Chemical and Pharmaceutical Bulletin

Fluorometric Study on the Metal Chelates of Flavone Derivatives. III. Crystal Structures of 4'-Bromo-3-hydroxyflavone and 4'-Bromo-5-hydroxyflavone

TOKISHI HAYASHI, SATOSHI KAWAI, TAKEO OHNO, YOICHI IITAKA, TOSHIO AKIM ...

1974 Volume 22 Issue 6 Pages 1219-1226
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1219

JOURNAL FREE ACCESS

Show abstractHide abstract

X-ray crystal structure analysis of 4'-bromo-5-hydroxyflavone and 4'-bromo-3-hydroxyflavone was carried out to investigate the structures of pyrone ring and hydrogen bonding which may have some relation to the fluorescence emission. The bond lengths of the carbonyl groups in 4'-bromo-5-hydroxyflavone and 4'-bromo-3-hydroxyflavone were found to be 1.245 and 1.232 A respectively. This is consistent with the fact that 5-hydroxyl group forms a stronger hydrogen bond than 3-hydroxyl group. On the other hand, as described in the previous paper, the carbonyl absorption bands of type I compounds occurred in shorter wavelength region than those of type II, and a similar phenomenon was also observed in 4'-bromo-5-hydroxyflavone and 4'-bromo-3-hydroxyflavone. The serious inconsistency between the bond lengths measured by X-ray analysis and the stretching frequencies observed in infrared spectra for the carbonyl group is considered to be caused by a coupling effect. The differences in planarity and aromaticity between type I and type II were not considered to be significant, but the aromaticity of pyrone ring in type II is presumed to be increased remarkably in their metal chelates, which explains the strong fluorescence emission observed in their metal chelates. The 4'-bromo-3-hydroxyflavone forms an intermolecular hydrogen bonding only in crystalline state.

View full abstract

Download PDF (809K)
On the Mass Spectra of Several Furanocoumarins having Various Isoprenoidal Residues

YASUHISA SAIKI, MITSUO UCHIDA, OSAMU OKEGAWA, SEIGO FUKUSHIMA

1974 Volume 22 Issue 6 Pages 1227-1232
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1227

JOURNAL FREE ACCESS

Show abstractHide abstract

Mass spectra of several disubstituted furanocoumarins, namely phellopterin, byakangelicol, byakangelicin, anhydrobyakangelicin, neobyakangelicol and alloisoimperatorin were elucidated. The mass spectra of these compounds are characteristic respectively, especially on cleavages of their side chains. The results are shown in Fig. 1-6 and Chart 1-6.

View full abstract

Download PDF (608K)
Studies on Pentenomycins. II. The Structures of Pentenomycin I and II, New Antibiotics

KIMIO UMINO, NOBUYUKI TAKEDA, YUKIO ITO, TOMOHARU OKUDA

1974 Volume 22 Issue 6 Pages 1233-1238
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1233

JOURNAL FREE ACCESS

Show abstractHide abstract

The structures of pentenomycins I and II, new antibiotics produced by Streptomyces eurythermus MCRL 0738, were proposed to be 4, 5-dihydroxy-5-hydroxymethyl-cyclopent-2-en-1-one and 5-hydroxy-5-hydroxymethyl-4-acetoxy-cyclopent-2-en-1-one respectively by chemical and spectroscopic methods.

View full abstract

Download PDF (659K)
Equilibrium Studies of 5-Substituted 4-Hydroxy-2-methylpyrimidines. I. The Ionization Constants in Aqueous Solution

TAKAYASU KITAGAWA, SATOSHI MIZUKAMI, EIZO HIRAI

1974 Volume 22 Issue 6 Pages 1239-1255
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1239

JOURNAL FREE ACCESS

Show abstractHide abstract

The ionization constants of 5-substituted 4-hydroxy-2-methylpyrimidines (1-11) and some of their methyl derivatives, 4-methoxy-2-methylpyrimidines, 1, 2-dimethyl-4 (1H)-pyrimidones and 2, 3-dimethyl-4 (3H)-pyrimidones were determined. From the ionization constants, the degree of lactim-lactam tautomerism in the 4-hydroxypyrimidines was estimated. It was found that each of the pyrimidines exist mainly as a mixture of lactam forms (4 (1H)-pyrimidone and 4 (3H)-pyrimidone) in approximately equal amounts, in aqueous solution (ca. 1×10^-4M). The results were also supported by ultraviolet absorption spectroscopy. The substituent effect on the tautomerism was discussed in connection with the Hammett equation for the basicity of the pyrimidines.

