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Volume 79, Issue 3
Displaying 1-37 of 37 articles from this issue
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Cleavage of Diphenyl Ether Derivatives by Hydrazine Hydrate. (4)Kenji Ikawa1959 Volume 79 Issue 3 Pages 269-272
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrazinolysis of nine kinds of nitro-chlorodiphenyl ether derivatives, having chlorine in different position of the phenol ring without nitro group was examined. Of these, the compounds possessing a nitro group in the para-position to the chlorophenoxyl group, i. e. 4-nitro-chlorodiphenyl ether derivative (I), easily undergoes hydrazinolysis by hydrazine hydrate, irrespective of the position of chlorine, to form 4-nitrophenylhydrazine (II) and chlorophenols (III), while under a high pressure, 4-amino-chlorodiphenyl ether (IV) is partly formed.
In case of (V), where the nitro group is present in the meta-position, hydrazinolysis is not effected either at ordinary or higher pressure and reduction of the nitro group occurs under pressure, forming 3-amino-chlorodiphenyl ether (VI). When the nitro group is present in the ortho-position, hydrazinolysis proceeds to form 2-nitrophenylhydrazine (VIII) and chlorophenol (III), and (VIII) is further dehydrated to 1-hydroxybenzotriazole (VIIIa).View full abstractDownload PDF (617K) -
Cleavage of Diphenyl Ether Derivatives by Hydrazine Hydrate. (5)Kenji Ikawa1959 Volume 79 Issue 3 Pages 273-276
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrazinolysis of dinitrodiphenyl ether derivatives, possessing nitro groups in different positions on the two phenyl rings, was examined. When the nitro group is present in the ortho-position to the phenoxyl, the ether bonding in the compound (I) is preferentially cleaved by hydrazine hydrate to form 2-nitrophenylhydrazine (II) and the corresponding nitrophenol derivatives (III). (II) easily undergoes dehydration to form 1-hydroxybenzotriazole (IIa).
When the nitro group is in the para-position to the phenoxyl, as in (IV) and (V), hydrazinolysis is also effected to form 4-nitrophenylhydrazine and p- or m-nitrophenol (VII or VIII). In this case, the cleavage reaction proceeds more easily under a high pressure than at atmospheric pressure.
When the nitro group is in the meta-position to the phenoxyl, hydrazinolysis does not proceed at all, either at ordinary or higher pressure, and only reduction of the nitro group occurs to form the amine (XII).View full abstractDownload PDF (685K) -
Necessary Amount of Coating and Toxicity of Coating AgentsTadao Ida1959 Volume 79 Issue 3 Pages 276-280
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExaminations were made on the amount to be used and toxicity of various protective coating agents, whose syntheses have already been described, in order to use them for practical application.
For examination of the amount of the coating necessary to give a perfect coating, tablets were coated and relationship between the number of coating, and the amount of coating and thickness of the coated agent was examined. Measurements were also made on the amount of moisture absorption by tablets with different number of coatings. The time it takes for disintegration of tablets with different number of coatings was examined in distilled water and simulated gastric juice.
It was thereby found that a coating of 60-100μ in thickness gave the perfect coating and such a coating was sufficient as a protective agent. Toxicity tests with these coating agents using mice showed them to be free from toxicity.View full abstractDownload PDF (644K) -
Practical Application to Pharmaceutical PreparationsTadao Ida1959 Volume 79 Issue 3 Pages 281-286
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe useful protective coating agents synthesized earlier were used on various preparations and their effect was examined. Coating of hygroscopic drugs, such as diphenhydramine hydrochloride, with these agents was found to prevent moisture absorption by these tablets and various defects arising from moisture absorption. Coating of thiamine, ascorbic acid, acetylsalicylic acid, and oxytetracycline tablets was effective in preventing periodical change of these drugs and to stabilize the tablets. Moisture absorption and decrease of content in sugar-coated and gelatine-coated tablets were prevented and tablets stabilized by giving preliminary protective coating, as well as preventing periodical change of componental drugs. It was also found that this protective coating can be used with granular preparations to prevent moisture adsorption and decomposition of granules, effect stabilization, and to mask the taste and odor of drugs, thereby making it easier to take. This also eliminated mutual action of drugs in mixed granular preparations and stabilize the drugs.
The preparations coated with the foregoing protective agents were found to undergo rapid disintegration in simulated gastric juice.View full abstractDownload PDF (832K) -
Makoto Suzuki1959 Volume 79 Issue 3 Pages 286-290
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAryl esters (aryl=m-tolyl, o-methoxyphenyl, 4-isopropyl-3-methylphenyl, and 2-isopropyl-5-methylphenyl) of p-aminosalicylic acid (PAS) and 4-amino-2-chlorobenzoic acid (o-Cl-PABA), and their p-succinamido compounds, p-maleylamidosalicylic acid, and p-phthalylamidosalicylic acid were prepared and their in vitro tests were carried out with tubercle bacilli, using Dubos medium and strains E5, H37Rv, and H37Rv-R-PAS. The aryl ester of o-Cl-PABA had antibacterial activity against the H37Rv-R-PAS strain, differing from PAS compounds, but its p-succinamido compounds, with the exception of p-isopropyl-m-cresyl and thymyl esters, had almost no such antibacterial activity. p-Maleylamidosalicylic and p-phthalylamidosalicylic acids showed comparatively good antibacterial activity.
