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Minoru Yoshimura, Hisao Tsukamoto
1963 Volume 11 Issue 6 Pages
689-693
Published: June 25, 1963
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5-Ethyl-, 5-methyl-5-cyclohexenylhydantions (ECH and MCH), are prepared from the corresponding cyanoacetamide or malonamide using the Hofmann reaction. These 5, 5-disubstituted hydantions haveing cyclohexenyl group appear to display narcotic action with 300 mg./kg. in the rabbit. These hydantoins are metabolized to oxo-compounds in the rabbits (about 14.0%), which are identical with the CrO
3-oxidation product of ECH or MCH respectively. It is finally concluded that the biological and chemical oxidation of the drugs having cyclohexenyl group preferentially takes place on the position 3 in the cyclohexenyl group, and the keto formation abolishes the characteristic pharmacologial action of the drugs in animal. Accordingly, this biological oxidation reaction is considered to be significant only as a detoxication mechanism.
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Masatomo Hamana, Bunsuke Umezawa, Kanji Noda
1963 Volume 11 Issue 6 Pages
694-699
Published: June 25, 1963
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Modified King reaction of 2-picoline 1-oxide gave pyrido [1', 2' : 3, 4] imidazo [1, 2-α] pyridinium iodide instead of 1-[ (1-oxido-2-pyridyl) methyl] pyridinium iodide (Ia). Selective reduction of N-oxide or pyridinium group of Ia was investigated.
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Hiroshi Ueki, Seigoro Hayashi, Yosoji Ito
1963 Volume 11 Issue 6 Pages
700-703
Published: June 25, 1963
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The binding of insulin with quinones and its derivatives was quantitatively measured by chromatography on dextran gel column and it was found that the rate of binding increased with increasing concentration of free quinones in the range of 0.1 to 1 mM of quinones. The binding of quinones with insulin was also studied by using sedimentation, electrophoretic, and paper electrophoretic analysis. From these results, it was assumed that quinone derivatives might bind to insulin, produce some change in molecular form of insulin, and promote the association of insulin molecule.
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Toyozo Uno, Katsunosuke Machida, Kazuhiko Hanai, Michihiro Ueda, Shige ...
1963 Volume 11 Issue 6 Pages
704-708
Published: June 25, 1963
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The infrared spectra of N-(2-pyridyl)-, N-(2-thiazolyl)-, N-(2-pyrimidinyl)- and N-phenyl-sulfonamide derivatives and their N-deuterated compounds, as well as N
1- or ring N-methylsulfonamide derivatives were measured. The spectral changes on N-deuteration suggest that pyrimidine derivatives take the amido form, while pyridine and thiazole derivatives take the imido form. The SO
2 symmetric stretching bands of sulfanilamide derivatives may be divided into the two regions, 1170 to 1145 cm
-1 and 1145 to 1130 cm
-1, according to the amido form and the imido form, respectively.
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Toyozo Uno, Michihiro Ueda
1963 Volume 11 Issue 6 Pages
709-712
Published: June 25, 1963
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A new glucuronide of sulfathiazole was isolated from human urine after administration of sulfathiazole. This glucuronide was isolated as its ammonium salt with melting point 176∼178°(decomp.). It was confirmed that the conjugate is sulfatiazole-N
1-glucuronide by the data of ultraviolet and infrared spectroscopy.
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Mikio Honjo, Yoshiyasu Furukawa, Hiroki Moriyama, Kuniyoshi Tanaka
1963 Volume 11 Issue 6 Pages
712-720
Published: June 25, 1963
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Five NAD analogs have been synthesized in which the adenosine portion of NAD was replaced by deoxyadenosine, guanosine, cytidine, uridine and thymidine, and their comparative coenzymatic activity with that of NAD was investigated with yeast alcohol dehydrogenase, beef liver glucose dehydrogenase and rabbit muscle lactic dehydrogenase. The influence of the analogs on the reaction rate of NAD was also studied.