View full abstract

Download PDF (1561K)
Reductive Cleavage Reaction of N, N'-, N, O- and N, S-Linked Alkylidene Compounds by Sodium Borohydride

KUNIAKI SHIMIZU, KEIICHI ITO, MINORU SEKIYA

1974 Volume 22 Issue 6 Pages 1256-1260
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1256

JOURNAL FREE ACCESS

Show abstractHide abstract

Sodium borohydride reduction was undertaken with a variety of N, N'-, N, O- and N, S-linked alkylidene compounds in aqueous ethanolic medium at room temperature. It has been realized that reductive cleavage of one of these two alkylidene carbon-heteroatom bonds is generally effected in this reduction, disclosing which alkylidene bond is initially cleaved when the two bonds are different.

View full abstract

Download PDF (651K)
Methanesulfonic Acid Derivative of p, p'-Diaminodiphenylsulfone. II. Pharmacokinetics and Availability of Parental Drug in Rabbit

YUKIHISA KURONO, KEN IKEDA, KANETO UEKAMA

1974 Volume 22 Issue 6 Pages 1261-1264
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1261

JOURNAL FREE ACCESS

Show abstractHide abstract

Pharmacokinetic studies on various methanesulfonic acid derivatives of p, p'-diamino-diphenylsulfone (Da) were carried out on rabbit and the liberation of parental Da was pursued. The general formula of the studied derivatives is NaO₃SHC__RHN-C₆H₄-SO₂-C₆H₄-NHC__RHSO₃Na, where R are H-, CH₃-, HOCH₂ (CHOH)₄-(promin) and C₆H₅-. The time courses of the blood concentration for all the derivatives and parental Da administered intravenously were represented in biexponential equations. The elimination rates of the water-soluble derivatives were about 10-fold larger than that of parental Da. The distribution volume of central compartment for Da was larger than those of the derivatives. No detectable amount of Da was found in blood after the i. v. administrations of promin and the derivative of R=H. From the viewpoint of drug availability, the area under liberated Da vs. time curve was compared to that of intact Da and deconvolution calculation was also carried out.

View full abstract

Download PDF (501K)
Studies on the Smiles Rearrangement. XIV. Novel Reactions of 1, 3-Dimethyl-5-nitro-6-chlorouracil with 2-Aminothiophenol

YOSHIFUMI MAKI, TOKIYUKI HIRAMITSU, MIKIO SUZUKI

1974 Volume 22 Issue 6 Pages 1265-1268
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1265

JOURNAL FREE ACCESS

Show abstractHide abstract

The reaction of 1, 3-dimethyl-5-nitro-6-chlorouracil with 2-aminothiophenol in benzene containing an excess of triethylamine gave 1, 3-dimethyl-10H-pyrimido (5, 4-b) (1, 4) benzothiazine-2, 4 (1H, 3H) dione quantitatively via the Smiles rearrangement. The reaction in acetic acid, however, resulted in the formation of 2-methyl-4-nitropyrimido (4, 3-b) benzothiazoline-1, 3 (2H, 10H)-dione in 78% yield, involving an unusual uracil-ring cleavage which appears to occur in a benzothiazoline intermediate in the course of the acid-catalized Smiles rearrangement.

View full abstract

Download PDF (578K)
Photochemical Synthesis of Condensed Triazole N-Oxide

YOSHIFUMI MAKI, MIKIO SUZUKI, KEIJI IZUTA, SHUNJI IWAI

1974 Volume 22 Issue 6 Pages 1269-1274
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1269

JOURNAL FREE ACCESS

Show abstractHide abstract

Photolysis of 1, 3-dimethyl-5-nitro-6-benzylidenemethylhydrazinouracil (IV) resulted in the formation of 1, 5, 7-trimethyl-3-phenyl-4, 6 (5H, 7H)-pyrazolo (3, 4-d) pyrimidinedione (V) and 3, 4, 6-trimethyl-5, 7 (4H, 6H)-triazolo (4, 5-d) pyrimidinedione 1-oxide (VI). Upon irradiation of 1, 3-dimethyl-5-nitro-6-acetophenylidenemethylhydrazinouracil (VIII), however, VI was obtained exclusively in excellent yield. On the basis of mechanistic consideration on these photocyclizations, a new photochemical synthesis of condensed 3-alkyltriazole 1-oxides was developed.

