YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
79 巻 , 4 号
選択された号の論文の39件中1~39を表示しています
  • 成田 九州男, 石井 正子
    1959 年 79 巻 4 号 p. 407-410
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Use of nickel or cobalt oxide as auxiliary combustion agent is being recommended for nitrogen determination by the micro-Dumas method. Hydrous manganese dioxide, prepared from potassium permanganate and manganese sulfate, liberates a large amount of pure oxygen by pyrolysis. In this method, a sample is weighed into platinum boatcovered with ca. 50mg. of manganese dioxide, and the air that comes into the combustion tube at the time of insertion of platinum boat is expelled in 15 seconds by half-way flash-back system, without receiving hot air. The boat is moved to the position with quartz magnetic boat-carrier, two azotometers are connected to the combustion tube, and combustion is effected by the double procedure, shortening the time required. Movable furnace reaches the temperature of 950° after 10 minutes, when electricity is cut off, and N2 gas is expelled 15 minutes later. By continuous operation, 3-4 runs per hour are possible.
  • 鈴木 友二, 田中 文彦
    1959 年 79 巻 4 号 p. 410-415
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Decomposition of penicillin G by rabbit liver was examined. By perfusion through surviving rabbit liver, it was found that penicillin G is hydrolyzed in rabbit liver to penicilloic acid. Perfusion for 2hours, with initial concentration of the penicillin in flowing fluid at 900γ/cc., resulted in the decrease of penicillin concentration to 250γ/cc. and formation of ca. 400γ/cc. of penicilloic acid. Formation of penicilloic acid was identified from paper electrophoresis and from Rf values in paper chromatography using butanol, isobutanol, or isoamyl alcohol, saturated with 0.2M phosphate buffer (pH 6.0), as a developing solvent. Coloration of the chromatogram utilized the reduction of arsenomolybdic acid to blue color and coloration of the spot to brown by spraying 0.1N ammonia water and silver nitrate.
    Penicillin also changed to penicilloic acid on application of liver homogenate but the penicillin-decomposing enzyme is so rapidly inactivated that the liver must be homogenized under ice-cooling immediately after killing of the animal and reacted at once with penicillin. Optimal pH of this reaction is 6.9 and the reaction rate is proportional to the concentration of the homogenate used. No decomposition of penicillin occurred when the homogenate was heated at 100° for 3minutes. When liver homogenate and penicillin G were reacted, 3.2mg. of penicillin per 1g. wet weight of the liver was hydrolyzed and 3mg. of penicilloic acid was formed. Excess of penicillin did not inhibit this reaction. Ferric nitrate and calcium nitrate, which inhibit penicillinase of bacteria, do not inhibit hydrolysis of penicillin by liver homogenate and, therefore, penicillin-decomposing enzyme present in the liver is different in nature from bacterial penicillinase.
  • 山本 隆一, 高橋 哲也
    1959 年 79 巻 4 号 p. 415-418
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Stability and hygroscopic properties of thiamine were determined with powders of vitamin B group compounded with various thiamine salts and with such powders added with L-ascrobic acid.
    Addition of nicotinamide to such a powder was found to decrease the stability of thiamine and the stability of acid salt (di-salt) of thiamine was especially lowered by addition of calcium pantothenate. It was found that the stability of thiamine in vitamin B complex preparations maintained in low humidity was the worst in thiamine hydrochloride.
    In the powder of B group added with ascorbic acid, stability of both thiamine and ascorbic acid are the best when sparingly soluble acid salts of thiamine is added. These results seem to indicate that the stability of thiamine in such powders is affected chiefly by the amount of moisture absorbed.
  • 山本 隆一, 高橋 哲也
    1959 年 79 巻 4 号 p. 419-422
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the relationship between apparent change of various thiamine salts by absorption of humidity and stability of such salts in powders. Dihydrochloride, dinitrate, mononitrate, and naphthalenedisulfonate of thiamine were compounded with lactose, sucrose, or calcium pantothenate and the powders were maintained in a state of variety of humid conditions. Thiamine was then oxidized with gaseous cyanogen bromide and ammonia and the state of thiamine salt in the powder was observed by the resultant thiochrome fluorescence. When the thiamine salt retains the crystalline state in the powder, it is highly stable, while diffusion of thiamine into the powder by humidity absorption and resultant dissolution results in lowering of stability. In the powder compounded with calcium pantothenate, the mono-salt of thiamine, formed on absorption of humidity and subsequent neutralization, is insoluble in the case of thiamine dinitrate and remains stable without diffusion, but is unstable in the case of thiamine naphthalenedisulfonate by solution and diffusion.