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Takenari Nakagome
1963 Volume 11 Issue 6 Pages
721-725
Published: June 25, 1963
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N-Oxidation of 6-chloro-3, 4-dimethylpyridazine afforded two kinds of product (V and VI), the latter being in a very low yield. 6-Methoxy-3, 4-dimethylpyridazine gave sole N-oxide (VIII). Catalytic dehalogenation of V and VI yielded 3, 4-dimethylpyridazine N-oxide, II from V and III from VI respectively, both II and III being also obtained by N-oxidation of 3, 4-dimethylpyridazine. V was derived to VIII. N-Oxide group in II, V and VIII was concluded to be in the position adjacent to the methyl group from the derivation of V into 1, 3, 4-trimethyl-6 (1H)-pyridazinone 2-oxide (X) by hydrolysis with dilute sodium hydroxide, followed by methylation with dimethyl sulfate and dilute alkali hydroxide. The structure of X was confirmed by the formation of 1, 3, 4-trimethyl-6 (1H)-pyridazinone (XI) by catalytic reduction which was prepared by methylation of 3, 4-dimethyl-6 (1H)-pyridazinone. Consequently, the nitrogen further removed from the methyl group is oxidized in III and VI.
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Takenari Nakagome
1963 Volume 11 Issue 6 Pages
726-730
Published: June 25, 1963
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Nitration of 3, 4-dimethyl (Ia), 6-chloro-3, 4-dimethyl (Ib), 6-methoxy-3, 4-dimethylpyridazine 2-oxide (Ic), 3, 4-dimethyl (Id) and 3-methylpyridazine 1-oxide (Ie) was examined and it was proved that Ia, Ib, Ic and Ie afforded γ-nitropyridazine N-oxides (IIa∼IIe), whereas Id in which γ-position was substituted gave α-nitro N-oxide (IId). All of these nitro derivatives were derived to aminopyridazines (IIIa∼IIIe) by catalytic reduction over Raney-nickel in methanol or over palladium-charcoal in dilute hydrochloric acid. Ultraviolet spectra of several aminopyridazines are also given.
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Tomoharu Okuda, Makoto Suzuki, Tamotsu Furumai, Hiroko Takahashi
1963 Volume 11 Issue 6 Pages
730-736
Published: June 25, 1963
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Thermal degradation and isomerization studies on cycloheximide and its stereoisomers were carried out, and the results obtained did support chemically the absolute configuration of cycloheximides proposed previously.
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Yoshihiro Nitta, Fumio Yoneda
1963 Volume 11 Issue 6 Pages
737-740
Published: June 25, 1963
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Infrared spectra confirmed that the products arising from reaction of maleic hydrazide with substituted benzyl chloride are O-benzyl compounds.
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Fumio Yoneda, Takayuki Ohtaka, Yoshihiro Nitta
1963 Volume 11 Issue 6 Pages
740-744
Published: June 25, 1963
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Durch die Einwirkung von Anilinen auf 3, 6-Dichlorpyridazin wurden verschiedenartige 3-Chlor-6-anilinopyridazine dargestellt. Die letzteren lieferten durch Einwirkung von Natrium-Benzylalkoholat 3-Benzyloxy-6-anilinopyridazine, die durch Zersetzung mit Salzsaure in 6-Anilino-3 (2H)-pyridazinone ubergefuhrt wurden. Die so erhaltene 6-Anilino-3 (2H)-pyridazinone lieferten beim Einwirkenlassen von Methyljodid 2-Methyl-6-anilino-3 (2H)-pyridazinone. 3-Chlor-6-anilinopyridazine ergaben bei der katalytischen Hydrierung mit Palladium-Kohle 3-Anilinopyridazine. Ferner wurden einige 3-Alkoxy-6-benzylaminopyridazine hergestellt.
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Yoshihiro Nitta, Reiko Tomii, Fumio Yoneda
1963 Volume 11 Issue 6 Pages
744-748
Published: June 25, 1963
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The infrared absorption spectra of the two aminopyridazines were observed and compared with those of the three aminopyridines and aniline. The amino-form of the two aminopyridazines was confirmed, and at the same time the structural similarity of 4-aminopyridazine with 4-aminopyridine was shown by their infrared spectra. Similarly, the spectrum of 3-aminopyridazine was close to that of 2-aminopyridine. In addition, the correlation between the position and the nature of substituent was discussed.
