YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
81 巻 , 5 号
選択された号の論文の38件中1~38を表示しています
  • 長瀬 雄三, 馬場 茂雄
    1961 年 81 巻 5 号 p. 619-621
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Isotopic dilution analysis of caffeine was carried out by the use of caffeine[1 N-methyl-14C], prepared by methylation of theobromine with methyl[14C] iodide. Satisfactory results were obtained by determination of 30-80mg. of caffeine, either alone or in the presence of acetylsalicylic acid, theobromine, aminopyrine, or acetophenetidine.
  • 長瀬 雄三, 松本 潮
    1961 年 81 巻 5 号 p. 622-626
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the precipitation and color reactions of 2, 3-dihydroxy-1, 4-naphthoquinone (isonaphthazarin) and metal ions, and limit of identification was determined. Of the 26 kinds of common metal ions, isonaphthazarine reacted with BiIII and CuII at pH 3.2, and with BiIII, CuII, HgII, CdII, SnIV, NiII, CoII, ZnII, MnII, FeIII, AlIII, MgII, CaII, SrII, and BaII at pH 6.8, forming a bathochromic violet to blue precipitate or colored solution. The reaction with CuII, BiIII, MnII, CoII, NiII, and ZnII was comparatively sensitive and pH at which these metal ions begin to color or form precipitate with isonaphthazarin and the pH at which these reactions are completed were measured. The pH at which the reaction begins was 0.9-1.9 with BiIII, 2.7-2.9 with CuII, and above 4.2-6.0 with other metals. Consequently, specific or selective detection of BiIII and CuII can be made by adjusting pH of the reaction mixture.
  • 長瀬 雄三, 松本 潮
    1961 年 81 巻 5 号 p. 627-630
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the precipitation and color reactions of 2-hydroxy-3-amino-1, 4-naphthoquinone (3-aminolawsone) and metal ions, and their limit of identification was determined. Of the 26 Kinds of common metal ions, the naphthoquinone reacted with BiIII and HgII at pH 3.2 and with BiIII, HgII, CuII, ZnII, FeIII, and AlIII at pH 6.8 to produce bathochromic violet to blue precipitate or color. The reaction with BiIII, CuII, and FeIII in neutral solution was comparatively sensitive. The pH at which these metal ions begin to form precipitate or coloration with the naphthoquinone and pH at which the reaction completes were measured. The pH at which the reaction begins was 0.2 with BiIII, 2.7-2.9 with HgII, 3.2-3.3 with CuII, 4.7 with FeIII, 4.8-4.9 with AlIII, and 6.1-6.2 with ZnII. These facts reveal that selective detection of HgII and CuII, or specific detection of BiIII would be possible by adjustment of pH of the reaction mixture.
  • 長瀬 雄三, 松本 潮
    1961 年 81 巻 5 号 p. 631-635
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reactivity of 26 kinds of common metal ions in producing coloration and precipitation was examined and their limit of detection was determined. Lawsone shows fairly insensitive coloration with NiII, CoII, HgII, and CuII at pH 6.8, forms a lake with BiIII, AlIII, and FeIII, and a precipitate with HgII at pH 3.2, but reaction with other metal ions was insensitive. Juglone undergoes sensitive color action withre NiII, CuII, and CoII, and fairly sensitive coloration with ZnII, MnII, and MgII both at pH 6.8, and forms a lake with AlIII, FeIII, BiIII, and CuII, the reaction being generally mores ensitive than with lawsone. 3-Hydroxy juglone undergoes fairly sensitive coloration with CuII, NiII, CoII, MgII, and MnII, at pH 6.8, forms a lake with AlIII, FeIII, BiIII, and CuII, and precipitate with HgII at pH 3.2. Binding ratio of the compound to metal ion was determined by the method of continuous variation for juglone with NiII and CuII, and for lawsone with NiII and HgII in neutral solution and all showed the ratio 1:2 for metal to quinone.
