YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
79 巻 , 12 号
選択された号の論文の47件中1~47を表示しています
  • 白川 研蔵
    1959 年 79 巻 12 号 p. 1477-1482
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Several kinds of 2-nitroaminopyrimidines were prepared by the condensation of nitroguanidine with β-diketone or β-keto esters. These 2-nitroamino compounds underwent reaction with primary or secondary amines to form 2-substituted amino-pyrimidines.
  • 白川 研蔵
    1959 年 79 巻 12 号 p. 1482-1487
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 2-hydrazino-4-methylpyrimidine (I) and orthoformic acid ester afforded 7-methyl-[1, 2, 4] triazolo [4, 3-a] pyrimidine (VI) and 5-methyl-[1, 2, 4]triazolo[4, 3-a]pyrimidine (VII), and their isomerization gave 5-methyl-[1, 2, 4]triazolo[2, 3-a]pyrimidine (III) from (VI) and 7-methyl-[1, 2, 4] triazolo[2, 3-a]pyrimidine (IV) from (VII). The condensation product of 5-amino-1, 2, 4-triazole-(VIII) and ethyl 2-acetyl-3-ethoxyacrylate was proved to be 6-ethoxycarbonyl-7-methyl-[1, 2, 4]triazolo[2, 3-a]pyrimidine (XI). At the same time, hydrolysis of the reaction product of (VIII) and ethyl acetopyruvate gave two kinds of carboxylic acid (XIV and XV) of [1, 2, 4]triazolo[2, 3-a]pyrimidine.
  • 白川 研蔵
    1959 年 79 巻 12 号 p. 1487-1492
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of formic acid to 2-hydrazino-4, 5-tetramethylene-6-hydroxypyrimidine (I) gave 5-hydroxy-6, 7-tetramethylene-[1, 2, 4]triazolo[4, 3-a] pyrimidine (II) and 5, 6-tetramethylene-7-hydroxy-[1, 2, 4]triazolo[4, 3-a] pyrimidine (III). Fusion of (II) produces 5, 6-tetramethylene-7-hydroxy-[1, 2, 4]triazolo[2, 3-a]pyrimidine (IV) which is identical with the condensation product of 5-amino-1, 2, 4-triazole (VII) and ethyl 2-oxocyclohexa-necarboxylate (VIII). Boiling of (II) with formic acid for a long time afforded (IV) with a minute amount of (III). Condensation of (VII) and 2-formylcyclohexanone (XV) afforded 5, 6- and 6, 7-tetramethylene-[1, 2, 4]triazolo[2, 3-a] pyrimidine (XVIII and XVI). The condensation product of (VII) and ethyl 2-oxocyclopentanecarboxylate (XXII) was proved to be 5, 6-trimethylene-7-hydroxy-1, 2, 4-triazolo[2, 3-a] pyrimidine (XXIII). Examinations were also made on the reaction product of 2-hydrazino-4, 5-trimethylene-6-hydroxy-pyrimidine (XXIV) and ethyl orthoformate.
  • 井川 健二
    1959 年 79 巻 12 号 p. 1493-1497
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hydrazinolysis of mononitro-monomethoxydiphenyl ether, having one nitro and methoxyl on each of the two benzene rings, with hydrazine hydrate was examined. Irrespective of the position of the methoxyl group, compounds (I) with nitro group in the position para to the phenoxyl underwent cleave of the ether-oxygen forming the diphenyl ether to form 4-nitrophenylhydrazine (II) and the corresponding hydroxyanisole derivative (III). Application of higher pressure effected acceleration of this hydrazinolysis and a small amount of 4-amino-methoxydiphenyl ether derivative (V) was obtained besides (II) and (III) (cf. Chart 1).
    The compound (VI) with nitro group in the position meta to the phenoxyl failed to undergo hydrazinolysis, either at ordinary or higher pressure, and only the reduction of nitro group occurred to form 3-amino-methoxydiphenyl ether derivative (VII) and a small amount of a reduction product (VIII) or (IX) (cf. Chart 2).