  • 増田 克忠
    1959 年 79 巻 4 号 p. 423-425
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    α-Phenylbutyric acid and α-(p-biphenylyl) butyric acid inhibit biological synthesis of cholesterol and lower the amount of cholesterol in the blood. New compounds were synthesized in which these acids were bonded to amino acid like methionine or taurine, or bonded with amino sugar like glucosamine to form an acid amide.
  • 橘川 郁男
    1959 年 79 巻 4 号 p. 425-428
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Racemic form of laurotetanine (II), an aporphine-type secondary phenolic base contained in Litsea citrata BL. (Lauraceae), was prepared and its N-methylation afforded dl-N-methyllaurotetanine (I). During Pschorr's phenanthrene cyclization, dl-1-(3-hydroxy-4-methoxybenzyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (III) was obtained as a by-product.
  • 金子 主税
    1959 年 79 巻 4 号 p. 428-432
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    As the final product of nitration of quinoline 1-oxide and its derivatives with benzoyl nitrate, benzoates of 2-hydroxyquinoline 1-oxide (III)-system was obtained. Therefore, infrared absorption spectra of 2-hydroxyquinoline 1-oxide (III), 4-hydroxy-quinoline 1-oxide (IV), 2, 4-dihydroxyquinoline (V), and their nitro and acyl derivatives were examined. It was revealed by this examination that compounds of (III)- and (IV)-system take the N-hydroxyquinolone type (IIIb) and the betaine type (IVc), respectively. The acylated derivatives of (III)-and (IV)-systems exhibit absorption of C=O stretching vibration due to N-acyloxyl group at a shorter wave-length region than the acyloxyl group in ordinary phenols and this was found to be helpful in discriminating them from acylated derivatives of 2, 4-dihydroxyquinoline (V)-system.
  • 金子 主税
    1959 年 79 巻 4 号 p. 433-436
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ultraviolet spectra of mononitroquinolines in ethanol solution, as indicated in Fig. 1, exhibit only one absorption maximum in α-nitroquinolines, while two maxima are present in those of β-nitroquinolines. This differentiation was found to be present in mononitroisoquinolines, too, as indicated in Fig. 2. On the other hand, comparison of ultraviolet spectra of various haloquinolines with that of quinoline, as indicated in Fig. 3, shows that haloquinolines exhibit similar absorption as that of quinoline, irrespective of the number of halogens substituted in the ring, with a shift of the two absorption maxima (A and B) in the longer wave-length region by 3-6mμ to a longer wave-length region according to the number of halogens but there is no marked difference in the absorption due to position of the halogens substituted.
  • 田中 照夫
    1959 年 79 巻 4 号 p. 437-439
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 2-chloro-5, 6-benzo-1, 3, 2-dioxaphosphorin-4-one (I) with alcohols and subsequent hydrolysis of its product affords the corresponding phosphorous acid monoesters. In a similar manner, riboflavin affords riboflavin 5′-phosphite and its oxidation with potassium permanganate gives riboflavin 5′-phosphate.
  • 掛見 喜一郎, 宇野 豊三, 山科 肇
    1959 年 79 巻 4 号 p. 440-443
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Colorimetric determination of Azacyclonol (α-(4-piperidyl) benzhydrol hydrochloride), one of the tranquilizers, in aqueous solution and in urine was carried out. To 5cc. of aqueous solution of the sample, 1cc. of 0.3% sodium β-naphthoquinone-4-sulfonate and 1cc. of 10% sodium carbonate are added, the mixture is allowed to stand for 1 minute at room temperature, cooled in ice, and extracted with 4cc. of chloroform. The chloroform layer is dried over anhyd. sodium sulfate and its absorbance at 458mμ is measured. In the case of urine, 10cc. of the test urine is added with 4g. of ammonium sulfate and 8cc. of 10% sodium hydroxide, and the mixture is extracted with chloroform. The chloroform layer is washed with the Clark-Lubs buffer of pH 9.0 and shaken with 5cc. of 0.1N hydrochloric acid. This hydrochloric acid solution is colored as in the case of aqueous solution and the colored material is extracted with carbon tetrachloride. The latter is submitted to measurement of absorbance at 428mμ. This method is used in determination of the amount excreted after administration of 20 and 30mg. of the drug and it is found that 50-60% of the amount administered is excreted within 24 hours after administration.