  • 堀井 善一, 渡辺 利郎
    1961 年 81 巻 5 号 p. 636-639
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    A series of 2-(diethylamino) acetamides were prepared and their oxytocic activity was examined but there were none more active than N-(1, 2, 3, 4-tetrahydro-2-naphthyl)-2-(diethylamino) acetamide (621 I. S.).
  • 新美 仁作, 仙福 健治, 桜根 亘子
    1961 年 81 巻 5 号 p. 640-647
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Some model compounds of bis(benzyltetrahydroisoquinoline)-type bases with biphenyl structure in the molecule were synthesized. dl-4, 4′-Bis(2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-1-isoquinolylmethyl)biphenyl (XII) was synthesized by the route shown in Chart 1 from 3, 4-dimethoxyphenethylamine (VI) and 4, 4′-biphenyldiacetyl chloride (VII), through bis-acetamide (VIII) and bis-3, 4-dihydroisoquinoline (IX). Through the second route shown in Chart 2, 2, 2′-dimethoxybiphenyl (XIV) was derived to 2, 2′-dimethoxy-5, 5′-diacetylbiphenyl (XV) and then to 2, 2′-dimethoxybiphenyl-5, 5′-diacetic acid (XVII) by the Willgerodt-Kindler method, and further to bis-acetamide (XIX) and bis-3, 4-dihydroisoquinoline (XX) from (XVII) and 3, 4-dimethoxyphenethylamine (VI). (XX) was finally derived to the objective dl-5, 5′-bis(2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydrol-isoquinolylmethyl)-2, 2′-dimethoxybiphenyl (XXIII) via amino-1, 2, 3, 4-tetrahydroisoquinoline (XXI) or 3, 4-dihydroisoquinoline dimethiodide (XXII).
    The ultraviolet spectra of (XII) and (XXIII) so obtained were examined comparatively with tiliacorine (III) assumed to possess biphenyl structure in its molecule and dauri-cine (XXIV) possessing diphenyl ether structure in its molecule.
  • 角 保男
    1961 年 81 巻 5 号 p. 647-651
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Leucoriboflavin, reduced form of riboflavin, is easily oxidized to riboflavin when shaken with air. To retain the leuco state, riboflavin was reduced with sodium dithionite or with zinc in acid solution to the leuco compound and its acylation with acetic anhydride or benzoyl chloride gave leucoriboflavin acylate. These compounds were stable in solid state but were easily decomposed to riboflavin acylate on exposure to sunlight or by heating, regaining the yellow color. Several decomposition products of leucoriboflavin acylate are described.
  • 角 保男
    1961 年 81 巻 5 号 p. 652-655
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Leucoriboflavin 5′-phosphate derivatives were prepared by reductive acylation of riboflavin 5′-phosphate. These compounds were rather unstable and were easily hydrolyzed to riboflavin 5′-phosphate derivatives, regaining the yellow color. On heating with 17% hydrochloric acid, leucoriboflavin 5′-phosphate tetraacetate and monoethylformate yielded riboflavin 2′, 5′-anhydride, m.p. 300-302°. This substance was sensitive to light and formed lumichrome as the photo-decomposition product on exposure to light.
  • 長谷川 斉
    1961 年 81 巻 5 号 p. 656-658
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In a previous paper, seven factors were cited as the reasons for variation of Rf values in partition-type paper chromatography and some brief mention was made of the characteristics of filter paper as one of the factors. In the present series of work, the characteristics of filter paper were divided into two, the amount of moisture retained according to relative humidity and the rate of void space. Relationship between atmospheric moisture and water content of the paper was examined by drawing adsorption and desorption isotherms of vapor, using Toyo Roshi No. 51 filter paper. It was thereby revealed that this No. 51 is a filter paper suitable for paper partition chromatography, that the theory of BET and of capillary condensation, applicable to powder, are also applicable to filter papers, and that the weight of filter paper at the time of absolute dryness, G1 (necessary when using Zaffaronitype impregnated filter paper), can be derived from equation (1) or from the adsorption isotherm (Fig. 1).