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Tetsuro Ikekawa
1963 Volume 11 Issue 6 Pages
749-751
Published: June 25, 1963
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Emodin afforded a dimeric product, 2, 4, 4', 5, 5', 7'-hexahydroxy-2', 7-dimethyl-1, 1'-bianthraquinone, which was named isoskyrin, on oxidative coupling by introducing oxygen in the alkaline solution or by the action of silver oxide.
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Kiyoshi Sakai
1963 Volume 11 Issue 6 Pages
752-754
Published: June 25, 1963
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Es wird eine Umlagerungsreaktion der Doppelbindung an C
24 (28) der Sterinseitenkette beschrieben. Die Doppelbindung an C
24 (28) des Fucosterylacetates bzw. des 24-Methylencholesterylacetates laβt sich durch Einwirkung von Jod in die 24 (25)-Stellung umlagern.
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Akihiro Ohta, Yukio Ogihara, Kiyoshi Nei, Shoji Shibata
1963 Volume 11 Issue 6 Pages
754-758
Published: June 25, 1963
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The 1-phenylnaphthalene derivatives which possess methyl group (s) at the position of 3, 4, 5, 6, 7, 3, 2', 3, 6', 3, 7, 4, 4', 4, 6, 4, 7, 3', 4', and 2, 3' were prepared by the general procedure involving the Grignard reaction of the α-tetralone derivatives and bromobenzene substituted with methyl group (s) in appropriate position (s).
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Shoji Shibata, Mitiiti Fujita, Hideji Itokawa, Osamu Tanaka, Tatsuo Is ...
1963 Volume 11 Issue 6 Pages
759-761
Published: June 25, 1963
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Panaxadiol, C
30H
52O
3, a sapogenin of Ginseng roots was acetylated to afford monoacetate, C
32H
54O
4, which was oxidized with chromium trioxide to give panaxanolone acetate, C
52H
52O
4. On Wolff-Kishner reduction, panaxanolone acetate was converted into panaxanol, C
30H
52O
2, which was heated with hydrochloric acid in glacial acetic acid to furnish anhydropanaxanol acetate, C
32H
52O
2. On catalytic hydrogenation of anhydropanaxanol, isotirucallenol (X) was obtained, which was established by infrared and gaschromatography. A trimethyltetrahydropyrane ring system in panaxadiol was proved by mass-spectrometry, and the oxygen ring was cleaved by the action of hydrochloric acid on panaxanol. The α, β-unsaturated ketonic system was proved ultraviolet spectroscopically in the product derived from panaxanolone acetate by the action of sulfuric acid in glacial acetic acid. Thus the hindered hydroxyl of panaxadiol should be present at the 12-position. Consequently, it has been concluded that panaxadiol is a new tetracyclic triterpene of dammarane series having hydroxyls at the 3- and 12-positions and trimethyltetrahydropyrane ring at C
(17), as represented by the formula (T).
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Shoji Shibata, Osamu Tanaka, Masahiro Nagai, Tatsuo Ishii
1963 Volume 11 Issue 6 Pages
762-765
Published: June 25, 1963
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The treatment of panaxanolone acetate with caustic alkali showed that it possesses a less-hindered stereochemical structure. The Dreiding Model suggested three possible less-hindered structures for panaxanolone which included trans C/D 17α-H system (X), cis C/D 17β-H system both chair (Y') and boat (Z') C-ring (Fig. 1). The infrared spectral analysis showed that the hydroxyl at the 12-position of panaxadiol (12β-OH) as well as that of 12-epi-panaxadiol (12α-OH) are hydrogen-bonded with the oxygen of trimethyltetrahydropyrane ring attached at C
(17). Moreover, the atomic distance between 12-OH and tetrahydropyrane ring oxygen is shown by the Dreiding Model as being much closer in the case of 12β-OH than 12α-OH, which is proved by the resistance of panaxadiol against acetylation at 12-OH. This can only be explained by the stereochemical system of cis C (chair)/D, 12β-OH, 17β-H for panaxadiol (II), and cis C (boat)/D, 12α-OH, 17β-H for 12-epi-panaxadiol (III).