p-Succinamido compounds, whose in vitro antibacterial power was weaker than that of sodium-PAS and which was expected to increase the antibacterial power by inhibiting the TCA-cycle of tubercle bacilli, did not show any better antibacterial activity than the free amino compounds.View full abstractDownload PDF (705K) -
Syntheses of Oxazolopyridines and Related Compounds. (2)Torizo Takahashi, Akira Koshiro1959 Volume 79 Issue 3 Pages 291-295
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1) 3-Amino-4-hydroxy-5-bromopyridine (II) was heated with acid anhydrides and 3-acylamino-4-hydroxy-5-bromopyrimidines (III to VI) and 2-alkyl (or aryl)-7-bromoxazolo[4, 5-c]pyridines (VII to X) were prepared. The latter compounds were converted to the corresponding monomethiodides (XI to XIV) by reaction with methyl iodide.
2) Reaction of (II) with potassium methylxanthate in methanol afforded 2-mercapto-7-bromoxazolo[4, 5-c]pyridine (XV) which was reacted with alkyl halides to form the corresponding thioethers (XVI to XVIII).
3) Reaction of (II) with cyanogen bromide, either in anhyd. ethanol or water, afforded 3-cyanamido-4-hydroxy-5-bromopyridine and not 2-amino-7-bromoxazolo-[4, 5-c]pyridine. It was assumed that, in this case, a reaction between (II) and diethyl iminocarbonate, formed by the reaction of ethanol and cyanogen bromide, might occur to produce 2-ethoxy-7-bromoxazolo[4, 5-c]pyridine as a by-product but the latter compound was not isolated.View full abstractDownload PDF (837K) -
Formation of Thiamine Anhydride from Thiamine. (3)Chikataro Kawasaki, Isao Tomita1959 Volume 79 Issue 3 Pages 295-297
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSApplication of alkaline benzenesulfonyl chloride to thiamine results in the formation of thiamine anhydride (IV), but it had been surmised that this reaction proceeds through intermediate formation of O, O′-bis (benzenesulfonyl) thiamine disulfide (II) or O-benzenesulfonylthiamine (III). In order to compare the change of (II) and (III) to (IV) in alkaline medium quantitatively, N sodium hydroxide solution was added to 1-100mg% solution of (II) and (III), and residual amount was determined (Table I). (III) almost completely disappeared on being made alkaline and formation of (IV) was detected by paper chromatography. (II) changed only slightly in alkaline medium and 15-35% remained 60 minutes later. (III) underwent decomposition at above pH 8, while (II) decomposed above pH 11 (Table II). These results suggest that (III) is produced as an intermediate for the formation of (IV) from thiamine and that (III) undergoes cyclization in alkaline medium.View full abstractDownload PDF (473K) -
The Structure of SclerotiorinYuzuru Yamamoto, Noriko Nishikawa1959 Volume 79 Issue 3 Pages 297-302
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe structure of sclerotiorin, C21H23O5Cl, found in the metabolic product of Penicillium implicatum was discussed. Sclerotiorin reacted with ammonia and changed to sclerotioramine (II). From the acetate of (II), 2, 4, 5-pyridinetricarboxylic acid was obtained by treatment with ozone, followed by potassium permanganate. Tetrahydrosclerotiorin was degradated by alkali to a quinone compound which was determined as β-dihydroxynaphthoquinone. The relation of substituted groups (OH, OH, Cl, CH3) in aposclerotioramine (IV) was cleared and a tentative structural formula (I) is forwarded for sclerotiorin.View full abstractDownload PDF (967K) -
Catalytic Synthesis of C-AlkylhomopiperazinesTakeo Ishiguro, Masaki Matsumura1959 Volume 79 Issue 3 Pages 302-304
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1) High-pressure, catalytic condensation reaction of trimethylenediamine and glycols, using Raney nickel as a catalyst, afforded C-alkylhomopiperazines. Condensation of trimethylenediamine with propylene glycol and 2, 3-butanediol respectively afforded 2-methylhomopiperazine (yield, 6.6%) and 2, 3-dimethylhomopiperazine (yield, 13.7%).
2) Reaction of alkanolamines and acrylonitrile afforded 3-(2-hydroxyalkylamino)-propionitrile, whose catalytic reduction over Raney nickel gave N-(2-hydroxyalkyl)-1, 3-propylenediamines (yield, 70-78% from acrylonitrile). Dehydrative cyclization of these compounds in an autoclave afforded 2-methylhomopiperazine (yield, 44.7%) and 2, 3-dimethylhomopiperazine (yield, 39.1%).