  • 高野 忠義
    1959 年 79 巻 4 号 p. 443-446
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was assumed that the structure of trachelogenin is different from known lignans because of the reaction products of its oxidation with sodium hypobromite and reaction with lead tetraacetate, and non-formation of naphthalene ring in spite of the presence of a 3, 4-dimethoxyphenyl group. It was found that on warming trachelogenin with alkali, the corresponding iso-compound is formed. Oxidation of methyltrachelogenin with chromium trioxide afforded a γ-keto ester, which showed the presence of a secondary hydroxyl in γ-position to the carbonyl in γ-lactone, and it was found from its infrared absorption spectrum, the carbon bearing the secondary hydroxyl is not directly bonded to an aromatic ring. Based on these facts and considering the general type of lignans, an assumed structure was proposed for trachelogenin.
  • 高野 忠義
    1959 年 79 巻 4 号 p. 447-450
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Barbier-Wieland reaction of methyl methyltrachelogenate afforded a β-diketone. From this fact and the measurement of infrared spectrum and pK′ of bromotrachelogenic acid, obtained by bromination of the acid, the formula proposed in the preceding paper seemed to be more certain. The by-product, C24H28O7, obtained during the formation of methyltrachelogenin, was found to be a compound formed by liberation of one methoxyl and this has revealed the original position of the methoxyl. Bromination of trachelogenin, followed by dehydrobromination to form an unsaturated compound and its oxidation to effect cleavage afforded 3-methoxy-4-bromophenylacetic acid. This reaction revealed the position of secondary hydroxyl group with respect to the aromatic ring holding phenolic OH, and the structure of the original glycoside, tracheloside, was presumed.
  • 能登 武治, 沢田 弘, 佐藤 善重, 福田 仲美
    1959 年 79 巻 4 号 p. 451-453
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Menadione sodium bisulfite is given as containing 2 moles of crystal water in J.N.F. II, and as 3 moles in U.S.P. XV. Therefore, a sample containing 2.03 moles of water was submitted to isotherm reaction with water vapor. Absorption of water vapor on this sample was carried out at 29.5° and the amount absorbed and equilibrium pressure were measured with a quartz spring balance and mercury manometer. Absorption curve showed a very slow rate in reaching equilibrium and the curve did not overlap the desorption curve, from which the absorption was found to be a reaction. Since the desorption curve and resorption-desorption curve were identical, reversible, and the time required to reach the equilibrium was so short that the curve is assumed to be a physical desorption curve, and the level portion of 19.0-19.5% of water content, was taken as that of crystal water. Relationship between the amount and time of reaction was determined by varying the temperature and humidity, and the value became constant 19.6% of water at a low temperature and humidity, at 0° and 90%, which agreed well with a theoretical value of 19.54% for 3 moles of crystal water. When the temperature became higher and humidity lower, dehydration reaction occurs and, therefore, the sample used containing 2.03 moles of water must be a product, in which a part of 3 moles of crystal water had been dehydrated.
  • 水上 聰, 平井 瑛三
    1959 年 79 巻 4 号 p. 454-457
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separatory determination of isonicotinic acid hydrazide (INAH) and sulfisoxazole by non-aqueous titration was attempted and a method utilizing the difference in the basicity and solubility of their acetylated compounds was established. Treatment of the mixture of these two compounds with acetic anhydride in acetic acid converts both to acetylated compounds but that of INAH is easily soluble in acid while acetylsulfisoxazole is insoluble. By separating these acetylated compounds, INAH is titrated as a base and acetylsulfisoxazole as acid with perchloric acid and sodium methoxide respectively.
