

1958 Volume 6 Issue 3 Pages 229-234
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.229

JOURNAL FREE ACCESS

Show abstractHide abstract

Direct differential potentiometric titrations in nonaqueous solutions were carried out using two glass electrodes, one of which is used as a retarded electrode. One and the greatest disadvantages of nonaqueous potentiometric titrations employing a reference electrode whose solvent is different from that of the solution or of the titrant, the fluctuation of liquid junction potentials between the two solutions of different solvents, can be overcome by this method. This method applied to the determinations of four derivatives of 1-phenyl-3-methyl-3-pyrazolin-5-one and several acid salts of diphenhydramine in anhydrous acetic acid solution with perchloric acid in acetic acid or p-dioxane as the titrant, was shown to give satisfactory and reproducible results.

View full abstract

Download PDF (618K)
4, 5-Substituted Pyridazines. IV. The Effect of Some Substituents at the 4-Position on the Ultraviolet Absorption Spectrum of 3, 6-Dichloropyridazine.

Tsukasa Kuraishi

1958 Volume 6 Issue 3 Pages 234-237
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.234

JOURNAL FREE ACCESS

Show abstractHide abstract

Ultraviolet absorption spectra of some 4-substituted 3, 6-dichloropyridazines were measured and qualitative explanation of the bands was presented. Solvent effect and substituent effect at the 4-position of pyridazine ring were compared with those of 3, 6-dichloropyridazine.

View full abstract

Download PDF (462K)
Studies on Cholestapolyenes. VI. 3-Cyclohexylcholestane and its Derivatives.

Ko Arima

1958 Volume 6 Issue 3 Pages 238-240
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.238

JOURNAL FREE ACCESS

Show abstractHide abstract

3β-Cyclohexylcholestane was prepared from cholest-5-ene-3β-carboxylic acid and the fact is that the carbanion formed in the Grignard reagent of 3β-chlorocholest-5-ene was β-oriented in reaction with cholestan-3-one, i.e. the conformation at 3-position is retained. Discussions were also made on the structure of 3β-cyclohexylcholestan-3α-ol and 3-cyclohexylcholest-2-ene.

View full abstract

Download PDF (462K)
Studies on Cholestapolyenes. VII. Bicholestane and its Derivatives.

Ko Arima

1958 Volume 6 Issue 3 Pages 241-245
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.241

JOURNAL FREE ACCESS

Show abstractHide abstract

It has been found that the reaction of cholestan-3-one and the Grignard reagent of 3-chlorocholestane afforded 3β, 3'β-bicholestan-3α-ol, irrespective of the α-or β-conformation of the 3-position in the starting material. It was thereby established that the carbanion formed in the Grignard reagent of 3β-chlorocholestane was β-oriented.

View full abstract

Download PDF (632K)
Studies on Cholestapolyenes. VIII. Separation of Stereoisomers of Bicholestane.

Ko Arima

1958 Volume 6 Issue 3 Pages 245-248
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.245

JOURNAL FREE ACCESS

Show abstractHide abstract

Three kinds of stereoisomers of bicholestane were isolated from the Grignard coupling reaction of 3-chlorocholestane and one of these was a new stereoisomer, not found in any literature to date. These three isomers are invariably formed, irrespective of the α-or β-conformation of the chlorine atom in the starting 3-chlorocholestane.

View full abstract

Download PDF (478K)
Studies on Percutaneous Absorption. II. Effect of the Incorporated Substance.

Hisashi Nogami, Manabu Hanano

1958 Volume 6 Issue 3 Pages 249-255
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.249

JOURNAL FREE ACCESS

Show abstractHide abstract

1. The percutaneous absorption of salicylic acid from several solutions was influenced by the material incorporated in it. The largest obstructive effect was shown in the case of polyethylene glycol 400 and Carbowax 6000. The same effect was shown in propylene glycol and glycerol, and the effect of propylene glycol was larger than that of glycerol. Glucose did not show any effect. The absorption decreased with concentration of the material which showed a pronounced obstructive effect. 2. Degrees of absorption from various aqueous solutions were parallel to the degree of partition between benzene and their solution. 3. Effect of viscosity and surface tension on abosorption was not shown within the region of this experiment.

View full abstract

Download PDF (740K)
Studies on the Components of Rhodea japonica ROTH. XI. Structure of Rhodeasapogenin. (4).