The C-alkylhomopiperazines obtained by the foregoing two kinds of reaction were found to be identical by mixed fusion of their respective derivatives.View full abstractDownload PDF (464K) -
Surface Acidity and Catalytic Vapor-phase Decomposition of IsopropanolTakeo Ishiguro, Akinobu Otsuka1959 Volume 79 Issue 3 Pages 305-307
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeveral kinds of catalyst of cadmium phosphate-silica system of different componential ratio were prepared and their surface acidity was measured by the indicator-absorption method. Using these catalysts, catalytic vapor-phase decomposition of isopropanol was carried out to examine their activity. It was thereby discovered that by mixing cadmium phosphate in silica, which had a very weak surface acidity and had virtually no activity of dehydrating isopropanol, surface acidity appeared and such a catalyst had marked activity of dehydrating isopropanol. The surface acidity of the catalyst of this system was stronger than that of alumina alone but weaker than that of a catalyst of silica-alumina system. On the other hand, in the catalyst of cadmium phosphate-acid clay system, the catalyst surface failed to form active center of dehydrogenation until the content of cadmium phosphate reached around 40%, and the catalytic vapor-phase decomposition of isopropanol was mainly the dehydrogenation reaction.View full abstractDownload PDF (539K) -
Properties of Alumina as a Carrier of CatalystTakeo Ishiguro, Akinobu Otsuka1959 Volume 79 Issue 3 Pages 308-309
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeveral catalysts of cadmium phosphate-alumina system of different componential ratio were prepared, and the size of their surface area and their activity in catalytic vapor-phase decomposition of isopropanol were examined. In this system, the activity is about the same as that of cadmium phosphate alone when the content of cadmium phosphate is approximately over 45%. From such a fact, it was surmixed that alumina acts as a carrier of cadmium phosphate. It was also found that the addition of alumina increased mechanical strength of the catalyst and served in increasing suitability as a practical catalyst.View full abstractDownload PDF (299K) -
Synthesis of 2, 2′-Biquinoline Derivatives. (1)Saburo Nakano1959 Volume 79 Issue 3 Pages 310-313
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS2-Bromoquinoline (from quinoline), 2-bromolepidine, and 2-bromo-3, 4-dimethyl-, 2-bromo-4, 6-dimethyl-, 2-bromo-4, 7-dimethyl-, and 2-bromo-4, 8-dimethyl-quinolines were synthesized from aniline and o-, m-, and p-toluidine, through acetoacetanilide and carbostyril derivatives, by reacting finally with phosphorus pentabromide or phosphoryl bromide. 2, 2′-Biquinoline derivatives, cuproine, 2, 2′-bilepidine, and 4, 4′, 6, 6′-tetramethyl-, 4, 4′, 7, 7′-tetramethyl-, and 4, 4′, 8, 8′-tetramethyl-2, 2′-biquinolines, were synthesized by the application of hydrazine hydrate to 2-bromoquinoline derivatives obtained above, in 5% ethanolic (or methanolic) potassium hydroxide in the presence of palladium-calcium carbonate. Of these, seven compounds are new substances. Synthesis of 2, 2′-biquinoline derivatives using bromo compounds is the first of such reaction and a good yield of 25-57% was obtained. Attempted preparation of 3, 3′, 4, 4′-tetramethyl-2, 2′-biquinoline showed that the methyl groups in 3- and 3′-positions effected steric hindrance, preventing the bonding of quinolines at 2- and 2′-positions.View full abstractDownload PDF (709K) -
Syntheses of 2, 2′-Biquinoline Derivatives. (2)Saburo Nakano1959 Volume 79 Issue 3 Pages 314-317
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFive kinds of biquinolines were prepared by application of hydrazine hydrate to 2-bromoquinoline derivatives in 5% methanolic (or ethanolic) potassium hydroxide, in the presence of palladium-calcium carbonate catalyst. With the exception of 4, 4′-diphenyl derivative, 4, 4′-diphenyl-6, 6′-, -7, 7′-, and 8, 8′-dimethyl-2, 2′-biquinolines, and 4, 4′-dimethyl-6, 6′-dimethoxy-2, 2′-biquinoline are all new compounds. Preparation of 6, 6′-dimethylbiquinoline from quinoline, by application of metallic sodium was followed. During this synthesis, 3 kinds of new bromo derivatives, 6-methyl-, 7-methyl-, and 8-methyl-4-phenyl-2-bromoquinolines, were obtained. For the starting materials, benzoylaceto-m (and p)-toluidide, 6-methyl-4-phenyl-2-quinolinone, 7-methyl-4-phenyl-2-quinolinone, 2-bromo-4-phenylquinoline, and 2-bromo-4-methyl-6-methoxyquinoline, and related compounds were prepared.View full abstractDownload PDF (757K) -
Alkaloids of Berberis Tschonoskiana REGEL. (1). The Isolation of BasesMasao Tomita, Takehiko Kugo1959 Volume 79 Issue 3 Pages 317-321
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAlkaloids contained in the domestic Berberis Tschonoskiana REGEL. (Japanese name ‘Ohba-megi’) were examined and 9 kinds of bases listed in Table II were isolated. Of these, 3 kinds of tertiary bases, obamegine, obaberine, and of m.p. 89-92° are new bases first discovered from this plant (cf. Table III).View full abstractDownload PDF (777K) -
Alkaloids of Berberis Tschonoskiana REGEL. (2). Structure of ObamegineTakehiko Kugo1959 Volume 79 Issue 3 Pages 322-324
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe structure of obamegine, the new phenolic tertiary base isolated from Berberis Tschonoskiana REGEL., was examined. This base is a biscoclaurine-type phenolic base indicated by the molecular and empirical formulae of C36H38O6N2=C32H24 (OCH3)2-(OH)2(-O-)2(NCH3)2. O, O-Dimethylobamegine, obtained by its methylation with diazomethane, is identical with isotetrandrine.