  • 水上 聰, 平井 瑛三
    1959 年 79 巻 4 号 p. 457-460
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Determination by non-aqueous titration was examined with sparingly soluble organic acid salts and hydrochlorides of chlorpromazine, promethazine, and diethazine, and their preparations. It was found that the use of neutral or almost neutral solvents, like acetone and acetonitrile, was better than acid solvents like glacial acetic acid in the titration of these salts of phenothiazine bases and a good result was obtained by the use of a mixed indicator of methyl violet and bromocresol green. One mole of these salts was titrated as one equivalent with glacial acetic acid solution of perchloric acid, except promethazine methylenedisalicylate, whose one mole was titrated as two equivalents. Good result was obtained with powders of sparingly soluble organic acid salts by back-titration with glacial acetic acid solution of triethylamine.
  • 坂口 武一, 関口 慶二, 花木 昭, 斎藤 昭好
    1959 年 79 巻 4 号 p. 461-467
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction of tetracyclines with boric acid-sulfuric acid was applied to oxytetracycline and this was found to form a boron chelate with absorption maximum at 480mμ. At the same time, another chelate with absorption maximum at 570mμ was formed on standing or heating the mixture. Chemical properties of these two chelates were examined and both were found to be a boron chelate of the same anhydro-oxytetracycline. In order to examine the manner of condensation of boric acid, the same reaction was carried out with boron trioxide, metaboric acid, and borax, and the same boron chelate compound was obtained from each one of them. Moreover, the bonding ratio of these chelates was 1:1 in both the chelate with absorption maximum at 480mμ and that with at 570mμ. The formation constant, log K, of the chelate with absorption at 480mμ was 1.5. From these experiments, a structure for the boron chelate was proposed.
    The crystals obtained by application of fuming sulfuric acid (50%) to boric acid were washed once with conc. sulfuric acid and the same reaction was carried out with a reagent obtained by dissolving this crystal in conc. sulfuric acid with warming, by which a coloration was effected, the colored solution showing absorption maximum at 495mμ.
  • 高木 誠司, 安田 博幸
    1959 年 79 巻 4 号 p. 467-470
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ten kinds of R-COCH2-R′(R=phenyl, p-tolyl, anisyl, α-naphthyl, β-naphthyl, R′=methyl, ethyl, phenyl) was formylated with ethyl formate by the usual procedure to form α-formyl-ketone (I) and application of hydroxylamine hydrochloride to (I) in ethanol afforded isoxazole compounds (II) instead of oxime or dioxime of (I). Application of sodium ethoxide to (II) effected cleavage to form α-cyano-ketone (III) whose hydrolysis with dilute alkali hydroxide resulted in the formation of R-COOH and R′-CH2CN. This proved that (II) is a 4, 5-disubstituted isoxazole with R′ in 4- and R in 5-position. This process seemed to be applicable as a general procedure for synthesis and detection of 4, 5-disubstituted isoxazoles.
  • 奥井 誠一, 鈴木 茂生
    1959 年 79 巻 4 号 p. 471-475
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The present series of work was carried out in order to obtain fundamental knowledge on the compounds formed by peptide bonded to sugar in vivo, more specifically the ester-type bonding in which the hydroxyl group of the sugar is bonded to carboxyl in the amino acid. For this purpose, examination was made on the preparation of 6-glycylglucose, the representative compound of the most simple monosaccharide and amino acid, and the object was attained in the following manner:
    1, 2;3, 5-Di-O-benzylidene-D-glucofuranose was reacted with N-benzyloxycarbonylglycine, used as reagent for peptide synthesis, and diethylphosphorous or isovaleric anhydride, and the amorphous 6-O-(N-benzyloxycarbonylglycyl)-1, 2;3, 5-di-O-benzylidene-D-glucofuranose so obtained was converted to the crystalline 6-O, N-benzyloxycarbonylglycyl)-D-glucose. Catalytic reduction of this product finally afforded the objective 6-O-glycylglucose which was extremely labile and turned brown at room temperature to be decomposed rapidly into glucose, glycine, and glycylglycine. It was therefore impossible to obtain this compound in pure state or change it to its various derivatives, such as acetylated compound.
