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Showing papers in "Chemical & Pharmaceutical Bulletin in 1963"


Journal ArticleDOI
TL;DR: 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).
Abstract: Panaxadiol, C30H52O3, a sapogenin of Ginseng roots was acetylated to afford monoacetate, C32H54O4, which was oxidized with chromium trioxide to give panaxanolone acetate, C52H52O4. On Wolff-Kishner reduction, panaxanolone acetate was converted into panaxanol, C30H52O2, which was heated with hydrochloric acid in glacial acetic acid to furnish anhydropanaxanol acetate, C32H52O2. 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).

131 citations


Journal ArticleDOI
TL;DR: An amorphous glucoside, named paeoniflorin, which was isolated from the roots of Paeonia albiflora PALLAS yielded crystalline tetraacetate, C31H36O15, and pentaacetate C33H38O16.
Abstract: An amorphous glucoside, named paeoniflorin, which was isolated from the roots of Paeonia albiflora PALLAS yielded crystalline tetraacetate, C31H36O15, and pentaacetate, C33H38O16. Alkaline hydrolysis showed that paeoniflorin possesses a benzoyl group. On treatment with lithium aluminium hydride, the acetates afforded product A, C16H24O10. Methylation of paeoniflorin tetraacetate yielded a methyl ether, C32H38O15 (product E acetate). By the action of lithium aluminium hydride, the product E acetate was converted into product F, C17H26O10. On treatment with sulfuric acid, the product F was hydrolyzed to yield an amorphous aglycone (aglycone F) liberating D-glucose. Oxidation of the aglycone F with cromium trioxide afforded a yellow crystalline quinonic compound (aglycone H), C10H10O4. The nuclear magnetic resonance spectral analysis of aglycone H leucodimethyl ether showed that it should be represented as 2-(4-methyl-2, 5-dimethoxyphenyl) or 2-(3-methyl-2, 5-dimethoxyphenyl) propionic acid. Paeoniflorin was shown to be D-glucoside of benzoylated C10-compound (C10H14O5).

102 citations


Journal ArticleDOI
TL;DR: In this paper, a new synthetic method for various 4-substituted-3-chromenes was proposed, where phenyl propargyl ethers underwent intramolecular cyclization to give 4-chromene derivatives by heating with diethylaniline.
Abstract: This is a new synthetic method for various 4-substituted-3-chromenes : phenyl propargyl ethers underwent intramolecular cyclization to give 4-chromene derivatives by heating with diethylaniline. The reaction mechanism was clarified by the study of substituted phenyl propargyl ethers under the consideration of their electronic effects on the yields of resulting 3-chromene ; in general, the presence of +R group enhanced the cyclization, whereas -R group gave much lower yields of the corresponding chromenes. Therefore, this intramolecular cyclization is concluded to be an electrophilic reaction.

100 citations



Journal ArticleDOI
TL;DR: The biosyntheses of monascorubrin and monascoflavin by a strain of Monascus genus have been studied and the two pigments have shown to be derived from the linear condensation of acetic acid units.
Abstract: The biosyntheses of monascorubrin and monascoflavin by a strain of Monascus genus have been studied and the two pigments have shown to be derived from the linear condensation of acetic acid units. The results confirm the proposed structure of both pigments.

49 citations


Journal ArticleDOI
TL;DR: In this paper, two new crystalline compounds were obtained from the roots of Sophora japonica in good yields and named B2 and C2, respectively, and the chemical structures of these four compounds were established.
Abstract: In the previous paper, it was reported that two crystalline compounds, tentatively named B1 and C1, were isolated from Sophora subprostrata in poor yield. In the present wark, two new crystalline compounds were obtained from the roots of Sophora japonica in good yields and named B2 and C2, respectively. The chemical structures of these four compounds were established as follows : B1 : l-Maackiain-mono-β-D-glucoside, C1 : l-pterocarpin, B2 : d-maackiain-mono-β-D-glucoside and C2 : dl-maackiain. B1 seems to be identical with trifolirhizin which was recently reported by J.B. Son Bredenberg et al. B2 is one of the diastereomers of trifolirhizin and so the name sophojaponicin was proposed.

47 citations


Journal ArticleDOI
TL;DR: In this paper, solid nickel peroxide has been shown to be capable of oxidizing primary amines to the corresponding azo-compounds in benzene solution, and the mechanisms of these oxidations were discussed.
Abstract: Solid nickel peroxide has been shown to be capable of oxidizing aromatic primary amines to the corresponding azo-compounds in benzene solution. Benzylamine and its derivatives bearing a substituent in the benzene ring could be easily oxidized by the same oxidant to give the corresponding nitriles in good yields regardless of the position and the variety of a substituent. Alkyl amines also underwent similar oxidation. In addition, the mechanisms of these oxidations were discussed.