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Bunji Shimizu, Akira Ogiso, Issei Iwai
1963 Volume 11 Issue 6 Pages
766-769
Published: June 25, 1963
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Cyclyzation of 3-methyl-9-(p-methoxyphenethyl)-3-azabicyclo [3. 3. 1] nonan-9-ol (Va : R=H) with polyphospholic acid gave a spiro compound of azabicyclononane (VI), but not a hydrophenanthrene derivative (VI'). The evidence for the structure of the cyclization product was provided by the fact that on oxidation with chromic acid, VI gave the 1-indanone (IX) showing the infrared absorption at 1706 cm
-1 and the lactam ketone (X) showing the absorptions at 1705 cm
-1 and 1600 cm
-1.
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Akira Ogiso, Bunji Shimizu, Issei Iwai
1963 Volume 11 Issue 6 Pages
770-774
Published: June 25, 1963
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1-(p-Methoxyphenyl)-3, 5-dimethyl-3-azabicyclo [3. 3. 1] nonane-⊿
9, α-acetaldehyde was synthesized from 1-(p-methoxyphenyl)-3, 5-dimethyl-3-azabicyclo [3. 3. 1] nonan-9-one (VI) by reaction with ethoxyethynyllithium and partial hydrogenation of the ethoxyethynyl carbinol (IX) followed by treatment with phosphorus tribromide. This α, β-unsaturated aldehyde would be a suitable starting material for the synthesis of diterpenoid alkaloids, because cyclization of a derivative having a tertiary hydroxyl group at C-9 position of the phenylazabicyclononane did not form an expected compound.
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Akira Ogiso, Bunji Shimizu, Issei Iwai
1963 Volume 11 Issue 6 Pages
774-779
Published: June 25, 1963
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Catalytic reduction of 1-(p-methoxyphenyl)-3, 5-dimethyl-3-azabicyclo [3. 3. 1] nonane ⊿
9, α-acetaldehyde (II) gave two epimeric saturated aldehydes (IIIa) and (IIIb). Both epimers were converted into the stereoisomeric hydrophenanthrene derivatives, VIa and VIb, respectively, by reduction with lithium aluminum hydride followed by cyclization with polyphospholic acid. The conformation of the stereoisomers was confirmed by determining the configuration of two epimeric alcohols (Va) and (Vb) from which these hydrophenanthrene compounds were derived. The A/B trans-fused isomer bears the common skeleton of the atisine-type alkaloids.
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Toshihiko Okamoto, Masaaki Hirobe, Chieko Mizushima, Akio Ohsawa
1963 Volume 11 Issue 6 Pages
780-785
Published: June 25, 1963
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1-(N-Monosubstituted amido) pyridinium compounds derived from novel quaternary salts of pyridine, N-aminopyridinium compounds, were quite reactive to nucleophilic agents at 2- and 4-positions of their pyridine rings, especially at 4-position. The 1-(N-monosubstituted amido) pyridinium salts were reacted with cyanide ion to give N-monosubstituted amides and cyanopyridines, (predominantly 4-cyanopyridine), both in good yields. The reaction may involve dihydro-type intermediates and one intermediate 1-(N-methylacetamino)-4-cyano-1, 4-dihydropyridine could be obtained stably. By utilizing this reaction, it would be possible to introduce a cyano group at 4-position of various pyridine derivatives and to obtain various primary amines.
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Toshihiko Okamoto, Michiya Itoh
1963 Volume 11 Issue 6 Pages
785-792
Published: June 25, 1963
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4-Nitroquinoline 1-oxide and related compounds react easily with SH-group of thioglycolic acid affording the corresponding sulfides of these compounds. With these nitro compounds, the present authors studied the nucleophilic substitution reaction between 4-nitro group and thioglycolic SH-group, and determined the reaction rate constants, energies of activation and entropies of activation in several kinds of solvent system. On the other hand, 4-nitroquinoline 1-oxide and some related compounds have been known to be skin cancer producing agents. Then, the chemical activity of 4-nitro groups which were obtained were discussed on comparison with the carcinogenic activity.