    It was considered that the formation of a hysteresis loop by the desorption isotherm is an indication of the presence of a bottle-neck type capillary and that the approximate identity of the Kelvin radius calculated from the equilibrium vapor pressure of the starting point of hysteresis with theoretical value shows there was only a small experimental error.
  • 藤村 一, 大幡 勝也, 疋田 英昭, 野村 彰, 霜村 末隆, 長沢 久充
    1961 年 81 巻 5 号 p. 659-663
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Screening tests were carried out, with special emphasis on toxicity and analgesic action, on numerous 2-anilinoacetamide derivatives, prepared for the purpose of decreasing the toxicity and increasing solubility of acetanilide and acetophenetidine with increase or retention of their pharmacological effect. Two compounds were found to satisfy these objectives; GB-105 and GB-302.
  • 関口 慶二
    1961 年 81 巻 5 号 p. 664-669
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Solubilizing action of the sodium salt of benzoic acid, o-, m-, and p-hydroxy-, methoxy-, amino-, nitro-, and chloro-benzoic acid, and nicotinic acid on caffeine was determined and the effect of the kind and position on the solubilization was examined. The solubilizing action was found to be in the descending order, in molar equivalent of the salt, of salicylate≅m-chloro-, p-chloro-, m-hydroxy-≅p-hydroxy-≅m-methoxy-≅p-methoxy-, m-nitro-, p-nitro-, o-amino-, and p-amino-benzoate, benzoate, m-aminobenzoate, nicotinate, and o-chloro-, o-methoxy-, and o-nitro-benzoate. The solubilizing action of these benzoates is assumed to be not due to formation of a complex of established composition but due to the formation of a hydrogen bond between caffeine and benzoate, with the water molecule of the solvent acting as the hydrogen-bond donor.
  • 関口 慶二
    1961 年 81 巻 5 号 p. 669-674
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thermal analysis was carried out on 26 kinds of binary systems, having caffeine as one component and various carboxylic acids as the other. Molecular compounds were formed by caffeine with o-, m-, and p-hydroxybenzoic acid, gallic acid, m-me-thoxybenzoic acid, m-nitrobenzoic acid, o-, m-, and p-aminobenzoic acid, phenylacetic acid, malonic acid, oxalic acid dihydrate, and maleie acid. Caffeine did not form a molecular compound with benzoic and phthalic acids. Comparison of the result of thermal analysis and the report of Higuchi and others regarding caffeine complex in aqueous solution suggested that there is some difference in the behavior of caffeine between anhydrous state and in aqueous solution.
  • 関口 慶二
    1961 年 81 巻 5 号 p. 675-680
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thermal analysis was carried out on 39 kinds of binary system, consisting of theophylline, theobromine, or 2, 3-dihydroxypropyltheophylline as one component and benzoic acid, substituted benzoic acids, nicotinic acid, phenylacetic acid, or dicarboxylic acids as the other component. Theophylline formed a molecular compound with benzoic, phthalic, m-chlorobenzoic and p-nitrobenzoic acids, with which caffeine does not combine. Theobromine formed a molecular compound with o-, m-, and p-hydroxybenzoic acid, gallic acid, and malonic acid. Thermal analysis with 2, 3-dihydroxypropyltheophylline as one component failed to give distinct phase diagram but it seemed that the compound formed a molecular compound with m- and p-hydroxybenzoic acid.
  • 関口 慶二
    1961 年 81 巻 5 号 p. 681-686
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thermal analysis was carried out on 32 kinds of binary system consisting of caffeine, theophylline, or theobromine as one component and phenols, aromatic amines, or substituted benzoic acid esters as another. These methylxanthines form molecular compounds with phenols easily but does not with aromatic amines, except only nitroaniline and benzidine form binary compound with caffeine. There seemed to be no affinity with esters and only theophylline formed a molecular compound with ethyl p-aminobenzoate. It was assumed from the present series of results that two carbonyls take part in caffeine while only one takes part in theophylline and theobromine, and that the combination seemed possible with the NH group at 7-position in theophylline.