Hayao Nawa

1958 Volume 6 Issue 3 Pages 255-263
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.255

JOURNAL FREE ACCESS

Show abstractHide abstract

Several years ago the author isolated rhodeasapogenin, a new steroidal sapogenin, from the leaves of Rhodea japonica ROTH. and presumed its structure to be 5β, 22b-spirostane-2β, 3α-diol. In the present work it was found that isorhodeasapogenic acid is identical with tokorogenic acid and that isorhodeasapogenin has a structure of 1β, 3b-dihydroxy-5β, 25D-spirostane. Further, finding that rhodeasapgenin is degradated to methyl 1β, 3β-diacetoxyetiocholanate, the author corrected the previously proposed structure of rhodeasapogenin to 1β, 3β-dihydroxy-5β, 25L-spirostane. The two reactions of isorhodeasapogenin which appeared unusual could be well explained by assigning the above structure to this compound.

View full abstract

Download PDF (905K)
Studies on Naphthyridines. I. Synthesis of 1, 6-Naphthyridine.

Nobuo Ikekawa

1958 Volume 6 Issue 3 Pages 263-269
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.263

JOURNAL FREE ACCESS

Show abstractHide abstract

A new synthetic process is described for building up the pyridine ring by the utilization of an active methyl group and a carboxyl adjacent to it in the pyridine ring. The reaction of ethyl 2-methylnicotinate and formaldehyde (or acetaldehyde) gave a lactone which was led to an amide, and its oxidation gave 5-hydroxy-1, 6-naphthyridine. 1, 6-Naphthyridine and 7-methyl-1, 6-naphthyridine were synthesized from their 5-hydroxy derivatives via the chloro and hydrazino compounds. Methyl-1, 6-naphthyridine N-oxide obtained by the Skraup reaction of 4-amino-2-picoline 1-oxide was established as the 5-methyl derivative.

View full abstract

Download PDF (813K)
Studies on Naphthyridines. II. Synthesis of 2, 7-Naphthyridine.

Nobuo Ikekawa

1958 Volume 6 Issue 3 Pages 269-272
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.269

JOURNAL FREE ACCESS

Show abstractHide abstract

Reaction of 4-methylnicotinic acid with formaldehyde or acetaldehyde gave a lactone, which was led to the amide, and this was oxidized to 1-hydroxy-2, 7-naphthyridine. 2, 7-Naphthyridine and 3-methyl-2, 7-naphthyridine were synthesized from 1-hydroxy derivatives via 1-chloro and 1-hydrazino compounds.

View full abstract

Download PDF (534K)
Synthese von Derivaten der Cinchona-Alkaloide. XXVIII. Synthese von 2'-Hydroxydihydronichin.

Yoshiro Kobayashi

1958 Volume 6 Issue 3 Pages 273-277
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.273

JOURNAL FREE ACCESS

Show abstractHide abstract

Dihydronichin wurde nach der Benzoylierung mit Wasserstoffperoxyd in Eisessig-Losung oxydiert. Das entstandene Mono-und Dibenzoyldihydronichin-N-oxyd wurde durch Behandlung mit phosphoroxychlorid in Chloroform-Losung in die entsprechenden 2'-Chlordihydronichin-Derivate ubergefuhrt. Die beiden letzteren gaben beim Verseifen das 2'-Hydroxydihydronichin.

View full abstract

Download PDF (667K)
Studies on Decomposition and Stabilization of Drugs in Solution. II. Chemical Kinetic Studies on Aqueous Solution of Methantheline Bromide.

Hisashi Nogami, Masayoshi Horioka, Shoji Awazu, Hideo Yamada

1958 Volume 6 Issue 3 Pages 277-282
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.277

JOURNAL FREE ACCESS

Show abstractHide abstract

1. It was evidenced by the ultraviolet absorption spectral analyses that the decomposition of Methantheline Bromide (M.B.) in aqueous solution was the hydrolysis of ester linkage. 2. The determination of M.B. was carried out separating from its decomposed substances by the colorimetric procedure using ethylene dichloride as a solvent, bromocresol purple as a complexing dye, in a buffer solution of pH 6.5. 3. The decomposition was recognized as a first-order reaction at any given pH value and the reaction was catalyzed by hydrogen ion, hydroxyl ion, and water. The constants were determined as follows : [numerical formula] [numerical formula]

View full abstract

Download PDF (654K)
Studies on Decomposition and Stabilization of Drugs in Solution. III. Chemical Kinetic Studies on Aqueous Solution of 2-Diethylaminoethyl Diphenylglycolate Methobromide

Hisashi Nogami, Noriyasu Nakajima

1958 Volume 6 Issue 3 Pages 283-286
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.283

JOURNAL FREE ACCESS

Show abstractHide abstract

1. It was evidenced by the ultraviolet absorption spectral analyses that the decomposition of 2-diethylaminoethyl diphenylglycolate methobromide in aqueous solution is the hydrolysis of ester linkage. 2. The determination of 2-diethylaminoethyl diphenylglycolate methobromide was carried out, separating it from its decomposed substances, by a colorimetric procedure using ethylene dichloride and bromocresol purple in a buffer solution of pH 6.5. 3. The decomposition was recognized as a first-order reaction and catalyzed by hydrogen ion, hydroxyl ion, and water. The constants were determined as follows : [numerical formula] [numerical formula]

View full abstract

Download PDF (449K)
Detoxication and Excretion of Radioactive Strontium. IV. Effect of Sodium Calcium Citrate and the Mode of Action of Citrate.