44 citations


Journal ArticleDOI
TL;DR: Thin layer chromatography on silica gel-gypsum was applied to steroid saponins and their derivatives such as peracetates and permethylates, finding that the method has many advantages over paper chromatography in speed, sensitivity, and in resolving power of the closely related high molecular weight saponin and of the slightly polar derivatives.
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.

44 citations


Journal ArticleDOI
Masao Tomita1, Tohru Kikuchi1, Kiyoshi Bessho1, Toshio Hori1, Yasuo Inubushi1 
TL;DR: 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.
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.

43 citations


Journal ArticleDOI
TL;DR: The distribution of alkylphthalides in the roots of Ligusticum acutilobum SIEB, Apium graveolens L., Levisticum officinale KOCH, and Angelica anomale LALIEMENT have been surveyed.
Abstract: The distribution of alkylphthalides in the roots of Ligusticum acutilobum SIEB. et Zucc., Ligusticum acutiloba var. sugiyamae HIKINO, Cnidium officinale MAKINO, Apium graveolens L., Levisticum officinale KOCH, and Angelica anomale LALIEMENT have been surveyed. From the roots of Angelica anomale no alkylphthalides could be found. The results are summarized in Table II.

37 citations


Journal ArticleDOI
TL;DR: From the ultraviolet absorption spectra, it was shown that benzimidazole N-oxide exists as the N- oxide form in aqueous solution and as theN-hydroxyl form in ethanol solution.
Abstract: Previously unknown 1-substituted benzimidazole 3-oxides were synthesized by reductive ring-closure of N-acyl-N-substituted-o-nitroanilines. From the ultraviolet absorption spectra, it was shown that benzimidazole N-oxide exists as the N-oxide form in aqueous solution and as the N-hydroxyl form in ethanol solution.

Journal ArticleDOI
TL;DR: Timosaponin A-III, the crystalline steroid saponin isolated from a commercial crude drug Timo, has been shown to be sarsasapogenin O-β-D-glucopyranosyl-(1→2)-D-galactopyrside.
Abstract: Timosaponin A-III, the crystalline steroid saponin isolated from a commercial crude drug Timo (Anemarrhenae Rhizoma), has been shown to be sarsasapogenin O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside. The biose which forms the sugar moiety of timosaponin A-III was obtained as crystals from the partial hydrolyzate of the saponin and named timobiose.

Journal ArticleDOI
TL;DR: The structure was confirmed by desulfurization with Raney nickel according to give 6-deoxy-1, 5-anhydro-D-sorbitol tracetate, which was synthesized from 6- deoxy-6-acetylthio-2, 2, 3, 4-tetra-O- acetyl-β-D,glucopyranose, and potassium thiolacetate.
Abstract: 1, 6-Anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was synthesized by alkali-degradation and successive acetylation of 6-O-tosyl-2, 3, 4-tri-O-acetyl-β-D-glucopyranosyl ethylxanthate and 6-O-tosyl-1-deoxy-1-acethylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose, which were prepared from 6-O-tosyl-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide with potassium ethylxanthate and potassium thiolacetate respectively. On desulfurization of 1, 6-anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose with Raney nickel, 6-deoxy-1, 5-anhydro-D-sorbitol tracetate was obtained. 1, 6-Dideoxy-1, 6-diacetylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was prepared from 6-deoxy-6-acetylthio-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide, which was synthesized from 6-deoxy-6-acetylthio-1, 2, 3, 4-tetra-O-acetyl-β-D-glucopyranose, and potassium thiolacetate. The structure was also confirmed by desulfurization with Raney nickel according to give 6-deoxy-1, 5-anhydro-D-sorbitol.



Journal ArticleDOI
TL;DR: In this article, it was shown from the nuclear magnetic resonance data of 23 kinds of androst-4-ene and pregn-4ene derivatives that NMR can be applied to determination of the position and the configuration of unknown hydroxyl groups in steroidal molecules.
Abstract: It is shown from the nuclear magnetic resonance data of 23 kinds of androst-4-ene and pregn-4-ene derivatives that nuclear magnetic resonance can be applied to determination of the position and the configuration of unknown hydroxyl groups in steroidal molecules.

Journal ArticleDOI
TL;DR: In this paper, 3, 6-dichloropyridazine (III) with sodium azide resulted in the formation of a mixed azido-tetrazolo compound (IV).
Abstract: Treatment of 3, 6-dichloropyridazine (III) with sodium azide resulted in the formation of a mixed azido-tetrazolo compound (IV). 3-Azidopyridazine 1-oxide (X) and 6-azidopyridazine 1-oxide (XIX) were synthesized from the corresponding hydrazino compounds (XII, XVII) with nitrous acid, and also from chloro compound IX with sodium azide. Then several reactions, such as ionic reaction, catalytic hydrogenetion, thermal decomposition, reactions with phosphorus trichloride and with phosphorus oxychloride, and reaction with DPPH of these azides were examined.