View full abstract

Download PDF (759K)
Intramuscular Absorption of Drugs from Oily Solutions in the Rat

TAEKO TANAKA, HIROSHI KOBAYASHI, KATSUHIKO OKUMURA, SHOZO MURANISHI, H ...

1974 Volume 22 Issue 6 Pages 1275-1284
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1275

JOURNAL FREE ACCESS

Show abstractHide abstract

Oily solutions of various kind of drugs were injected into the hind leg of rats and the intramuscular absorption was investigated by the local clearance method. The intramuscular absorption of drugs having moderate lipid solubility was more rapid than that of the oily solvent itself and proceeded by the apparent first-order process. Apparent absorption rate constants were affected mainly by injection volume and by the physicochemical properties of drugs and oily solvents. The kinetic results are also consistent with a postulate that the drug was mainly absorbed after being transferred from the oily phase to the aqueous phase, and a fairly good correlationship between partition coefficient and the apparent absorption rate constant was obtained. In the case of drugs having extremely high partition coefficient, the absorption rates were very slow, for which the solubility of the drugs in the tissue fluid appeared to be a critical factor.

View full abstract

Download PDF (905K)
Photodynamic Action of Phloxine on Mitochondrial Respiration

FUMIO OBATA

1974 Volume 22 Issue 6 Pages 1285-1290
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1285

JOURNAL FREE ACCESS

Show abstractHide abstract

Photodynamic action of phloxine on mitochondrial respiration was examined, using rat liver mitochondria. Rat liver mitochondria were suspended in a medium containing phloxine, and irradiated with visible light in the presence of oxygen. The respiratory activities of the photooxidized mitochondria were assayed. The results are summarized as follows. (1) Phloxine-sensitized photooxidation of mitochondria inhibited 2, 4-dinitrophenol (2, 4-DNP)-released respiration. It can be deduced, from an approximate calculation, that the released respiration was inhibited by 10% as every 3 nmoles of oxygen per mg of mitochondrial protein was consumed by photooxidation. (2) Phloxine-sensitized photooxidation of mitochondria released the suppressed respiration. The supernatant obtained by centrifugation of photooxidized mitochondria also released the suppressed respiration of intact mitochondria. This suggests that certain uncoupling factors were released from photooxidized mitochondria. Uncoupling factor in question may be unsaturated fatty acids or U-factor, because bovine serum albumin abolished the respiration-releasing effect of the supernatant of photooxidized mitochondria.

View full abstract

Download PDF (718K)
Rearrangement in Dihydroresorcinol Derivatives. XI. Photolysis and Thermolysis of 3-Azido-2-cyclohexen-1-ones and 2-Cyclopenten-1-ones

YASUMITSU TAMURA, SHOICHI KATO, YOSHINOBU YOSHIMURA, TADASHI NISHIMURA ...

1974 Volume 22 Issue 6 Pages 1291-1296
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1291

JOURNAL FREE ACCESS

Show abstractHide abstract

Both photolysis and thermolysis of 2-alkylsubstituted 3-azido-2-cyclohexen-1-ones and -2-cyclopenten-1-ones in methanol gave mainly the α-aminoketal derivatives, although the corresponding 2-unsubstituted compounds gave the Curtius-type rearrangement products.

View full abstract

Download PDF (786K)
Drug Interactions. II. Binding of Some Pyrazolone and Pyrazolidine Derivatives to Bovine Serum Albumin

SHOJI OZEKI, KIKUO TEJIMA

1974 Volume 22 Issue 6 Pages 1297-1301
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1297

JOURNAL FREE ACCESS

Show abstractHide abstract

The binding of some pyrazolone and pyrazolidine derivatives to bovine serum albumin was investigated by a dynamic dialysis method. The drugs used were aminopyrine, antipyrine, 4-aminoantipyrine, phenylbutazone, and oxyphenbutazone. Analysis of the binding data indicated that albumin possesses a single strong binding site and secondary classes of several sites with a much lower affinity for the drugs examined and the values for the association constant of the pyrazolidine derivatives are much greater than that of the pyrazolone derivatives. The affinity of binding is also shown to depend on the hydrophobic character of each drug, as expressed by a partition coefficient. The thermodynamic parameters indicated that these interactions are exothermic and occur spontaneously under the experimental conditions used. It is possible that the pyrazolone derivatives compete with pyrazolidine derivatives for plasma protein binding. However, the extended calculation for the whole body indicates that the plasma protein binding of pyrazolone and pyrazolidine derivatives probably play only a minor role in clinical medication.