  • 山口 一孝, 太幡 利一, 庄司 初枝
    1959 年 79 巻 4 号 p. 476-478
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    An attempt was made for fluorometric determination of reserpine which had been separated on a filter paper by electrophoresis. The fluorescence intensity of reserpine is stronger in acid solution than in neutral or alkaline solution. Various amounts of reserpine were spotted on a Whatman No. 1 filter paper and submitted to paper electrophoresis, with 5 N acetic acid as electrolyte, at 700 V for 2 hours. After migration, the paper with separated reserpine spot was heated at 105° in mixed vapor of hydrogen peroxide and acetic acid. It was thereby found that a linear relationship held between the amount of reserpine and intensity of fluorescence. The amount of reserpine present in several alkaloidal fractions of the Rauwolfia extract was also examined. In this case, the reserpine fraction must be separated from strong bases by extraction with buffered solution before electrophoresis in order to avoid error.
  • 村岡 三郎, 柿本 年雄, 佐竹 正年
    1959 年 79 巻 4 号 p. 479-483
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Arginosuccinase (splitting enzyme) was purified from the acetone-dried powder of hog kidney, and the decomposition and formation of canavanosuccinic acid was examined with this enzyme. Decomposition of canavanosuccinic acid by purified arginosuccinase is far more inferior than that of arginosuccinic acid. Using 6 units of the enzyme at 37° for 60 minutes, 5 micromoles of arginosuccinic acid was decomposed to 76% while the same amount of canavanosuccinic acid was decomposed to only 6%. In order to decompose the latter to the same extent as the former, it required 40-50 times the amount of enzyme. The reaction was not promoted by extension of the reaction time or the presence of arginase. Formation of canavanosuccinic acid from canavanine and fumaric acid is 54% when using 125 micromoles of the substrate with reaction time of 120minutes, which was relatively close to the formation rate of 75% of arginosuccinic acid. This showed that the formation of canavanosuccinic acid is more easily promoted than its decomposition. Effect of canavanin and canavanosuccinic acid in the decomposition of arginosuccinic acid was examined but they did not seem to have any obstructive effect.
  • 鈴木 友二, 村岡 三郎
    1959 年 79 巻 4 号 p. 483-487
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    By irradiation of ultraviolet ray on Escherichia coli K 12-W, a double-requiring mutant iv-17, requiring isoleucine and valine, was isolated. The genetic block of this strain is between hydroxy acid to keto acid. Its growth was inhibited by excess of isoleucine and antagonized by valine. Growth inhibition by isoleucine was examined with the iv-17 strain and 11A16, M 42-37, 20A19, 48-62, and 92-21 strains of E. coli, and 16117 and 7110 strains of Neurospora crassa. Of these, 20A19 and 48-62 strains of E. coli and both of N. crassa were inhibited and these strains were characterized by strict requirement of valine. Inhibitory action of isoleucine in E. coli iv-17 was recovered by addition of leucine and this phenomenon was observed in other microörganisms whose growth is inhibited by isoleucine. Ketoleucine was also found to have this action.
  • 古川 淳
    1959 年 79 巻 4 号 p. 487-491
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction of 2-styrylpyridine 1-oxide or 2-propenylpyridine 1-oxide, containing a double bond conjugated to the ring, with acetic anhydride respectively afforded 1-(2-pyridyl)-2-phenylethane-1, 2-diol and 1-(2-pyridyl)propane-1, 2-diol, the α-glycols, as the chief product, and β-hydroxy compounds as a by-product.
  • 古川 淳
    1959 年 79 巻 4 号 p. 492-499
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In connection with rearrangement reaction in picoline 1-oxides, the first step of rearrangement is the addition of CH3CO+ to N-O and this is largely influenced by basicity of N-oxides, the reaction being difficult under mild conditions in compounds with negative pKa values. Rate-determining step in this reaction was assumed to be the severance of N-O bond in N-OCOCH3. Reaction rate of quinaldine 1-oxide to 2-quinolinemethanol acetate was examined and it was revealed that the reaction was of the first order and progressed in a sharp, straight line. It was thereby concluded that this rearrangement is an ionic reaction and that the rearrangement of picolines to alcohol acetates also progressed by similar ionic reaction.
  • 高橋 幸太郎, 田辺 良久, 福山 忠男
    1959 年 79 巻 4 号 p. 500-502
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new dicarboxylic triterpenoid, hovenic acid, C30H46O5, m.p. 323° (decomp.), was isolated from the wood of Hovenia dulcis THUNBERG. Hovenic acid possesses a double bond >C=CH2, an alcoholic hydroxyl, and two carboxyl groups. By the action of formic acid, it was converted to an allo-type compound. It was therefore assumed that hovenic acid would be a carboxybetulic acid, derived from betulic acid by a replacement of one of methyl groups with a carboxyl.