Ethylation of obamegine with diazoethane and treatment of O, O-diethylobamegine (m.p. 196-198°) so obtained, to cleavage reaction with sodium in liquid ammonia afforded l-N-methyl-O, O-diethylcoclaurine (VII) and d-N-methylcoclaurine (VIII) as the bisected bases.
It follows, therefore, that the structure of obamegine can be indicated by formula (V), a phenolic base of the berbamine type, as one of the bases of biscoclaurine type, and that steric configuration (optical orientation) of the two asymmetric centers in its molecule is (-, +).View full abstractDownload PDF (504K) -
Alkaloids of Michelia fuscata BLUME. (1)Kazuo Ito, Tomoko Aoki1959 Volume 79 Issue 3 Pages 325-329
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAlkaloid in the leaves of Michelia fuscata BLUME (syn. Magnolia fuscata ANDR.) (Japanese name ‘Toh-ogatama’), a plant of Magnoliaceae family of Chinese origin, was examined and a large amount of magnolamine (I) was found as the tertiary phenolic base.
It had earlier been shown that tetramethylmagnolamine (-, -), obtained by the Ullmann condensation of l-6′-bromolaudanosine and l-armepavine, is an antipode of tetramethylmagnolamine (+, +) (II) obtained from the natural source. Cleavage reaction of natural tetramethylmagnolamine (II) with sodium in liquid ammonia in the present series of experiments afforded d-laudanosine (III) and d-armepavine (IV). This fact reconfirmed the fact that the structure of magnolamine would be indicated by formula (I) and that the steric configuration (optical orientation) of the two asymmetric centers in its molecule is (+, +).View full abstractDownload PDF (1157K) -
Masao Tomita, Sugako Matsumura, Yoshio Sasaki, Emiko Kinoshita1959 Volume 79 Issue 3 Pages 329-334
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSApplication of metallic sodium to tetrahydroberberine (I) in liquid ammonia results in the formation of two kinds of phenolic bisected bases, A and B (cf. Table I). The ratio of the formation of these two bases was found to differ somewhat according to reaction conditions (cf. Table II).
In order to determine the structure of these two bases, various decomposition reactions were carried out and synthesis of such decomposition products was attempted. This proved the structure of A-base to be represented by (XIII) and that of B-base as (XIV). Therefore, reaction of tetrahydroberberine (I) with sodium in liquid ammonia first results in cleavage of methylenedioxy group to a definite direction to form the A-base (XIII), and according to reaction condition, this A-base undergoes secondary demethylation to form the B-base (XIV).View full abstractDownload PDF (1308K) -
Reaction of the Propionitrile Derivatives with Hydrazine Derivatives. (1)Akira Takamizawa, Sadao Hayashi1959 Volume 79 Issue 3 Pages 334-338
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of 2-(1-ethoxy-1-methoxymethyl)-3-ethoxypropionitrile (I), 2-methoxymethylene-3-ethoxypropionitrile (II), and 2-(1-ethoxy-1-methoxymethyl) acrylonitrile (III) in ethanol, in the presence of hydrochloric or sulfuric acid, with phenylhydrazine, p-nitrophenylhydrazine, or m-nitrophenylhydrazine respectively affords the 1-phenyl (IV), 1-p-nitrophenyl (VI), or 1-m-nitrophenyl (X) compound of 4-cyanopyrazole, and not the anticipated hydrazone (XII) or 5-aminopyrazole compound (XIII). This means that a new reaction for a pyrazole condensation had been found. (IV), (VI), and (X) are new compounds and their structure is supported from infrared and ultraviolet spectra, elementary analytical values, and their reactions.
The properties of 4-carboxy compound (V), hydrolysis product of (IV), agreed well with those given in past literature.
The product from nitration of (IV) with sulfuric and nitric acids was identified with the 4-carboxy compound (VIII) obtained by hydrolysis of (VI), while catalytic reduction of (VI) over palladium-chardoal results in absorption of 3 moles of hydrogen to form the amino compound (IX). These facts show that the structure of (VI) and (X) is unequivocal.