View full abstract

Download PDF (632K)
Studies on Tetrahydroisoquinolines. VI. Synthesis of (±)-Thaliporphine and (±)-Glaucine via a p-Quinol Acetate

OSAMU HOSHINO, TADASHI TOSHIOKA, BUNSUKE UMEZAWA

1974 Volume 22 Issue 6 Pages 1302-1306
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1302

JOURNAL FREE ACCESS

Show abstractHide abstract

Acid-catalyzed (conc. sulfuric acid-acetic anhydride) reaction of p-quinol acetate (IIb) prepared by lead tetraacetate oxidation of (±)-codamine (Ic) was found to give (±)-4-acetoxy-O-acetylthaliporphine (VII) and (±)-O-acetylthaliporphine (IX), respectively. Both VII and IX were converted into (±)-thaliporphine (IV), whose methylation gave (±)-glaucine (X).

View full abstract

Download PDF (651K)
Studies on Tetrahydroisoquinolines. VII. Synthesis of Homoaporphine via a p-Quinol Acetate ; Total Synthesis of (±)-Kreysigine

OSAMU HOSHINO, TADASHI TOSHIOKA, KEIKO OHYAMA, BUNSUKE UMEZAWA

1974 Volume 22 Issue 6 Pages 1307-1312
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1307

JOURNAL FREE ACCESS

Show abstractHide abstract

Acid treatment (conc. H₂SO₄-Ac₂O) of a p-quinol acetate (VIII) derived from phenolic (±)-1-phenethylisoquinoline (III) by means of Pb (OAc)₄ oxidation was found to afford readily (±)-O-acetylhomoaporphine (I). consequently, synthesis of (±)-kreysigine (II) was accomplished via the corresponding p-quinol acetate (XV).

View full abstract

Download PDF (799K)
Studies of Nucleosides and Nucleotides. LVII. Purine Cyclonucleosides. (20). Synthesis and Reactions of 8, 5'-S-Cycloadenosine Derivatives

MORIO IKEHARA, YASUYUKI MATSUDA

1974 Volume 22 Issue 6 Pages 1313-1318
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1313

JOURNAL FREE ACCESS

Show abstractHide abstract

Starting from 2', 3'-isopropylidene-8, 5'-anhydro-8-mercaptoinosine (II), synthesized from the corresponding adenosine derivative (I) by deamination with sodium nitrite, various 6-substituted analogs were synthesized. Compound (II) was converted to 6-chloropurine derivative (III) by the reaction with POCl₃ and tri-n-butylamine at refluxing temperature in 75% yield. Compound (III) was allowed to react either with methylamine, dimethylamine or sodium methylmercaptide to give N⁶-methyl (IV), N⁶-dimethyl (IX) and 6-methylmercapto (X) derivatives, respectively. Ultraviolet spectrum, circular dichroism and mass spectra of these compounds are listed. Compound (IV) was alternatively obtained by a Dimroth type rearrangement of N¹-methyl derivative of I by heating in sodium hydroxide solution at pH 8-9. The same type of rearrangement occured also with unprotected 1-methyladenosine-8, 5'-S-cyclonucleoside to give compound (VIII).

View full abstract

Download PDF (722K)
Studies on Microcapsules. XVII. Effect of Chemical Structure of Acid Dichlorides and Bisphenols on the Formation of Polyphenyl Ester Microcapsules

YOSHIKO WAKAMATSU, MASUMI KOISHI, TAMOTSU KONDO

1974 Volume 22 Issue 6 Pages 1319-1325
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1319

JOURNAL FREE ACCESS

Show abstractHide abstract

Polyphenyl ester microcapsules were prepared by the interfacial polycondensation reactions between each of 2, 2-bis (4-hydroxyphenyl) propane and 4, 4'-dihydroxydiphenyl sulfone and each of p-phthaloyl dichloride and sebacoyl dichloride in the presence of alkali under various conditions. The percentage of reacted bisphenols, and the size distribution and mean diameters of the microcapsules formed were determined and factors affecting them were studied. The size distribution of the microcapsules was found to depend strongly on chemical structure of the reactants used. This was plausibly explained by taking account of the percentage of reacted bisphenols with the acid dichlorides. The mean diameters varied with the percentage of reacted bisphenols in a way similar to that for the size distribution.