Journal ArticleDOI
TL;DR: The spectral changes on N-deuteration suggest that pyrimidine derivatives take the amido form, while pyridine and thiazole derivativestake the imido form.
Abstract: 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 N1- 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 SO2 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.

Journal ArticleDOI
TL;DR: Aqueous sodium tungstate and alum were successfully used in the deproteinization of blood or serum to determine the sugar value with 3, 6-dinitrophthalic acid.
Abstract: Aqueous sodium tungstate and alum were successfully used in the deproteinization of blood or serum to determine the sugar value with 3, 6-dinitrophthalic acid. They were easily prepared and preserved, and fitted for clinical tests. The deproteinizing agent could also be used in a powdered state.

Journal ArticleDOI
TL;DR: By condensing aliphatic and alicyclic ketones with glutarimide-β-acetaldehyde, several cycloheximide analogous compounds listed in Table I were synthesized.
Abstract: By condensing aliphatic and alicyclic ketones with glutarimide-β-acetaldehyde, several cycloheximide analogous compounds listed in Table I were synthesized. The paper also dealt with improved synthesis of glutarimide-β-acetaldehyde.



Journal ArticleDOI
TL;DR: Washburn's equation of penetrating rate could be applied to the penetrating in the capillary of a tablet due to the decrease of surface tension.
Abstract: The effects of the penetrating rate on tablet disintegration were examined. Viscosity, surface tension, contact angle of liquid and the mean capillary diameter of tablet were measured and their effects on disintegration were discussed. In high viscosity solution, the rate of penetration decreased and the disintegration was not well. The viscosity of gastric juice was measured and tablet disintegration in human gastro-intestinal tract was examined by X ray. It was estimated that a tablet disintegration might be affected by the viscosity of gastric juice. The rate of penetration of powder in a surfactant solutions and the penetration of the powder coated by surfactant in pure water were measured. The effect of surfactant on disintegration could not be generally expected due to the decrease of surface tension. The mean diameter of open capillary in a tablet was measured by air permeametry. The diameter was decreased by a large compressional force in tableting and increased by a large quantity of disintegrator. The equation of penetrating rate was discussed theoretically to apply it for the penetrating in tablet capillary. It was concluded that Washburn's equation of penetrating rate could be applied to the penetrating in the capillary of a tablet.

Journal ArticleDOI
TL;DR: Pyridazine N-oxide derivatives have been studied by NMR spectroscopy as mentioned in this paper, and the structures determined from the results are consistent with the dipole moment studies, which can be easily assigned by first order treatments.
Abstract: Pyridazine N-oxide derivatives have been studied by NMR spectroscopy. In all cases the spectra were simple patterns, which could be easily assigned by first order treatments. In order to obtain a complete assignment of the ring proton signals, a number of pyridazine N-oxide derivatives were examined, and the structures determined from the results are consistent with the dipole moment studies. Analysis of N-oxidation reaction mixtures of pyridazine derivatives was performed by NMR spectroscopy. Substituent effects on the chemical shifts are discussed in relation to the other aromatic ring systems. The electronic distribution of pyridazine N-oxide and diamagnetic anisotropy effect of N-O group are also discussed briefly.




Journal ArticleDOI
TL;DR: The most appropriate explanation for the results obtained was the promotion of hydroxylation in the first and middle stages of DAB feeding, although there were yet several problems.
Abstract: The biliary excretion of DAB metabolites was first examined by paper chromatography, colorimetry, and by other methods. Presence of a selectivity in rat liver was recognized such as the main excretion of DAB metabolites retaining the azo bond into the bile and seven kinds of DAB metabolites (AB, 4'-OS-DAB, 4'-OS-MAB, 4'-OS-AB, 4'-OG-MAB, 4'-OG-MAB, 4'-OG-AB) were identified. Second, influence of DAB feeding on the amount of these seven kinds of DAB metabolites was examined by the method of newly devised separatory determination using DEAE ion-exchanger and other methods. The most appropriate explanation for the results obtained was the promotion of hydroxylation in the first and middle stages of DAB feeding, although there were yet several problems.


Journal ArticleDOI
TL;DR: The physiological disposition and the metabolic fate of hypnotic, 2-methyl-3-o-tolyl-4 (3H)-quinazolinone (MTQ), were studied in man, rat and rabbit.
Abstract: The physiological disposition and the metabolic fate of hypnotic, 2-methyl-3-o-tolyl-4 (3H)-quinazolinone (MTQ), were studied in man, rat and rabbit MTQ is rapidly absorbed from the gastrointestinal tract in man and rat The concentraton of the drug in depot fat is remarkably high compared with that in other tissues in rat The drug is almost completely metabolized in the body and the rate of biotransformation of the drug is relatively slow Glucuronides excretion after oral administration of 200 mg/kg of MTQ was about 20% in a rabbit