  • 鎌田 皎, 松本 光雄
    1959 年 79 巻 4 号 p. 503-510
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to study some of the important factors contributing to solubilization system, a modified solubilization titration based on the theory of Winsor was carried out. Experimental results and considerations on the following four factors affecting surface active agents of the polyoxyethylene nonylphenyl ether type are described: (1) Concentration of the surfactant (Fig. 2), (2) nature of the solubilizate (Figs. 3, 4) (3) effect of temperature (Fig. 5), and (4) combination of surfactants (Fig. 6 and Table II). HLB values of various NP-type surfactants were calculated from Griffin's formula and these values were examined with the result obtained in the examination of the above (4) (cf. Table II). In solubilization of xylene, the optimal combination of this type of surfactants with different moles of ethylene oxide bonded to each surfactant, HLB values of a system with combinations of 7.5-9, 7.5-15, and 5-9 moles of polyoxyethylene nonylphenyl ethers gave approximately agreeing values, while the combination with 5-15 moles gave a different value. In the former three combinations, the best result was obtained from that with 7.5-9 moles. This fact has shown that HLB value, which was believed to show the characteristics of a surfactant, is not sufficient as an indicator for selection of a solubilizing system. With consideration of Winsor's theory of solubilization and the present solubilization titration, attempt was made for elucidation of this phenomenon of solubilization and it was pointed out that this titration method is an effective means in determining various factors in actual preparations.
  • 鎌田 皎, 松本 光雄
    1959 年 79 巻 4 号 p. 510-516
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The modified solubilization titration, based on the theory of Winsor on solubilization, was found to be a good means for the study of solubilization system by measuring the critical temperature of solubilization. The surfactants used were 7.5, 9, and 15 moles of NP, the solubilizate was xylene, and cyclohexanol was used as the solubilization adjustor. It was thereby found that the critical temperature of solubilization at NP 9 moles was approximately intermediate of those with 7.5 and 15 moles (Figs. 1 and 5). The relationship between combination of surfactants and critical temperature of solubilization showed approximately linear change in the combination of NP-9 and 7.5 moles or NP-9 and 15 moles, but the relationship between combination and temperature was not linear in the combination of NP-7.5 and 15 moles. These results indicate that there is a difference between the HLB value calculated and the value obtained from actual emulsification or solubilization tests according to the kind of combination of surfactants and it was thought necessary to consider the foregoing relationship of curves and to bear this in mind when using the HLB system in actual practice.
  • 青木 大, 岩山 陽治
    1959 年 79 巻 4 号 p. 516-521
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Cloud point was measured in various concentrations and in mixtures of polyoxyethylene monoisoöctylphenyl ether with different number of epoxyethylene group. The cloud point was also measured in the presence of various organic matter. The results obtained suggested that the clouding phenomenon is not merely the result of dehydration but is due mainly to complex formation of a nonionic surface active agent and the substances present and a complex effect of mixing of these substances.
    It was proved that the cloud point of nonionic surface active agent itself is affected not only by the distribution of polymerization degree of its epoxyethylene group but also to the occlusion of polyethylene glycols. In general, nonionic surface active agents with smaller number of epoxyethylene group show lowering of cloud point in the presence of polyethylene glycols while those with larger number or epoxyethylene group show higher cloud point. The larger the average molecular weight of polyethylene glycols present, the stronger becomes the action of lowering the cloud point, and the smaller the average molecular weight, the stronger became the action of elevating the cloud point.
  • 青木 大, 岩山 陽治
    1959 年 79 巻 4 号 p. 522-526
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Various reports have appeared regarding the two-phase titration of ionic surface-active agents using a pigment as an indicator but all of these methods had difficulty in determing the end point. The procedure developed by the present authors allows observation of a sharp end point, with the chloroform layer appearing in crimson color, and there is less likelihood of error.