  • 関口 慶二
    1961 年 81 巻 5 号 p. 687-692
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thermal analysis was carried out on 36 kinds of binary system with caffeine, theophylline, or theobromine as one component and acid amides, imides, pyrazolone derivatives, sulfanilamides, or ammonium benzoate as the other. None of the combinations of caffeine examined seemed to form a molecular compound except in the binary system of caffeine and iodoform. Theophylline formed a molecular compounds with benzamide, nicotinamide, phthalimide, and dimethylglyoxime, while theobromine did not show any tendency to form such a binary system.
  • 藤江 恭
    1961 年 81 巻 5 号 p. 693-698
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Seven derivatives of 2-diphenylmethoxyethylamines and six of 3-(diphenylmethoxy)-propylamines were synthesized and their papaverine-like antispasmodic activity was tested on some smooth muscle preparations such as rat uterus, mouse intestine, and guinea pig tracheal muscle. The index of thermodynamic activity of these compounds was obtained from the potency ratio and solubility of the bases in water. The ω-(diphenylmethoxy) alkylamines would belong to the second group of antispasmodics, which are strong bases, having pKa larger than 8, and act as cation on smooth muscle of ileum. Larger variability of the thermodynamic activity of these compounds might perhaps depend on the facts that they irreversibly inhibit the motility of smooth muscles, that the free bases easily decompose in aqueous solution, and that the preparation of saturated solution of the bases is very difficult.
    The smooth muscles of uterus would be similar to small intestines rather than to tracheal muscles from the mode of action of several antispasmodics and the ω-(diphenylmethoxy) alkylamines.
  • 藤江 恭
    1961 年 81 巻 5 号 p. 699-703
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Out of six N, N-dimethyl-2-alkoxyethylamines, only 2-ethoxy derivative exhibits acetylcholine like action and, among methyl, ethyl, and propyl ethers of choline, which have cholinomimetic activity, the ethyl ether has the maximum activity. These facts agree with the five-atom chain rule of Ing on cholinergic action. The higher members of these two series showed atropine-like activity and no partial agonist was found. The phase-boundary potential was estimated for the above alkoxyalkylamines, three N, N-dimethyl-ω-(diphenylmethoxy) alkylamines, five alkyltrimethylammonium salts, isopentyl phenylacetate, and potassium bromide. Definite relationship, as stated by Barnes and Beutner, was not found between the phase-boundary potential and acetylcholine-like activity, but it was found that the potential increases within homologous series of increasing molecular weight. It was concluded that the phase-boundary potential is no more than an expression of physicochemical properties of a molecule.
  • 伊藤 一男
    1961 年 81 巻 5 号 p. 703-707
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Presence of water-soluble quaternary bases was examined in the trunk bark of Mechelia compressa MAXIM. (Magnoliaceae) (Japanese name ‘Ogatamano-ki’) and a new base, named michepressine, was isolated as its iodide. Its chemical structure was established as l-1, 2-methylenedioxy-10-hydroxyaporphine (l-O-demethyllaureline methiodide), formulated as (VI).
  • 梁井 光二, 倉石 典, 木下 敏夫
    1961 年 81 巻 5 号 p. 708-711
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Starting from 3, 4, 6-trichloropyridazine, 4-pyridazinyl- (V), 3-methoxy-4-pridazinyl- (VIIIa), 3-ethoxy-4-pyridazinyl- (VIIIb), and 3, 6-dimethoxy-4-pyridazinyl-sulfanilamide (XIX) were prepared. (VIIIa) was also obtained from the 4-amino derivative formed by nitration of 3-methoxy- or 3-ethoxypyridazine through their 1-oxide and final reduction.