Since the velocity of acetalization of (II) and (III) is fairly rapid, it is assumed that the compounds first undergo acetalization to form (I) which takes part in the pyrazole condensation.View full abstractDownload PDF (981K) -
Reaction of the Related Compounds of Propionitrile Derivatives with ArylhydrazinesAkira Takamizawa, Sadao Hayashi1959 Volume 79 Issue 3 Pages 339-343
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFollowing the discovery for a formation of 1-aryl-4-cyanopyrazole by the reaction of 2-(1-ethoxy-1-methoxymethyl)-3-ethoxypropionitrile (I) and arylhydrazine, the behavior of the nitrile group and the alkoxyl in 2-position in this condensation reaction was examined. The reaction of 2-(1-ethoxy-1-methoxymethyl) propionitrile (IV), 2-(1-ethoxy-1-methoxymethyl) propylamine (V), and 2-(1-ethoxy-1-methoxymethyl)-3-ethoxypropylamine (VI) with phenylhydrazine or p-nitrophenylhydrazine afforded 1-aryl-4-methyl-5-aminopyrazoles (XIII) and (VII) from (IV), 1-aryl-4-methylpyrazoles (XII and IX) from (VI), and (IX) from (V). The structure of these products was established from their infrared and ultraviolet spectra, and elementary analytical values. Deamination of (VII) by diazotization gives (IX), oxidation of (IX) with potassium permanganate gives 1-p-nitrophenyl-4-carboxypyrazole (X), nitration of (XII) gives (IX), and reduction of (IX) over palladium-carbon affords the amino compound (XI). These facts indicate the correctness of the structure of the reaction products (VII), (IX), (XII), and (XIII).
Foregoing results indicate that the nitrile group in (IV) behaves in ordinary reaction type and the alkoxyl in (VI) does not take part directly in pyrazole condensation but acts toward aromatization. The compound (V) is somewhat less reactive than (VI) but both undergo cyclization to pyrazole compound accompanied by dehydrogenation. These facts are interesting in connection with results described in the preceding paper.View full abstractDownload PDF (1086K) -
Studies on Surface Tension of their Aqueous SolutionRyohei Hori1959 Volume 79 Issue 3 Pages 343-349
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSurface tension was measured of alkyl glycosides of D-xylose, D-glucose, D-galactose, and D-cellobiose, and fatty acid monoesters of D-glucose and D-galactose. The measurement was made with Du Noüy's apparatus but the values were so scattered that examinations were made on its reason. It was thereby found that the values were greatly affected by periodical change of tension due to surface adsorption of nonionic surfactant molecules, and homogenization of solution surface and internal concentration, and destruction of surface film by stirring. It was found that the maximum and minimum equivalence values are obtained by measurement of surface tension at standstill and under stirring, under definite conditions. If these facts were not taken into consideration, the values obtained will be scattered between these two limits. The presence of a surface film was assumed.
Reproducibility of these two limiting values was examined with four representative substances and a good result was obtained. Therefore, surface tension of various sugar derivatives prepared to date was measured in aqueous solution under these conditions. As a result, some compounds were found to have somewhat better activity than sodium laurylsulfate in reducing surface tension, the following compound reducing the surface tension of water at 15° to less than 45 dyne/cm. in a dilute solution of below 10-2 M: Octyl β-D-xyloside, oleyl β-D-xyloside, decyl β-D-galactoside, decyl β-D-glucoside, oleyl β-D-glucoside, decyl β-D-cellobioside, oleyl β-D-cellobioside, D-glucose 3-caproate, D-glucose 3-caprylate, D-galactose 6-caproate, D-galactose 6-caprylate, D-galactose 6-caprate, and D-galactose 6-laurate.View full abstractDownload PDF (1138K) -
Detection of the Anthelmintical ConstituentsKoji Daigo1959 Volume 79 Issue 3 Pages 350-353
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSClinical tests revealed that the decoction of Chondria armata (KÜTZING) OKAMURA (Rhodomelaceae) had a marked anthelmintic action and further examinations were made on the anthelmintic components of this seaweed. It was found that this anthelmintic principle transited from aqueous extract to hydrous methanol from which it is adsorbed on alumina and eluted from it by water. The principle is adsorbed on activated carbon from aqueous extract and eluted from it by methanol, or adsorbed on Amberlite IR-120 and eluted from it by alkali solution. Anthelmintic effective fraction was prepared by the use of these properties.
This effective fraction was submitted to paper partition chromatography and paper electrophoresis, and spots coloring yellow to ninhydrin were detected at Rf 0.31-0.32 and 0.54-0.56 in the former, and at migration distance of +52-+57 and +99-+102.