Yosoji Ito, Susumu Tsurufuji, Mikio Shikita, Sadahiko Ishibashi

1958 Volume 6 Issue 3 Pages 287-290
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.287

JOURNAL FREE ACCESS

Show abstractHide abstract

After the injection of radioactive strontium, a mixture of trisodium citrate and monosodium monocalcium citrate was injected into rats and the effect of monosodijm monocalcium citrate injection in accelerating the excretion of radiostrontium was compared with the effect of the injection of trisodium citrate only. Greatly enhanced excretion of radiostrontium into urine was found in the rats treated with sodium calcium citrate, without any symptom of hypocalcemia. When citrate was injected into rats in the form of either trisodium salt or sodium calcium salt, citrate level in blood plasma was greatly elevated and nearly one-half of injected citrate was found in the urine within six hours. Mechanism of the action of citrate on the excretion of radioactive strontium is discussed and attributed to its chelating ability.

View full abstract

Download PDF (516K)
Application of Chromatography. XXXIV. Structure of the Purple Fluorescent Substance produced by Eremothecium ashbyii.

Toru Masuda, Toyokazu Kishi, Mitsuko Asai

1958 Volume 6 Issue 3 Pages 291-299
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.291

JOURNAL FREE ACCESS

Show abstractHide abstract

Basing on various experimental results the authors corrected the conclusion made in previous papers. In the present work the photodecomposition product of V-compound produced by Er. ashbyii was established to be 2, 4, 7-trihydroxy-6-methylpteridine, and therefore the structure of V-compound was presumed to be as shown below.

View full abstract

Download PDF (801K)
Studies on Uncaria Alkaloid. XVIII. Structure of Uncarine. (13). Structure of Uncarine-A and Uncarine-B.

Toshikazu Nozoye

1958 Volume 6 Issue 3 Pages 300-306
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.300

JOURNAL FREE ACCESS

Show abstractHide abstract

A spiro-type ring was found to be attached to the 3-position of the oxindole ring in uncarine-A and -B from the fact that lithium aluminum hydride reduction of these compounds afforded indoline derivatives and that the application of methyl iodide in the presence of sodium methoxide afforded 1-methyluncarine-A and 1-methyluncarine-B methiodide. Examination was made as to which carbon in the uncarine molecule this spiro bonding existed and the possibilities of the formulae (XIV) and (XV) were considered. However, measuremnt of pK revealed that N_b and the carbonyl in the oxindole were in very close proximity in the uncarine-A molecule. Relationship between uncarine-A and -B would be well explainable by assuming 4-epimeric structures and conformational formulae (XXI) for uncarine-A and (XXII) for uncarine-B were for warded.

View full abstract

Download PDF (717K)
Studies on Uncaria Alkaloid. XIX. On Mitraphylline.

Toshikazu Nozoye

1958 Volume 6 Issue 3 Pages 306-308
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.306

JOURNAL FREE ACCESS

Show abstractHide abstract

Mitraphylline was extracted from Uncaria Kawakamii HAYATA. Mitraphylline was considered to be a steric isomer of uncarine since their compositions were the same and their ultraviolet and infrared spectra showed close similarity. It was assumed that mitraphylline is an isomer with steric configuration of 15-20 positions different from that in uncarine and a β-configuration was presumed for the 4-position by pKa measurement, same as in uncarine-B. From these experimental results, formula (III) was given to mitraphylline.

View full abstract

Download PDF (413K)
Studies on Uncaria Alkaloid. XX. Structure of Rhynchophylline. (5). Structure of Rhynchophylline and Isorhynchophylline.

Toshikazu Nozoye

1958 Volume 6 Issue 3 Pages 309-312
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.309

JOURNAL FREE ACCESS

Show abstractHide abstract

Reduction of rhynchophylline with lithium aluminum hydride afforded an indoline derivative, which indicated the 3-position of the oxindole ring in its molecule is a spiro type, and the formula (III) was forwarded for rhynchophylline in analogy with uncarine. Rhynchophylline and isorhynchophylline are considered to be 4-epimers, similar to uncarine-A and -B, because their compositions are the same, their ultraviolet and infrared spectra are in close similarity, and the two easily undergo isomerization. From the measurement of pK, the formula (V) for rhynchophylline and (IV) for isorhynchophylline are proposed.