View full abstract

Download PDF (821K)
Syntheses of Ring-substituted Flavonoids and Allied Compounds. XII. Synthesis of (±)-Fukugetin Heptamethyl Ether

KOICHI NAKAZAWA, KUMIKO(nee WADA

1974 Volume 22 Issue 6 Pages 1326-1330
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1326

JOURNAL FREE ACCESS

Show abstractHide abstract

3', 4', 5, 7-Tetramethoxyflavon-(8")-ylacetic acid (X), prepared from 2-hydroxy-4, 6-dimethoxyacetophenone (III) in five steps, was condensed with phloroglucinol dimethyl ether (XIV) by means of triphenylphosphine-carbon tetrachloride-triethylamine to give 3, 5-dimethoxyphenyl ester (XV), Fries rearrangement of wbich provided 8-(2"-hydroxy-4", 6"-dimethoxyphenacyl)-3', 4', 5, 7-tetramethoxyflavone (XIII). Condensation of the latter with anisaldehyde in the presence of potassium hydroxide in dimethyl sulfoxidemethanol, followed by cyclization with sulfuric acid afforded the flavonylflavanone derivative (II) identical with natural (±)-fukugetin heptamethyl ether.

View full abstract

Download PDF (677K)
Thiosugars. XVII. Syntheses of Maltose Derivatives having Sulfur Atom in the Reducing Moiety

MASAMI MORI, MASANOBU HAGA, SETSUZO TEJIMA

1974 Volume 22 Issue 6 Pages 1331-1338
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1331

JOURNAL FREE ACCESS

Show abstractHide abstract

Several maltose derivatives containing sulfur atom in C₁ and C₆ positions in maltose have been synthesized. Treatment of maltosan hexaacetate (II) with titanium tetrabromide in chloroform, followed by acetylation with mercuric acetate in acetic acid, afforded 1, 2, 3, 2', 3', 4', 6'-hepta-O-acetyl-β-maltose (III) in 41% yield. Heating of the corresponding 6-tosylate (V) with potassium thiolacetate in N, N-dimethylformamide afforded 1, 2, 3, 2', 3', 4', 6'-hepta-O-acetyl-6-S-acetyl-6-deoxy-6-thio-β-maltose (VII). Deacetylation of VII gave 6-deoxy-6-thio-maltose (IX) as a sirup which contained two products, disulfide and thiol. Starting from 6-mesylate (IV) or 6-tosylate (V), crystalline 1, 6-anhydro-2, 3, 2', 3', 4', 6'-hexa-O-acetyl-6-deoxy-6-thio-β-maltose (6-thiomaltosan hexaacetate) (XV) was synthesized by an analogous reaction sequence describing in the preparation of 6-thiolactosan hexaacetate ; S. Tejima, Carbohyd. Res., 20, 123 (1971). Deacetylation of XV afforded 1, 6-anhydro-6-deoxy-6-thio-β-maltose (6-thiomaltosan) (XIX) as amorphous powders. Acetolysisof XV gave 1, 2, 3, 2', 3', 4', 6'-hepta-O-acetyl-6-deoxy-6-thio-6-S-acetyl-α-maltose (XVIII). Reductive desulfurization of XV, followed by deacetylation, yielded 1, 5-anhydro-4-O-α-D-glucopyranosyl-6-deoxy-D-glucitol (XVII) as amorphous powders. Syntheses of several 1-thio-β-maltose derivatives have also been described.

View full abstract

Download PDF (1116K)
Saponin and Sapogenol. VIII. Photochemical Cleavage of Glycoside Linkage in Saponin. (1). Photolysis of Some Saponins and Their Structural Features

ISAO KITAGAWA, MASAYUKI YOSHIKAWA, YASUHIRO IMAKURA, ITIRO YOSIOKA

1974 Volume 22 Issue 6 Pages 1339-1347
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1339

JOURNAL FREE ACCESS

Show abstractHide abstract

In search of a new hydrolysis method of saponin, it has been found that ultraviolet irradiation is a convenient procedure for hydrolysis of some oleanane triterpenoid saponins resulting in liberation of their genuine sapogenols. The subsequent investigation on structure requirement for ready photolysis of glycoside linkage in saponin has revealed that an uronic acid moiety directly connected to the sapogenol is an essential constituent in the carbohydrate portion.