The behavior of the anthelmintic principles of Chondria armata was very similar to those (Rf 0.50 and migration distance +70) of kainic acid, the anthelmintic principle of Digenea. From these facts it was assumed that the anthelmintic principle of this seaweed is a substance related to kainic acid.View full abstractDownload PDF (711K) -
Isolation of an Anthelmintical ConstituentKoji Daigo1959 Volume 79 Issue 3 Pages 353-356
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAn odorless, and slightly acid and acrid component was extracted from Chondria armata (KÜTZING) OKAMURA (Rhodomelaceae) (Japanese name, “Hanayanagi” or “Domoi”) as colorless needle crystals, m.p. 217° (decomp.), [α]D12-109.6° (c=1.314, H2O), UV: λmaxH2O 242mμ (log ε 4.42), C15H21O6N⋅2H2O. Oral administration of 20mg. of this substance was found to be markedly effective in expelling ascaris and pinworm, without any observable side effects. This component was considered to be the anthelmintic principle of Chondria armata and was named “domoic acid.” The acid is soluble in water and acetic acid, easily soluble in dil. mineral acid and alkali solution, and dissolves in sodium carbonate and hydrogen carbonate solution with effervescence. It is sparingly soluble in methanol and ethanol, and insoluble in ether, petroleum ether, chloroform, benzene, and acetone. It discolors bromine water and potassium permanganate solution, indicating unsaturation. It colors yellow to ninhydrin, vanillin, and alloxane, red to Folin reagent, and indigo blue to Feigl's aliphatic secondary amine reaction. Domoic acid forms salts sparingly soluble in water with lead, copper, and mercury. pKa of its aqueous solution are 2.20, 3.72, 4.93, and 9.82. Tetrahydrodomoic acid, m.p. 273° (decomp.), and N-acetyldomoic acid, m.p. 121-123°, were prepared. Neutralization of the latter required 3 equivalents of alkali. Preparation of domoic acid betaine methiodide, m.p. 174°, indicated the presence of three methoxyls. These facts suggest that domoic acid is a tribasic imino acid with two hydrogenatable double bonds.View full abstractDownload PDF (1346K) -
Constitution of Domoic AcidKoji Daigo1959 Volume 79 Issue 3 Pages 356-360
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFor the determination of the structure of domoic acid, the acid was submitted to ozonolysis in aqueous solution. On concentration of the reaction mixture for separation of the reaction products, the procedure at as low a temperature as possible afforded Ls-arabo-2-carboxy-3-carboxymethyl-4-acetylpyrrolidine (IV), m.p. 197°, with propionaldehyde (III), proved as its 2, 4-dinitrophenylhydrazone. When the concentration was made under heat over a direct flame, Ls-xylo-2-carboxy-3-carboxymethyl-4-acetylpyrrolidine (V), m.p. 211°, was obtained besides propionaldehyde (III).
The ultraviolet and infrared spectral analyses of domoic acid indicated that the structure of domoic acid is Ls-arabo-2-carboxy-3-carboxymethyl-4-(1-methyl-2-car-boxy-1, 3-hexadienyl)pyrrolidine.View full abstractDownload PDF (657K) -
Determination of Domoic AcidKoji Daigo1959 Volume 79 Issue 3 Pages 360-364
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA method for the determination of domoic acid, the anthelmintic principle of Chondria armata (KÜTZING) OKAMURA (Rhodomelaceae), was examined. Domoic acid colors yellow (λmaxH2O 403mμ, λmaxiso-AmOH 413mμ) to ninhydrin, red (λmaxH2O 480mμ) to 1, 2-naphthoquinone-4-sulfonic acid, and yellow (λmaxAcOH 380mμ) to alloxane. It was found that domoic acid could be determined quantitatively by colorimetry of these colorations and by measuring the characteristic absorbance of domoic acid at λmaxH2O 242mμ.View full abstractDownload PDF (675K) -
Isolation of L-Citrulline and D-Aspartic AcidKoji Daigo1959 Volume 79 Issue 3 Pages 365-368
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSTwo crystalline components were isolated from Chondria armata (KÜTZING) OKAMURA (Rhodomelaceae) (Japanese name “Hana-yanagi” or “Domoi”). One melts at 222° with decomposition, [α]D11+4.1°(c=2.91, H2O), [α]D11+15.3°(c=2.51, 2M HCl), C6H13O3N3, and was identified with L-citrulline. The other melts at 260° with decomposition, [α]D7-22.8°(c=2.90, NHCl), [α]D7+3.0°(c=2.67, NNaOH), C4H7O4N, and was found to be D-aspartic acid.View full abstractDownload PDF (681K) -
Antibacterial Action of 2-Mercapto-3-hydrazinoquinoxaline Derivatives on Various BacteriaKazuo Asano, Sotoo Asai, Naoyuki Inoue1959 Volume 79 Issue 3 Pages 368-370
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHeterocyclic aldehydes and ketones of 2-mercapto-3-hydrazinoquinoxaline, hydrazones of sugars and α-and β-keto acids, and compounds with substituted hydrazino group in 3-position were prepared and their activity in inhibiting the growth in vitro was examined with Staphylococcus aureus, Escherichia coli, Candida, Aspergillus, Trichophyton, Mycobacterium tuberculosis 607, and human-type tubercle bacilli. None of the compounds so far tested showed stronger activity than 2-mercapto-3-hydrazinoquinoxaline. The antibacterial spectra of hydrazones differed according to the kinds of corresponding carbonyl compounds and aliphatic compounds were found to show antibacterial spectra and activity similar to those of the parent compounds. The derivatives of this system showed fairly strong antibacterial activity against humantype tubercle bacilli. The same difference between substituent group and antibacterial activity was found in 3-substituted hydrazino derivatives.View full abstractDownload PDF (520K) -