View full abstract

Download PDF (490K)
Synthesis in the Benzoquinolizine Group. XXIV. A Synthesis of rac-Dihydroisorotundine.

Kitaro Mizukami

1958 Volume 6 Issue 3 Pages 312-317
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.312

JOURNAL FREE ACCESS

Show abstractHide abstract

A synthesis of rac-dihydroisorotundine (F) was described. Thus β-3, 4-dimethoxyphenethylamine, formaldehyde, and methylmalonic acid were condensed to yield 2-methyl-2-(3, 4-dimethoxyphenethylaminomethyl) malonic acid (VI) in an excellent yield, which suffered a smooth decarboxylation when boiled with hydrous acetic acid. The resultant monocarboxylic acid (VII) was esterified and then condensed with ethoxycarbonylacetyl chloride, furnishing a good yield of the amide (VIII), which was cyclized and reduced to form the isoquinoline derivative (IX). The latter underwent a smooth Dieckmann condensation, giving the β-keto ester (X) which, in conformity with its structure, was soluble in dilute sodium hydroxide solution and gave a positive ferric chloride color test. When boiled with 10% hydrochloric acid this underwent ketone fission and the resultant ketone (XI) was isolated in a fair yield, of which the corresponding dimethylketal (XII) was prepared by treating with methyl orthoformate in the presence of dry hydrogen chloride. The latter was found rather stable to heat and could be distilled without decomposition, but suffered a loss of a molecule of methanol when heated with aluminum tert-butoxide at 220°, thus furnishing rac-dihydroisorotundine (F) as a faint yellow syrup, which was characterized through its crystalline methiodide.

View full abstract

Download PDF (722K)
A New Color Test for Yohimbine-type Compounds ; with Special Reference to Rauwolfia Alkaloids.

Hidehiko Kaneko

1958 Volume 6 Issue 3 Pages 318-319
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.318

JOURNAL FREE ACCESS

Show abstractHide abstract

The color developed by superimposing concentrated sulfuric acid, containing 0.5% of nitrite, over acetic acid solution of a sample of yohimbine-type alkaloids was found to be specific not only for tetrahydro-β-carboline type but also to anhydronium bases.

View full abstract

Download PDF (307K)
Reduction of 2, 4-Disubstituted Resorcinols

Koichi Tomino

1958 Volume 6 Issue 3 Pages 320
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.320

JOURNAL FREE ACCESS

Download PDF (245K)
A Certain Strain of Soil Bacteria capable of metabolizing D-Forms but not L-Forms of threo-2-Phenylserine and Its Benzoyl Derivative

Yukio Kameda, Etsuko Toyoura, Yukio Kimura, Yasuko Ohsumi

1958 Volume 6 Issue 3 Pages 321
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.321

JOURNAL FREE ACCESS

Download PDF (294K)
Microdetection of Carbon in Organic and Inorganic Compounds by Ignition with Sodium Amide

Tsutomu Momose, Yo Ueda, Yoshiko Mukai

1958 Volume 6 Issue 3 Pages 322
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.322

JOURNAL FREE ACCESS

Download PDF (257K)
A New Deoxygenation Reaction of an Aromatic Heterocyclic N-Oxides

Eisaku Hayashi, Hiroshi Yamanaka, Kazuko Shimizu

1958 Volume 6 Issue 3 Pages 323
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.323

JOURNAL FREE ACCESS

Download PDF (271K)
Isolation of Alkaloids from Vinca (Lochnera) rosea L. REICHB.

Masao Shimizu, Fumihiko Uchimaru

1958 Volume 6 Issue 3 Pages 324-325
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.324

JOURNAL FREE ACCESS

Download PDF (385K)
A New Triterpenoid Alcohol, 24-Methylenecycloartanol, as its Ferulate, from Rice Bran Oil

Genkichi Ohta, Masao Shimizu

1958 Volume 6 Issue 3 Pages 325-326
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.325

JOURNAL FREE ACCESS

Download PDF (336K)
Uber die Konstitution des Alkylphenanthrens vom Schmp. 89∼90°, eines Dehydrierungsprodukts des Anhydroignavinols bzw. Hypognavinols

Eiji Ochiai, Toshihiko Okamoto, Shoji Hara, Shinichiro Sakai, Mitsutak ...

1958 Volume 6 Issue 3 Pages 327-328
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.327

JOURNAL FREE ACCESS

Download PDF (357K)
Studies on Cycloheximide and its New Stereoisomeric Antibiotic

Tomoharu Okuda, Makoto Suzuki, Yoshiyuki Egawa, Kokichi Ashino

1958 Volume 6 Issue 3 Pages 328-330
Published: June 20, 1958
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.6.328

JOURNAL FREE ACCESS

Download PDF (406K)

Register with J-STAGE for free!