  • 中島 栄一, 森岡 正, 池上 佳彦, 田中 郁夫
    1961 年 81 巻 5 号 p. 712-716
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Fluidity of powdered pharmaceutics was examined from their sliding angle. Sliding angle becomes greater as the diameter of a granule becomes smaller and the degree of this change becomes more drastic. Sliding angle also increases with increasing rugosity. When two kinds of samples with different granular diameter are mixed, sliding angle increases in proportion to the mixing ratio until the ratio of granules with smaller diameter reaches a definite value and the value becomes constant after reaching the same value as the sliding angle of granules with smaller diameter, as indicated by equations (7) and (8). When more than two kinds of powder are mixed, sliding angle becomes greater, the smaller the average diameter of granules in the mixed sample and greater the range of distribution. Empirical formula indicated by equation (13) is established for relationship between these values.
  • 中島 栄一
    1961 年 81 巻 5 号 p. 717-723
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Sliding angle and flow rate from an orifice were measured in a mixture of glass beads with lactose, anhydrous dibasic calcium phosphate, talc, titanium oxide, magnesium oxide, starch, calcium p-aminosalicylate (PAS-Ca), and calcium carbonate. In general, mixing of powders resulted in greater sliding angle and smaller flow velocity, and this tendency was especially marked in magnesium oxide, calcium carbonate, and PAS-Ca, and smaller in titanium oxide, talc, and starch. The degree of this change became greater as the diameter of granules decreased. Apparent specific volume of a mixture seemed to suggest that mixing of powders resulted in aggregation of glass beads and formation of some kind of an internal structure in the mixture. A correlation was found to exist between the value obtained from equation (2), which is thought to indicate the degree of aggregation, and the sliding angle and flow velocity. Therefore, changes in fluidity, as indicated by sliding angle and flow rate, by mixing of powders is thought to be due to aggregation caused by binding of glass beads themselves by mixed powders.
  • 富田 真雄, 上田 伸一
    1961 年 81 巻 5 号 p. 724-728
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Tomita had discovered that all substances possessing a dibenzo-p-dioxin skeleton (XVI) gave blue to bluish green coloration with conc. sulfuric acid and potassium nitrate or other oxidation reagents and this is utilized for qualitative reaction of such compounds as the diphenylene dioxide reaction. However, octachlorodibenzo-p-dioxin (XVII) and octabromodibenzo-p-dioxin (XVII) prepared by the present author and others do not undergo this coloration reaction. In order to examine whether this failure is due to the insolubility of (XVII) and (XVIII) in conc. sulfuric acid or because these compounds cannot take the quinoid form required for coloration reaction in general by substitution of all the hydrogens in the benzene ring with halogen atoms, 1, 2, 3, 6, 7, 8-hexamethoxydibenzo-p-dioxin (VIII) and 1, 2, 3, 6, 7, 8-hexamethoxy-4, 9-diethyldibenzo-p-dioxin (XIII) were prepared by the route shown in Chart 1. Of these compounds, (VIII) naturally colored bluish green to this reaction but (XIII) colored violet, contrary to the usual coloration of blue, bluish green, or green in this reaction. Consequently, the reason for failure of the octahalogen derivatives (XVII and XVIII) to show this diphenylene dioxide reaction is due to their complete insolubility in conc. sulfuric acid.
  • 郡 定之, 河野 通文
    1961 年 81 巻 5 号 p. 728-732
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Narcotic preparations often contain ephedrine or methylephedrine and separatory determination of these and codeine or hydrocodeine is generally difficult. Quantitative separation of two kinds of alkaloids was effected in four combinations of codeine and ephedrine, hydrocodeine and ephedrine, codeine and methylephedrine, and hydrocodeine and methylephedrine by partition column chromatography through Celite, using citrate buffer of pH 5.3 as the stationary phase and chloroform and ammonia-saturated chloroform as the mobile phase.
  • 橘川 郁男
    1961 年 81 巻 5 号 p. 732-735
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Tomita and Kikkawa some time ago synthesized d-magnoflorine, a phenolic aporphine-type quaternary base contained in Menispermaceae plants and allied species, and d-laurifoline, a similar base contained in Cocculus laurifolius DC., both as racemic bases, the former as an iodide (I) and the latter as a chloride (II). The racemic bases of (I) and (II) produced two spots with different Rf values on paper chromatogram, one of which was in agreement with the spot of natural dextrorotatroy base. It was assumed from these evidences that optical resolution of the racemic compound had occured during paper chromatography.