View full abstract

Download PDF (1068K)
Studies on Dimethoxyphenylaminoalcohols. II. Syntheses and Relative Configulations of 1-Dimethoxyphenyl-3-(alkylamino) butanols

HIROAKI HAMANO, SHIGENOBU OKUDA

1974 Volume 22 Issue 6 Pages 1348-1359
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1348

JOURNAL FREE ACCESS

Show abstractHide abstract

1-Dimethoxyphenyl-3-(alkylamino) butanols were synthesized by the reduction of the corresponding β-aminoketones. 1-Dimethoxyphenyl-3-aminobutanols were synthesized via the hydrogenolyses of the corresponding N-benzyl derivatives. Diastereomers were respectively isolated and their relative configurations were determined by extensive nuclear magnetic resonance studies.

View full abstract

Download PDF (1242K)
Extracellular Polysaccharide of Cladosporium herbarum Studies on Fungal Polysaccharide. XIII

TOSHIO MIYAZAKI, YASUTA NAOI

1974 Volume 22 Issue 6 Pages 1360-1365
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1360

JOURNAL FREE ACCESS

Show abstractHide abstract

Major water-soluble extracellular polysaccharide of C. herbarum obtained by DEAE-cellulose column fractionation and zone electrophoresis using 1% Na₂B₄O₇ of crude polysaccharide is a galactomannan, [α]²⁵_D+27°(c=1.0, H₂O), which was composed of D-galactose and D-mannose=1.0 : 1.5. From the results of periodate oxidation, Smith-type degradation, and methylation studies showed that the polysaccharide has a highly branched structure and contains 1→2 main linkage of mannopyranose with 1→4 linked galactopyranose, and the glycan was branching at C4 position of mannose residue. The terminal residues are galactofranose and mannopyranose.

View full abstract

Download PDF (768K)
Studies on 3-Substituted-2-thiohydantoins as Analytical Reagent. II. Polarographic Investigation of Color Reaction of 3-Methyl-2-thiohydantoin

ATSUSHI SUGII, MASANOBU MATSUO, YOSHIHUMI OHARA

1974 Volume 22 Issue 6 Pages 1366-1371
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1366

JOURNAL FREE ACCESS

Show abstractHide abstract

Color reaction of 3-methyl-2-thiohydantoin (MTH) in alkaline solution was investigated by polarographic method. Hydrogen peroxide and bis (3-methyl-2-thiohydan-toinylidene-5) were confirmed in the autoxidation products of MTH and their apparent ratio was determined by this method. Effect of metal ions on the autoxidation of MTH was also studied and a reaction mechanism was proposed.

View full abstract

Download PDF (600K)
Ganglion Blocking Effect of Indole Alkaloids contained in Uncaria Genus and Amsonia Genus and Related Synthetic Compounds on the Rat Superior Cervical Ganglion in Situ

MASATOSHI HARADA, YUKIHIRO OZAKI, MASAYOSHI SATO

1974 Volume 22 Issue 6 Pages 1372-1377
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1372

JOURNAL FREE ACCESS

Show abstractHide abstract

Effects of some standard drugs, indole alkaloids contained in Uncaria Genus and Amsonia Genus and several related synthetic compounds on transmission were examined in the rat superior cervical ganglionic preparation in situ. In this preparation, standard drugs could produce typical actions to be expected. It was confirmed that this preparation could be routinely used and an arterial injection of drugs was preferable in order to examine their direct action on the ganglion. All indole compounds, administered arterially, showed a ganglion blocking action except one. Among these, hirsutine, 2, 3-seco-yohimbine, I and V exerted a relatively strong inhibitory effect comparable with that of hexamethonium.