    The compound (X) with the nitro group in the position ortho to the phenoxyl easily underwent hydrazinolysis at ordinary pressure to form 2-nitrophenylhydrazine (XI) and the corresponding hydroxyanisole derivative (III). Hydration reaction proceeded with (XI) and 1-hydroxybenzotriazole (XIa) was obtained (cf. Chart 3).
  • 井川 健二
    1959 年 79 巻 12 号 p. 1498-1502
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Diphenyl ether derivatives possessing hydroxyl in different positions, with the nitro group present in the position para to the phenoxyl, hardly submits to cleavage of ether-oxygen forming a diphenyl ether by the action of hydrazine hydrate at ordinary pressure which the reaction proceeds at higher pressure to form 4-nitrophenylhydrazine (II) and the corresponding amino-hydroxydiphenyl ether derivative (V). Under some conditions, (II) is further decomposed to nitrobenzene (IIa) and 4-nitroaniline (IIb) (cf. Chart 1).
    When the nitro group is present in the position ortho to the phenyl, hydrazinolysis occurs easily to form 2-nitrophenylhydrazine (IX) and the corresponding dihydrobenzene derivative. Of these, (IX) easily undergoes dehydration reaction to form 1-hydroxybenzotriazole (IXa) (cf. Chart 3).
  • 原 幸子, 岡本 仲子, 松村 剛, 水野 傳一
    1959 年 79 巻 12 号 p. 1502-1505
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new analytical method for organo-mercuric antiseptics was established using chemical and microbiological assay collaterally. Chemical analysis was carried out using the absorption decrease at 620mμ of dithizone solution in CCl4 after the sample and the reagent were mixed. Microbiological assay was done employing the cylinder plate method measuring the growth inhibition zone of Staphylococcus aureus 209P. Formaldehyde and phenol possibly present in the biological products did not interfere the method. Discussion was made to use the two methods collaterally.
  • 遠藤 文男
    1959 年 79 巻 12 号 p. 1505-1509
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    As one of the nature of gelation of benzylidene-d-sorbitol in various solvents, it was found that there is a difference in the coagulation temperature and deflocculation temperature at the time of transition from solution to gel. It was also found that there is some evolution of heat during gelation and this heat formation was observed in alcohols, nitrobenzene, and dioxane gel from the cooling curves of their solvent and solution. There was also found some difference in temperature and kind of solvent. From the cooling curves, the amount of heat formed was measured and gelation energy was calculated to examine the relationship between difference in these values and gelation ability.
  • 谷山 兵三, 竹村 庄司, 景山 公子, 舟木 正直
    1959 年 79 巻 12 号 p. 1510-1513
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    A strain of Actinomyces isolated from a soil in Cambodia was found by one (Funaki) of the authors to be a new strain not reported in any literature and this was named Streptomyces reticuli var. aquamyceticus. The antibiotic produced by this strain was named Aquamycin, which was found to be effective against Erhlich carcinoma. The structure of this antibiotic was clarified in the present series of work and the structure was confirmed by its synthesis. The ultraviolet and infrared spectra of Aquamycin (I), C4H4O2N2, suggested the presence of amide-I and conjugated unsaturated carbonyl. Catalytic reduction of (I) afforded a tetrahydro compound (II), C4H8O2N2, and its saponification with potassium hydroxide gave succinic acid. Consequently, (II) was assumed to be succinamide and this was identified with an authentic sample. Direct saponification of (I) afforded C4H2O4 (IV) which was identified with acetylenedicarboxylic acid obtained from dibromosuccinic acid. From these results, (I) was assumed to be acetylenedicarboxamide but constants of (I) differed slightly from those listed in the literature. Further reexamination of synthetic routes was made and comparison of (I) and synthesized product showed that they agreed in decomposition point, elemental analytical values, and ultraviolet and infrared spectra, thereby confirming the structure of Aquamycin to be acetylene-dicarboxamide.