    In the present series of work, a large quantity of the synthesized racemic compounds of the two bases were submitted to chromatography. The separated two spots were each extracted and the two were isolated and identified as dextro- and levorotatory magnoflorine iodide (Table I) and laurifoline chloride (Table II). This has given experimental evidence that the two racemic compounds underwent optical resolution by paper chromatography.
  • 桜井 寛, 梅田 益雄
    1961 年 81 巻 5 号 p. 736-740
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of narcotine and Chloramine-T, in dil. hydrochloric acidity, and adjustment of the solution to pH 6.8 with sodium sulfite results in red coloration. This coloration does not occur with morphine, codeine, or thebaine, but papaverine colors yellowish brown by the reaction. Limit of detection by the spot test is 0.8γ/0.05cc. and the reaction can be utilized for colorimetric determination of narcotine. The presence of one of morphine, codeine, and thebaine, in an amount below that of narcotine, has no effect but the presence of papaverine interferes in this reaction. The determination, therefore, is carried out after simple procedure for separation of papaverine. The determination is carried out as follows: To 1cc. of the test solution (60-600γ/cc.) placed in a 10-cc. measuring flask, 1cc. of 2.4N HCl is added and the mixture is maintained at 20° for 5 minutes. To this mixture, 1cc. of 1.2% Chloramine-T solution is added, mixed well, and maintained at 20° for 15 minutes. This mixture is again shaken vigorously. To this mixture, 3cc. of 20% Na2SO3 is added under vigorous shaking, shaking continues for further 30 sec., then 5% Na2HPO4 solution is added to bring the whole volume to 10cc., and optical density of the solution is measured at 515 mμ within 5 minutes. A control test is carried out with the same reagents and in the same manner, using 1cc. of ethanol in place of the test solution.
    In the presence of papaverine pretreatment of the sample with alkali and shaking with isoamyl acetate is carried out to separate papaverine, and the aqueous layer is rendered acid with HCl. This acid solution is basified, narcotine is extracted with CHCl3, and ethanol is added to the residue obtained on evaporation of CHCl3. This ethanol solution is used as the test solution.
  • 加瀬 佳年, 由井薗 倫一
    1961 年 81 巻 5 号 p. 740-747
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The pharmacology of d-N, N, 1-trimethyl-3-(ethylsulfonyl)-3, 3-diphenylpropylamine hydrochloride (A-5) was described in detail. A-5 showed a long-acting antitussive activity, duration of the effect being 18.9 times that of codeine (intravenous) and 13.5 times that of codeine (oral), though 50% antitussive dose is only 1.4 and 1.7 times that of codeine in dogs and cats, respectively. The site of action seemed to be the cough center per se. Toxicity in mice (subcutaneous) is 1.5 times that of codeine and 30% that of Methadone. No tendency to establish tolerance, cumulative action, or addiction liability was found by long-term administration. Analgesic action and other actions were discussed.
  • 掛見 喜一郎, 有田 隆一, 大橋 貞
    1961 年 81 巻 5 号 p. 748-750
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Potency determination of kanamycin solution was carried out as follows: To 5cc. of kanamycin solution in water, 0.5cc. of 20% sodium carbonate solution is added, followed by 0.5cc. of 1% solution of sodium 1, 2-naphthoquinone-4-sulfonate with cooling in ice water, and the mixture is allowed to stand at 0° to 2° for 20 minutes, protected from light. To this solution, 1.0cc. of acetone and 0.5cc. of 50% acetic acid are added and optical density of this solution, is measured at 420 mμ. As a control, the same procedure is carried out with distilled water in place of the sample solution. The potency of the sample solution is read from the calibration curve prepared with kanamycin of known potency.
    The same determination was carried on samples boiled with acid or alkali, and samples left at various temperatures. Comparison of the values so obtained with the values determined by the cup method, stipulated in the antibiotics standard, showed good agreement.