    In this method, 5-20mg. of alkylsulfate and alkylarylsulfonate is titrated with 0.005M cationic surface-active agent in buffer solution of pH 4.5, in the presence of chloroform, and erythrosin as an indicator. The accuracy is within 0.2% or less. This method can be applied to the analysis of various types of invert soap and long-chain aliphatic amines. Eosin and erythrosin, in a concentration range of 3×10-6 to 3×10-5M, can be used as a reagent for colorimetric determination of invert soap.
  • 青木 大, 岩山 陽治
    1959 年 79 巻 4 号 p. 526-530
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    In a two-phase titration using anionic surface-active agent as a titrant, toluidine blue was found to be the best indicator. Titration of a solution adjusted to pH 8, in the presence of chloroform, with this dye as an indicator results in the change of chloroform layer from crimson to blue and determination of the end-point can be made easily and accurately. Using 0.005M anionic surface-active agent as a titrant, 5-20mg. of cationic and anionic surface-active agent can be titrated with accuracy of ±0.2% or less. It was also shown that toluidine blue can be used as a reagent for colorimetric determination of anionic surface-active agents in a concentration range of 1×10-6 to 1.5×10-5M.
  • 掛見 喜一郎, 有田 隆一, 大橋 貞
    1959 年 79 巻 4 号 p. 531-533
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Potency determination of Viomycin had heretofore been chiefly made by biological method and in order to establish a colorimetric method of determining Viomycin, which would be comparatively simple, following procedure was attempted. In a test tube, 4cc. of an aqueous solution of Viomycin sulfate is cooled to 0° to 5°, 1cc. of 20% potassium hydroxide solution and 0.3cc. of 0.1% oxine solution are added, shaken thoroughly, and 0.5cc. of sodium hypobromite solution is added to effect coloration. This mixture is shaken for 1 minute and 2cc. of pyridine is added to stabilize the color. This solution has an absorption maximum at 507mμ and its absorbancy is proportional to potency. Determination of potency with a sample treated by this method and allowed to stand for a definite length of time gave values agreeing well with the potency determined by the biological assay.
  • 富永 保人, 横畑 明
    1959 年 79 巻 4 号 p. 534-536
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Morphological properties, and content of pyrethrin I and II were examined in the diploid and tetraploid plants of pyrethrum (Chrysanthemum cinerariaefolium BOCC.), and the triploid plant obtained by artificial pollination of the former two. The number of flowers per stand and dry weight of 100 flowers from the triploid were intermediate of the parental diploid and tetraploid but the content of pyrethrin was higher than either of the parent plants. In the case of 80% opened flowers, the content of pyrethrin I was 1.13 times and that of pyrethrin II was 1.26 times these of the diploid plant. Therefore, the triploid plant seemed to have excellent characteristics as a material for pyrethrin production. Examined from the degree of flower opening, the maximum content of pyrethrin was found in 50-80% opened flowers in the diploid and 80% in the triploid. In the tetraploid, difference in pyrethrin content due to the degree of flower opening was small but somewhat higher in 80-100% opened flowers.
  • 落合 英二, 池原 森男, 川添 豊, 菅野 順一郎, 宮坂 貞
    1959 年 79 巻 4 号 p. 537-539
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    If catalytic reduction of 4-tosyloxy-5, 6, 7, 8-tetrahydroisoquinoline (IV) could effect detosyloxylation to form the 5, 6, 7, 8-tetrahydroisoquinoline (V), it would be a new method for preparing (V) from coal-tar isoquinoline. (IV) was therefore prepared but it resisted to reduction under conditions similar to those in the case of 4-tosyloxyisoquinoline. Examination of catalyst and additives showed that the catalytic reduction could be effected by using the catalyst which was prepared by preliminary treatment of Adams' platinum oxide with hydrogen followed by addition of platinum chloride and shaking in hydrogen stream, all in ethanolic solution. By this means, (V) was obtained in a good yield.
  • 松野 隆男
    1959 年 79 巻 4 号 p. 540-541
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A substance was extracted from the fruit of Citrus medica L. var. Sarcodactylus SWINGLE (Rutaceae) in 0.007% yield occurring as colorless needles, m.p. 147.5°, C11H10O4. From its analytical values, chemical properties, and result of admixture, it was identified with limettin (5, 7-dimethoxycoumarin). Diosmin and hesperidin were detected as trace elements by paper chromatography.