View full abstract

Download PDF (688K)
Studies on the Sulfur-containing Chelating Agents. XXXIX. Determination of Stability Constants of Some Metal Complexes of N-Phenyl-and N-Ethyl-β-mercaptocinnamamide and Thiodibenzoyl-methane by Solvent Extraction Method

MASAHIKO CHIKUMA, AKIRA YOKOYAMA, HISASHI TANAKA

1974 Volume 22 Issue 6 Pages 1378-1385
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1378

JOURNAL FREE ACCESS

Show abstractHide abstract

Stability constants and extraction constants of some metal complexes of N-phenyl-β-mercaptocinnamamide (I), N-ethyl-β-mercaptocinnamamide (II) and thiodibenzoylmethane (III) were determined by solvent extraction method in chloroform and isoamyl acetate systems. The stability constants in I-metal and II-metal systems are smaller than those in III-metal system whereas the extraction constants in the former two systems are larger than those in the latter. In these ligands, the difference in the partition coefficients is regarded as a main factor to cause the remarkable difference in the extractability of metal ion. It was shown that the introduction of amide group makes the reagent hydrophilic to react readily with the metal ions in the extraction system.

View full abstract

Download PDF (758K)
Tetrahydronaphthylamines and Related Compounds. III. Synthesis of 1, 2, 3, 4-Tetrahydro-2-naphthylamine and 6-Amino-5, 6, 7, 8-tetrahydroquinoline Derivatives

KEIICHI NOMURA, JUN ADACHI, MICHIO HANAI, SACHIKO(nee NAKAYAMA, KEMMOT ...

1974 Volume 22 Issue 6 Pages 1386-1392
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1386

JOURNAL FREE ACCESS

Show abstractHide abstract

Amino substituted 1, 2, 3, 4-tetrahydronaphthalene and 5, 6, 7, 8-tetrahydroquinoline derivatives (1, 2, 3, 4-tetrahydro-6-methoxy-N-methyl-2-phenyl-2-naphthylamine, 1, 2, 3, 4-tetrahydro-6-methoxy-N, N-dimethyl-2-phenyl-2-naphthylamine, 5, 6, 7, 8-tetrahydro-6-(methylamino)-6-phenylquinoline and 5, 6, 7, 8-tetrahydro-6-(dimethylamino)-6-phenylquinoline) were synthesized. Thus, Michael adducts of methyl vinyl ketone and acrylonitrile to methyl 5-cyano-2-oxo-5-phenylcyclohexanecarboxylate (I) were used for formation of skeleton of naphthalene and quinoline, respectively. Quinoline derivative was also obtained by condensation of cyclohexanone derivative with 3-aminoacrolein. Amino function was derived from nitrile via Hofmann reaction of amide. Furthermore, an interesting tricyclic compound, 3, 8a-ethano-3, 4, 4a, 8a, 5, 6-hexahydro-3-phenyl-2, 7 (1H, 8H)-quinolinedione, was obtained on cyclization reaction of a Michael adduct (IIa).

View full abstract

Download PDF (884K)
ESR Studies on Bis (O, O'-diethyldithiophosphato) Oxovanadium [IV] in Ether Solutions

MITSUO SATO, TAKASHI KATSU, YUZABURO FUJITA, TAKAO KWAN

1974 Volume 22 Issue 6 Pages 1393-1397
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1393

JOURNAL FREE ACCESS

Show abstractHide abstract

ESR studies have been made on bis (O, O'-diethyldithiophosphato) oxovanadium [IV], VOdtp₂, in ethyl ether, isopropyl ether, η-butyl ether, and tetrahydrofuran solutions. It has been found that at lower temperatures VOdtp₂ reacts with each of the ethers to form an adduct, VOdtp₂·(R₂O), with structure characterized by the coordination of ether molecule to the equatorial position. The equilibrium constant for the VOdtp₂·(R₂O) formation has also been evaluated ; it increased with increasing basicity of the ether (tetrahydrofuran>ethyl ether>isopropyl ether-n-butyl ether).

View full abstract

Download PDF (535K)
Amino Acids and Peptides. XII. Phosphorus in Organic Synthesis. VIII. Reaction of Malonic Acid Half Esters with Diphenyl Phosphorazidate

KUNIHIRO NINOMIYA, TAKAYUKI SHIOIRI, SHUNICHI YAMADA

1974 Volume 22 Issue 6 Pages 1398-1404
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1398

JOURNAL FREE ACCESS

Show abstractHide abstract

Application of the modified Curtius reaction by DPPA to some malonic acid half esters revealed that esterification occurred in a one-step process but the rearrangement reaction took place in a two-in-one-reaction procedure, the results of which are summarized in Tables I and II. The latter procedure may provide a new simple method for the synthesis of α-amino acids.