  • 森坂 勝昭, 原田 多賀子
    1961 年 81 巻 5 号 p. 751-754
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    A. C. constant-current titration was carried out as a modification of A. C. polarization titration using platinum electrodes. Similar to the A. C. constant-voltage method reported in previous papers, it is necessary to make the variation of polarization resistance at the electrode as large as possible in order to increase sensitivity of titration and the titration curve shows a type approximately reverse of that in the constant-voltage method. The solution resistance is neglected in the constant-current method and there is no necessity of considering polarization resistance and solution resistance at the same time, as is made in the constant-voltage method. In this sense, the A. C. constant-current method is easy, both theoretically and experimentally.
  • 田村 千尋, 桑野 晴光
    1961 年 81 巻 5 号 p. 755-759
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was found that chloramphenicol palmitate, myristate, and caprylate come in two kinds of crystalline form and one amorphous form. These compounds were prepared and their transition conditions were examined.
    1) When the crystals is dissolved in a solvent and crystallized out, optional form of crystals can be obtained by controlling crystallization rate and this form is not affected by polarity or pH of the solvent. Crystals of α-form is obtained by rapid crystallization while the β-form is obtained by gradual crystallization. When a small amount is fused and cooled rapidly in a refrigerator, a vitrious substance is obtained.
    2) Transition between the solids occur only in the direction of amorphous to α-form to β-form, and there is no reverse progress. The transition rate is faster, the nearer the melting point. The mechanism of such a transition is thought to be the transition to a stable form by the heat motion of the molecule itself. The transition rate becomes suddenly rapid after formation of β-form crystal and this is considered to be due to added effect of catalytic transition.
  • 田村 千尋, 桑野 晴光
    1961 年 81 巻 5 号 p. 759-764
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    From the consideration of X-ray diffraction, infrared absorption spectra, and various transition conditions of long-chain esters of chloramphenicol, and some assumptions were made on their crystal structure.
    1) According to X-ray diffraction, all-trans configuration for the long-chain portion of the β-form molecule results in good agreement between the molecular models and the long axis by X-ray measurement. In the case of α-form, the long axis of the crystal cannot be explained unless the molecule is assumed to have some cis linkages or the long chain part is a trans structure but deeply twined with each other.
    2) Infrared absorption spectra suggest that the α-form is closely resembled to a solution state and crystals with a cis configuration, having distorted molecule, may be assumed. The β-form is considered to have a higher order molecular arrangement as a crystal and it is convenient to assume an all-trans configuration by X-ray measurement.
    3) Stability of the β-form can be assumed form the measurement of melting point and specific gravity. On the other hand, similarity to the α-form and solution state (or amorphous state) as found from transition conditions and these agree well with the above two measurements.
  • 桑野 晴光, 田村 千尋
    1961 年 81 巻 5 号 p. 764-767
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Polymorphism of chloramphenicol was examined by the X-ray diffraction method and quantitative relationship between the two crystal forms was examined. In general, proportionation of concentration to diffraction intensity can be quantitated in polymorphs but the method was inconvenient for use with organic compounds due to strict packing conditions. In the binary system (α- and β-forms) of chloramphenicol palmitate, specific intensity and specific concentration of the component were in proportion and quantitative straight line independent of packing codition was obtained. This was found to be effective in the range of over 3% of the β-form and precision is within 1%. As the quantitative linear equation: the following was obtained: xβ/xα=(0.347±0.005)⋅Iβ/Iα, where x is the concentration of the component and I is the intensity of reflection.
  • 市川 正孝, 高木 康, 一番ケ瀬 尚
    1961 年 81 巻 5 号 p. 768-771
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of ethyl 8-hydroxycoumarin-3-carboxylate (I) in glacial acetic acid solution affords ethyl 5-nitro-8-hydroxycoumari-3-carboxylate (III), m.p. 203.5-204°, and ethyl 7-nitro-8-hydroxycoumarin-3-carboxylate (IV), m.p. 201-202°. Methylation of (III) and (IV) with methyl iodide respectively gives 8-methoxy compounds, (VII) of m.p. 184-186°, and (VIII) of m.p. 152°, respectively. On the other hand, nitration of 3-methoxy-salicylaldehyde acetate (XVI) affords 4-nitro (IX), m.p. 92-93°, 5-nitro (X), m.p. 142°, and 6-nitro (XI), m.p. 104°, compounds. By condensation of (IX) and (XI) with ethyl malonate, in the presence of piperidine, the position of the nitro group in the foregoing (III) and (IV) was determined.