Rihei Fujimoto, Shinsuke Ose1959 Volume 79 Issue 3 Pages 371-374
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of ephedrine hydrochloride (I) with ninhydrin results in violet coloration at pH 8.0, while that at pH 5.0 remains colorless. On the other hand, reaction of ephedrone hydrochloride (II) and ninhydrin results in reddish violet coloration at pH 8.0, while that at pH 5.0 produces reddish brown precipitate sparingly soluble in water. This precipitate dissolves in amyl alcohol to form a pink solution. By using these reactions, determination of (I) in a mixture of (I) and (II) became possible. In this method, a mixture of (I) and (II) is submitted to colorimetry at pH 5.0 to determine the amount of (II), the mixture is measured again at pH 8.0, and the value of (II) obtained at pH 5.0 is subtracted from the value obtained at pH 8.0. The remained value is (I) in a mixture. If amyl alcohol solution, containing constant amount of a mixture of (I) and (II), is measured at pH 8.0, it is possible to determine both at one procedure from relationship between the mixture ratio and absorbancy of the two substances.View full abstractDownload PDF (582K) -
Purification by Zone ElectrophoresisHiroshi Moriya, Eiichiro Shimazawa1959 Volume 79 Issue 3 Pages 374-377
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe product H (70-80U./mg.), obtained from hog pancreas by the method using Acrinol (2-ethoxy-6, 9-diaminoacridinium lactate), was purified further by zone electrophoresis using starch as a carrier (Procedure VIII). In an electrophoresis box of 40×10×1.5cm., using veronal buffer, a constant current of 2mA/cm2 was passed for 15-22 hours. Separated components were cut out with starch, extracted with distilled water, and the solution was lyophilized. The effective portion was purified to an extreme purity of 570U./mg. and this product was found to be a homogeneous unity from paper electrophoretic and ultra centrifugal analyses. The purity of each zone obtained by this method agreed with the values estimated from paper electrophoretic analysis. This method showed good reproducibility in repeated experiments and recovery of potency was comparatively good.View full abstractDownload PDF (1369K) -
Shuichi Namba, Sanae Matsushima1959 Volume 79 Issue 3 Pages 378-381
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe gonadotropic hormone in the human pregnancy urine is adsorbed on weakly acid ion exchanger (Amberlite XE-64) from acid urine and is easily eluted from the resin on stirring the resin in a solution containing ammonium ion. Detailed examinations were made on the conditions of adsorption and desorption, and it was found that the optimal pH for adsorption is 3.5 and that the said hormone is almost completely adsorbed when using 2.5g of resin to 1L. of urine. The best result was obtained, both from the point of purity and yield, by desorption with 40% ethanol containing 10% of ammonium acetate. The purity of the product obtained by this procedure depends on the content of this gonadotropic hormone in the urine but a maximum of ca. 6000I.U./mg. product was obtained.View full abstractDownload PDF (1041K) -
Studies on the Structure of Sciadopitysin, a Flavonoid from the Leaves of Sciadopitys verticillata SIEB. et ZUCC. (5). Degradation of Sciadopitysin Trimethyl Ether in Ethanolic PotassiumTatsuo Kariyone, Nobusuke Kawano, Michiko Maeyama1959 Volume 79 Issue 3 Pages 382-385
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExaminations were made on reaction conditions for alkaline decomposition of sciadopitysin trimethyl ether and results listed in Table I were obtained. Condensation of phloroacetophenone and p-methoxyphenylacetonitrile by the Hoesch reaction afforded 2-hydroxy-3-acetyl-4, 6, 4′-trimethoxydesoxybenzoin (II). Since (II) differs from the ‘substance A’, one of the alkaline decomposition products of sciadopitysin trimethyl ether, the assumed structure of sciadopitysin reported earlier must be corrected. From the examination of ultraviolet and infrared spectra of (II), the presence of a 2-hydroxy-3-acetyl-4, 6-dimethoxyphenyl group in the ‘substance A’ is presumed.View full abstractDownload PDF (659K) -
Kenji Ikawa1959 Volume 79 Issue 3 Pages 386-388
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSBiguanido derivatives of six kinds of diphenyl ethers and diphenyl sulfides were prepared. Dicyanodiamide was reacted with 2-, 3-, and 4-aminodiphenyl ether hydrochloride, and 2-, 3-, and 4-aminodiphenyl sulfide hydrochloride, in ethanol and the hydrochlorides of corresponding biguanido derivatives were obtained. Their nitrates were obtained by the addition of ammonium nitrate to the hydrochlorides, and alkali treatment of the hydrochlorides afforded the free bases.View full abstractDownload PDF (568K) -
Tanekazu Kubota1959 Volume 79 Issue 3 Pages 388-392
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSElectronic structures and other various feature of heterocyclic N→O compounds were discussed using the molecular orbital method.
In this calculation, the following treatments are used. i) Differential overlap is neglected. ii) Coulomb integral of hetero-atom (αμ) is represented as αμ=α+kμβ, where kμ is chosen so as to satisfy the Jaffé's relation between Hamett's σ-values of N→O determined experimentally and π-electronic densities.