  • 野池 美哉
    1959 年 79 巻 12 号 p. 1514-1518
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    As a part of studies on the syntheses of substances with sparteine-like activity, quinolizidine derivatives possessing a basic side-chain at 3-position were prepared. Following the separation of ethyl 3-quinolizidinecarboxylate and ethyl 3-epi-quinoli-zidinecarboxylate, and determination of their configuration, respective hydrazides were prepared and their Curtius degradation afforded 3-aminoquinolizidine (VIa) and 3-epi-aminoquinolizidine. It was found during the course of this reaction that there was a difference in the mode of reaction to Curtius degradation according to the configuration of the hydrazide. 3-Benzylaminoquinolizidine was prepared by a difference route and formation of 3-epi-benzylamino compound was observed.
  • 野池 美哉
    1959 年 79 巻 12 号 p. 1519-1522
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Curtius degradation of the corresponding hydrazide of 3-amino-9, 10-methylenedioxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo[a]quinolizine, possessing a structure similar to 3-aminoquinolizidine described earlier, was reexamined by the method of Sugasawa and Tomisawa, and determination of the configuration of the two diastereoisomers and behavior of the two isomers to Curtius degradation were examined. It was found that there is a difference in the reaction due to configurational difference of 3-position, as in the case of 3-aminoquinolizidine, and 3-amino- (VIa) and 3-epi-amino-9, 10-methylenedioxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo[a]quinolizine (VIb) were prepared from the respective hydrazides.
  • 大木 貞雄, 野池 美哉, 大石 篤郎, 奈良 潔, 加藤 俊雄
    1959 年 79 巻 12 号 p. 1522-1525
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Michael condensation of diethyl 2-(2-pyridyl) ethylmalonate and 2-vinylpyridine afforded diethyl bis[2-(2-pyridyl)ethyl]malonate whose high-pressure catalytic reduction with Raney nickel catalyst finally gave 3, 3′-spirobiquinolizidine-4, 4′-dione. This compound was obtained in two kinds of stereoisomeric crystals of m.p. 174° and m.p. 152°. Reduction of the former one of m.p. 174° with lithium aluminum hydride gave 3, 3′-spirobiquinolizidine. The uterine-contracting activity of this compound was approximately 1/5 of that of sparteine sulfate.
  • 田村 善蔵, 松島 美一
    1959 年 79 巻 12 号 p. 1526-1528
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    As an agent accelerating excretion of radioisotopic strontium that has entered a living body, tricarballylic acid, 1, 1, 2, 3-propanetetracarboxylic acid, and 1, 2, 3, 4-butane-tetracarboxylic acid were prepared, and stability constants were calculated for the complexes formed between these acids with calcium and strontium. The measurement was carried out by the method using ion exchange resin, initiated by Schubert, at μ=0.156, 25°. Results thereby obtained are listed in Table I.
  • 松島 早苗, 難波 修一
    1959 年 79 巻 12 号 p. 1529-1536
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    ラット卵巣重量法は精度, 感度, 特異性, 方法の難易の諸点よりの総合的考察の結果信頼し得る方法であることが明らかになつたが, その精度に影響すると考えられる体重, 生後日数, 動物の系統等の諸因子はいずれも大きな影響を示さず, 僅かに異腹仔間に感度の差を見出すのみであつた. したがつて検定の精度を向上させるためには同腹仔を用いる場合の外は使用動物に対して厳密な条件を規定するよりむしろ緩和な条件で多数の動物を用いる方が有利であるという結論に達した. なお各用量に対する反応の変動な反応の量として対数をとることにより均一化することが出来た.
  • 松島 早苗
    1959 年 79 巻 12 号 p. 1536-1542
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Biological examinations were made on the gonadotropic hormone, obtained in a pure state from the placenta. This hormone was found to act on the ovary and testes, and to stimulate interstitial development but not tubuli seminiferi or follicle in hypophysectomized young rat. The hormone stimulated secretion of male hormone from the testes but not secretion of follicle hormone. Thus, the properties of this hormone were in accord with gonadotropic hormone obtained from pregnancy urine. Comparison was therefore made on biological properties of the gonadotropic hormone obtained from the placenta and that from the urine of pregnant woman. From the assay made by the measurement of increase of ovary weight in normal young rat, comparing relationship between the dose administered and the reaction, and by several other methods, it was shown that the two possessed completely identical biological properties. The gonadotropic hormone obtained from the placenta did not contain adrenocorticotropic, growth, or lactogenic hormone.