    Hydrolysis of (I), (III), and (IV) with hydrochloric acid respectively afforded 8-hydroxycoumarin-3-carboxylic acid, m.p. 292-293° (decomp.), 5-nitro-8-hydroxycoumarin-3-carboxylic acid, m.p. 292-293° (decomp.), 5-nitro-8-hydroxycoumarin-3-carboxylic acid (V), 257-258°, and 7-nitro-8-hydroxycoumarin-3-carboxylic acid (VI), m.p. 246-248°.
  • 高橋 三雄, 磯井 広一郎, 吉倉 正博, 大杉 利章
    1961 年 81 巻 5 号 p. 771-773
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The essential oil of ginseng, the peeled and air-dried radix of Panax Ginseng, was fractionated by distillation and two kinds of oil of b.p2 71-74° and b.p2 110-120° were obtained. The former was the known panacen, which was found to have >C=CH2 group. Presence of β-sitosterol glucoside was newly confirmed during separation of these oils and the glucoside was identified with daucosterin obtained from Daucus carota. Phytosterol described in the past literature was found to be β-sitosterol.
  • 川田 稔, 高梨 茂, 中島 靖夫
    1961 年 81 巻 5 号 p. 774-776
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ferrous [59Fe] D-glucuronate was prepared from glucuronic acid and ferrous [59Fe] carbonate which was obtained from 59FeCl3. In this reaction almost the whole process was carried out automatically in nitrogen atmosphere. Determination of glucuronic acid in ferrous glucuronate by naphthoresorcinol picrate was not disturbed by the presence of radioactive ferrous ion.
  • 郡 定之, 河野 通文
    1961 年 81 巻 5 号 p. 776-778
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Chromatographic separation of a combination of codeine and hydrocodeine was attempted in continuation of earlier works on codeine and ephedrine, codeine and methylephedrine, hydrocodeine and ephedrine, hydrocodeine and methylephedrine, and ephedrine and methylephedrine. The two bases were found to be separated quantitatively by the partition column chromatography over Celite, using phosphate buffer of pH 6.4 as the stationary phase and benzene-acetone mixture (50:1 by volume) and chloroform as the mobile phase.
  • 綾田 渙
    1961 年 81 巻 5 号 p. 778-783
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Resolution of dl-(2-hydroxy-3-cyanopropyl) trimethylammonium chloride (III) was carried out with d-tartaric acid or dibenzoyl-d-tartaric acid, and dextro- and levorotatory compounds of (III) were obtained. Hydrolysis of these optically active (III) with conc. hydrochloric acid by heating in a boiling water bath afforded the corresponding d- and l-(2-hydroxy-3-carboxypropyl) trimethylammonium chloride (VII). Of these, the levorotatory (VII) was found to correspond to the hydrochloride of natural carnitine (VIII). Infrared spectra of these compounds are given.
  • 山名 月中, 古池 宏
    1961 年 81 巻 5 号 p. 783-784
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Photometric method for the determination of 4-amino-6-chloro-m-benzenedisulfonamide, one of the hydrolysis products of benzothiadiazinines, was developed. The disulfonamide is determined by reaction with 4N hydrochloric acid and nitrous acid at 30°, and coupling of the diazonium compound formed with the Tsudareagent. The resulting red color which is read through a filter (535mμ) is linear in absorbance to the concentration of disulfonamide.
  • 今枝 一男, 木下 彌兵衛, 水谷 六郎
    1961 年 81 巻 5 号 p. 785
    発行日: 1961/05/25
    公開日: 2010/02/19
    ジャーナル フリー
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