Molecular orbitals and their energies thus calculated can interpret the various feature of N→O compounds. Especially, in order to explain the ultraviolet absorption of N→O, the interaction between the pyridine part and oxygen atom is calculated. Then, it seems reasonable to assume that ultraviolet absorptions at -281mμ of pyridine N-oxide originate from the contribution of charge transfer configuration due to the charge displacements from oxygen to pyridine nucleus.View full abstractDownload PDF (657K) -
Toyohiko Kawatani, Sanaenosuke Fujita, Tadaro Ohno, Norito Kuboki, Kaz ...1959 Volume 79 Issue 3 Pages 392-393
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFive kinds of Ephedra cultivated at Kasukabe, Ephedra distachya L., E. Gerardiana WALL., E. equisetina BUNGE, E. altissima DESF., and E. campylopoda C. A. MEY., were harvested in October, 1957, and the content of total alkaloid (as ephedrine) in the terrestrial green portion were 1.84%, 1.59%, 1.15%, 1.15%, and 1.25%, respectively. Somatic chromosome number of these plants was determined respectively as 28, 56, 28, 28, and 28. Growth of all five kinds of Ephedra was good.View full abstractDownload PDF (289K) -
Studies on the Component of the Leaves of Picea Glehnii MASTERS. (3). On the Occurrence of Picein and ResveratrolTatsuo Kariyone, Mitsuo Takahashi, Tokuzo Ito, Koichiro Masutani1959 Volume 79 Issue 3 Pages 394-395
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFrom the methanol extract of the leaves of Picea Glehnii MASTERS, picein, piceol (p-hydroxyacetophenone), and resveratrole were isolated besides piceid.View full abstractDownload PDF (304K) -
Attempted Diene-Synthesis of Hydroquinone Methyl Ether and 2, 6-Dimethyl-5-hydroxy-2, 3-dihydrobenzofuran with Maleic AnhydrideKeizo Kitahonoki1959 Volume 79 Issue 3 Pages 396-398
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn connection with the previous report on the formation of an adduct (I) from hydroquinone and maleic anhydride on heating, examination was made on whether this diene synthesis would be effected in monomethyl or dimethyl ether of hydroquinone. It was thereby found that an adduct with enol ether structure (II, R=CH3, or III, R=CH3) was not obtained. Two kinds of dihydrobenzofuran (IV and XII), which could be regarded as the monoether of hydroquinone, were prepared and reacted with maleic anhydride but neither formed an adduct.View full abstractDownload PDF (445K) -
Studies on Thiamine MonosaltsAkira Takamizawa, Shigekatu Nakazima, Hisao Satoh1959 Volume 79 Issue 3 Pages 399-403
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSWhen thiamine hydrochloride solution is completely neutralized with over 2 moles of sodium hydroxide, adjusted to around pH 6 with acetic acid, and salted out with alkali halide, thiamine halide precipitates out in a high yield. Thiamine chloride (IV) of cubic crystals, m.p. 135° (decomp.), thiamine bromide (V) of scaly crystals, m.p. 164-166°(decomp.), and thiamine iodide (VI) of scaly crystals, m.p. 160°(decomp.), respectively possesses 1, 1.5, and 1.5 moles of water of crystallization. Thiamine nitrate is also obtained in a high yield and its purification was satisfactorily effected from water containing 2% of acetic acid. When a solution of thiamine bromide (V) in 95% ethanol was maintained at 40°, cubic crystals of m.p. 190° (decomp.) were obtained. Its analytical values and other properties indicated it to be thiamine bromide (V) not containing any water of crystallization. Addition of acetone to this aqueous solution affords the original crystals melting at 164-166° with decomposition. These two kinds of crystals do not transit to each other even on adding crystalline nucleus at the time of recrystallization. When aqueous solution of thiamine nitrate (VII), coming in square prisms of m.p. 189°, is maintained at 50°, crystals of hexagonal prisms of m. p. 204°(decomp.) are obtained. Analytical values and other properties indicate both to be thiamine nitrate. When the aqueous solution of the latter is cooled in ice water, the original square prisms of m.p. 189°(decomp.) are obtained.View full abstractDownload PDF (915K) -
Masaiti Yasue, Yosisige Kato1959 Volume 79 Issue 3 Pages 403-405
Published: March 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAstilbin (d-dihydroquercetin 3-rhamnoside), myo-inositol, and quercetin were isolated from the leaves of Lyonia ovalifolia SIEB. et ZUCC. Var. elliptica HAND.-MAZZ. (Ericaceae). myo-Inositol is present only in the green leaves and not in withered leaves, while quercetin was detected in withered leaves. Hyperoside, glucose, and fructose were detected in the flower, and oleanolic acid and β-sitosterol from immature fruit. Presence of quercitrin (quercetin 3-rhamnoside) is reported in the literature but it was not detected from the materials handled in this experiment. This is probably due to the difference in origin.View full abstractDownload PDF (597K)
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