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Zenzo Tamura, Kozo Nagano
1963 Volume 11 Issue 6 Pages
793-796
Published: June 25, 1963
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Consecutive formation constants of Cd (II) complexes of isonicotinoylhydrazine (INH) were determined by the polarographic method. A series of solutions containing 0.001M Cd
2+, 1.0M NaNO
3 and INH in concentration varying from 0.05 to 1.0M were used for the measurement of i
d and E
1/2. The method of De Ford and Hume was modified for calculation of concentration equilidrium constants K
j'. The results were [numerical formula] These results, especially K'
3, however, did not agree with the constants obtained by pH titration method which will be shown in the later report.
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Kozo Nagano, Hirokazu Tsukahara, Hisashi Kinoshita, Zenzo Tamura
1963 Volume 11 Issue 6 Pages
797-805
Published: June 25, 1963
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Acid dissociation constants of isonicotinoylhydrazine (INH) and seven related compounds were determined by means of pH titration (ionic strength 1.0). Values of pKa obtained were as follows : INH : 2.13, 3.81, 11.03. nicotinoylhydrazine (NH) : 2.26, 3.63, 11.49. picolinoylhydrazine (PH) : 1.26, 3.07, 12.25. benzoylhydrazine (BH) : 3.27, 12.53. p-nitrobenzoylhydrazine (PNBH) : 2.90, 11.28. isonicotinamide (INA) : 3.82. 1-isonicotinoyl-1-methylhydrazine (N-Me-INH) : 1.03, 4.17. 1-isonicotinoyl-2-methylhydrazine (N'-Me-INH) : 2.46, 4.04, 10.96. The ultraviolet spectra of these compounds at various pH were measured, and the results showed a good parallelism with the pKa values. Some informations about their structures in aqueous solutions were obtained from the spectral data.
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Masashi Tomoda
1963 Volume 11 Issue 6 Pages
806-808
Published: June 25, 1963
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A method using pyrogallol-ferric chloride-hydrochloric acid-acetic acid reagent was described for the colorimetric determination of pentose, pentosan, or ribonucleic acid. Coloration by this method was 90% in D-ribose and 54% in L-arabinose of that of D-xylose. Pentoses can be determined up to 10∼50μg./ml. Hexuronic acid showed an absorption curve similar to that of pentoses but its coloration was much lower than that of pentoses. It is possible to eliminate the influence of other carbohydrates by estimating the difference in absorbances between 500 and 430 mμ. The presence of D-glucosamine, serum albumin, and sodium chloride does not interfere in this coloration.
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Masashi Tomoda
1963 Volume 11 Issue 6 Pages
809-812
Published: June 25, 1963
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A method using orcinol-ferric chloride-hydrochloric acid-acetic acid reagent was described for the colorimetric determination of pentose, pentosan, or ribonucleic acid. Coloration by this method was 92% in D-xylose and 89% in D-ribose of that of L-arabinose. Pentoses can be determined up to 10∼50μg./ml. Hexuronic acid showed an absorption curve similar to that of pentoses but its coloration was much lower than that of pentoses. Sialic acid shows a color with an absorption maximum at 580 mμ, but its absorbance at 665 mμ, which is the absorption maximum wave length of pentoses, is low. D-Glucose, D-glucosamine, and deoxyribonucleic acid do not undergo this coloration. Other carbohydrates have very little effect on pentose determination. The presence of serum albumin and sodium coloride does not interfere in the coloration. The present method is better in specificity than other methods which have been used until now.
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Isuke Imada
1963 Volume 11 Issue 6 Pages
815-816
Published: June 25, 1963
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Zen-ichi Horii, Masazumi Ikeda, Yasuhiko Yamawaki, Yasumitsu Tamura, S ...
1963 Volume 11 Issue 6 Pages
817-818
Published: June 25, 1963
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Wataru Nagata, Tadao Terasawa, Tsutomu Aoki
1963 Volume 11 Issue 6 Pages
819-822
Published: June 25, 1963
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Shoji Shibata, Eisaku Morishita, Yasuo Arima
1963 Volume 11 Issue 6 Pages
821-823
Published: June 25, 1963
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Yosisige Kato
1963 Volume 11 Issue 6 Pages
823-827
Published: June 25, 1963
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