View full abstract

Download PDF (892K)
Adsorption of Phenothiazines from Aqueous Solution by Aerosil

NAOKI NAMBU, SHOTARO SAKURAI, TSUNEJI NAGAI

1974 Volume 22 Issue 6 Pages 1405-1407
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1405

JOURNAL FREE ACCESS

Download PDF (457K)
Anomeric Proton Signals of the Component Monosaccharides of Free Oligoglycosides in Nuclear Magnetic Resonance Spectroscopy

KAZUMOTO MIYAHARA, TOSHIO KAWASAKI

1974 Volume 22 Issue 6 Pages 1407-1410
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1407

JOURNAL FREE ACCESS

Download PDF (526K)
Hypotensive and Radioprotective Properties of N⁶-Substituted Adenosine Derivatives

MIKIO SHIKITA, YOSHINARI TAKAGI, FUMIKO(nee HATANO, SANYA AKABOSHI

1974 Volume 22 Issue 6 Pages 1410-1413
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1410

JOURNAL FREE ACCESS

Download PDF (556K)
Reaction Products of 2-Oxoglutaric Acid with Diazotized Sulfanilamide

YOSUKE OHKURA, MASATOSHI YAMAGUCHI, TSUTOMU MOMOSE

1974 Volume 22 Issue 6 Pages 1414-1417
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1414

JOURNAL FREE ACCESS

Download PDF (569K)
Free Radical formed during the Reaction of L-Ascorbic Acid with Hydrazine

HIDEO UTSUMI, YUTAKA KIRINO, TAKAO KWAN

1974 Volume 22 Issue 6 Pages 1417-1419
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1417

JOURNAL FREE ACCESS

Download PDF (453K)
Addition Reactions of Heterocumulenes. I. Cycloaddition Reaction of Dimethylketene with α-Diimines

MASANORI SAKAMOTO, KYOKO MIYAZAWA, YOSHIKO ISHIHARA, YOSHIO TOMIMATSU

1974 Volume 22 Issue 6 Pages 1419-1421
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1419

JOURNAL FREE ACCESS

Download PDF (456K)
Studies on Quinolizine Derivatives. IX. Synthesis of Azacycl [3, 3, 3] azine Derivatives

HIROYOSHI AWAYA, CHIKATOSHI MASEDA, YOSHINORI TOMINAGA, REIKO NATSUKI, ...

1974 Volume 22 Issue 6 Pages 1424-1426
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1424

JOURNAL FREE ACCESS

Download PDF (434K)
Chemistry of Leucomycins. XI. Chemical Transformation of a Basic Macrolide to a Neutral Macrolide

AKIRA NAKAGAWA, KAZUHIRO SUZUKI, KATSUYOSHI IWASAKI, TOJU HATA, SATOSH ...

1974 Volume 22 Issue 6 Pages 1426-1428
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1426

JOURNAL FREE ACCESS

Download PDF (404K)
Pattern of Calcium Oxalate Crystals in the Leaves of Poligonum longisetum DE BRUYN and P. persicaria LINN. grown from 4000-year-old Seeds, and in the Leaves of Same Poligonum sp. Plants Now Growing

KOUICHIRO UMEMOTO

1974 Volume 22 Issue 6 Pages 1429-1430
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1429

JOURNAL FREE ACCESS

Download PDF (397K)
Photoreactions of Benzoylaminopyridines

KAZUHIKO ITOH, YUICHI KANAOKA

1974 Volume 22 Issue 6 Pages 1431-1432
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1431

JOURNAL FREE ACCESS

Download PDF (318K)
Studies on the Chlorinated α-Santonins. I

HARUO OGURA, HIROAKI TAKAYANAGI, AKIE YOSHINO, TOSHIHIKO OKAMOTO

1974 Volume 22 Issue 6 Pages 1433-1435
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1433

JOURNAL FREE ACCESS

Download PDF (460K)
Ambrosic Acid, a New Irritant Principle from Ambrosia arthemisiifolia

SEIICHI INAYAMA, TAMIKO OHKURA, TAKESHI KAWAMATA, MASAITI YANAGITA

1974 Volume 22 Issue 6 Pages 1435-1437
Published: June 25, 1974
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.22.1435

JOURNAL FREE ACCESS

Download PDF (432K)

Register with J-STAGE for free!