  • 高橋 真太郎, ヒキノ ヒロシ, 佐々木 靖子
    1959 年 79 巻 4 号 p. 541-543
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Steam distillation of the rhizomes of Atractylodes japonica KOIDZUMI (Compositae), growing in the central area of Japan, gave 0.32% of essential oil. Presence of acetaldehyde and 2-furaldehyde was proved in the aqueous layer obtained after removal of the essential oil. Fractional distillation of the essential oil under a reduced pressure was carried out and the presence of an oily, bicyclic sesquiterpenoid hydrocarbon, with a composition of C15H24, was presumed. However, the present series of experiments failed to detect the presence of atractylone, reported as a crystalline component of the essential oil from rhizome of Atractylodes spp. (usually described as Atractylis ovata but more correctly it should be termed Atractylodes japonica).
  • 高橋 真太郎, ヒキノ ヒロシ, 佐々木 靖子
    1959 年 79 巻 4 号 p. 544-547
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Steam distillation of the rhizomes of Atractylodes lancea DE CANDOLLE (Compositae) of Chinese origin afforded a crystalline essential oil in 3.5-5.6% yield. The aqueous layer obtained after separation of the essential oil contained 2-furaldehyde. The majority of the essential oil consisted of a sesquiterpenoid which was recrystallized to white needles, m.p. 61-63°, C15H26O. Its physical properties and few of its reactions suggested that this substance might be atractylol, reported as having been obtained from a crude drug hitherto erroneously designated as Atractylis ovata. It was shown by the present work that the atractylol reported to date was an impure product mixed with other sesquiterpenoids and the nature of such terpenoids was clarified.
  • 松野 隆男
    1959 年 79 巻 4 号 p. 547-549
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The rind of immature and mature citrus fruits (Citrus grandis OSBECK forma Mato×C. sulcata Hort ex TAKAHASHI?) yielded neohesperidin (1.5%), naringin (0.22%), and rhoifolin (trace) from the immature fruit, and neohesperidin (2.7%) and naringin (0.14%) from the mature one. Another kind of mature and immature citrus (scientific name unknown) yielded naringin (1.2%), rhoifolin (0.024%), and naringin (15%) respectively. The content of the foregoing flavanone glycoside was larger in the immature fruit. Naringin, the flavanone glycoside, forms the corresponding flavone glycoside, rhoifolin, with ripening of the fruit.
  • 木村 道也, 高野 良宏
    1959 年 79 巻 4 号 p. 549-552
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of 3-aminopyridine (II) with 30% hydrogen peroxide and conc. sulfuric acid, at room temperature, results in the formation of 3, 3′-azoxypyridine (III) and not the anticipated 3-nitropyridine (I).
    Derivation of 3, 5-dinitro-4-hydroxypyridine (IV) to its 4-chloro compound (V) by treatment with phosphoryl chloride and application of anhydrous hydrazine to (V) afforded 3, 5-dinitro-4-pyridylhydrazine (VI) as needle crystals, mp 161.5°. Heating of (VI) with silver acetate at 135-140° finally afforded 3, 5-dinitropyridine (VII), with a by-product of plate crystals melting at 168°, which was assumed to be 3-amino-5-nitropyridine.
  • 岩山 陽治
    1959 年 79 巻 4 号 p. 552-554
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ayers' method for colorimetric determination of fatty acids was examined and a fundamentally new method was established. The new method is based on the fact that the copper salt of fatty acid dissolves in chloroform in the presence of triethanolamine to show a stable blue color. This can be used for simple and rapid determination of saturated and unsaturated fatty acids of C10-C22 series as a chloroform solution. Ten cc. of 0.0005-0.02M chloroform solution of fatty acid is shaken with 5 cc. of copper-triethanolamine reagent (9 vol. of 1M triethanolamine, 1 vol. of 1N AcOH, and 10 vol. of 5% Cu(NO3)2) and optical density of the blue chloroform solution so obtained is measured. This color follows the Lambert-Beer's law within the above concentration range and reproducibility is good. This method can also be applied to the determination of free and conjugated fatty acids in fatty oils and nonionic surface-active agents.
  • 富永 敏夫, 吉村 一成, 西海枝 東雄, 久野 拓造
    1959 年 79 巻 4 号 p. 555-558
    発行日: 1959/04/25
    公開日: 2010/02/19
    ジャーナル フリー
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