  • 長野 晃三
    1959 年 79 巻 12 号 p. 1543-1548
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dielectric constant of acetic acid, containing less than 1.706% of water in various ratios, was measured in the temperature range of 10-50°C (Figs. 2 and 3). The temperature coefficient of dielectric constant was found to change from positive to negative as the content of water increases above ca. 1.0%, and the increased rate of dielectric constant by 1% increase of water content is extremely great. On the other hand, dielectric constants of several pure fatty acids were measured and their temperature coefficients were found to be of two kinds, positive and negative. Such a dielectric nature can be explained by assuming the formation of cyclic polymers in which the polarization of dipoles is cancelled by hydrogen bonding and of linear polymers in which the polarization of dipoles is strengthened, their distribution varying with the content of water and temperature. Such consideration is endorsed by observations made on the crystal, liquid, and vapor of such acids.
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1548-1554
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Detailed examinations were made on DC and AC polarography of folic acid, and its electrode reaction was clarified through controlled potential electrolysis, catalytic reduction, and pK values. The first reduction wave of pteroylglutamic acid (I) is due to two electron-two proton reduction to dihydropteroylglutamic acid (II). At pH over 10, a part of the lst wave shifts to negative potential by the dissociation of 4-hydroxyl group. The second wave which appears at below pH 7 corresponds to the two electron-three proton reduction from proton-adduct of (II) to 2-amino-4-hydroxy-6-methyldihydropteridine (III) and the cation of p-aminobenzoylglutamic acid (IV). In strong acidity, these reduction waves are overlapped. At pH above 8, a reduction wave due to transition from (II) to tetrahydropteroylglutamic acid (IX) is recog-nized. The third wave that appears at pH 2-7 is the two electron-two proton reduction wave from (III) to the tetrahydro compound (V). These reduction waves are accompanied by kinetic current due to proton addition at some pH. Dihydro-folic acid forms 2-amino-4-hydroxypteridine-6-carboxaldehyde (VIII) and (IV) by air oxidation.
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1554-1558
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Amino-4-hydroxy-6-methylpteridine (I) showed three groups of two electron-two proton reduction wave. Its first wave indicates E1/2=(-0.25-0.07 pH) V vs. N. C. E. and diffusion current constant, kD=3.15 (μA mM-1mg.-2/3sec.1/2), and is due to reduction of undissociated pteridine to 7, 8-dihydropteridine. The second wave replaces the first wave at pH above 9 and is due to reduction of the anion. The third wave indicates E1/2=(-0.93-0.064 pH) and is due to reduction of the proton adduct of dihy-dropteridine to 5, 6, 7, 8-tetrahydropteridine. Dihydropteridine, obtained by controlled potential electrolysis or chemical reduction of (I), showed the reduction wave similar to the third wave of (I), accompanied by a small anodic wave. The tetrahydro compound of (I) does not show any reduction wave but shows two electron-two proton oxidation wave of E1/2=(+0.27-0.06 pH) which is thought to be due to its oxidation to the dihydro compound of (I). The first wave above pH 9 and the third wave at above pH 5 in (I) indicate the nature of a kinetic current due to proton addition, and is affected greatly by the temperature, pH, kind and concentration of buffer solution, and pre-depolarizer. Oxidation of the dihydro compound of (I) is observed by rotating platinum electrode.
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1559-1564
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Xanthopterin undergoes two-electron reduction to form dihydroxanthopterin and its reduction wave is split into several steps by dissociation of the hydroxyls. The apparent pK' obtained from its wave height-pH curve are 11.25 and 11.9, which are larger than pK 6.84 and 9.46. This is explained as the kinetic current due to recombination reaction of proton. The reduction wave of non-dissociating molecule obtained at pH below 8 is accompanied with an adsorption wave and its wave height is not proportional to the concentration but to mercury pressure, decreasing in an organic solvent. Adsorption phenomenon was also confirmed from AC polarography and electrocapillary curve. From the adsorption wave height, the area of electrode occupied by adsorbed molecule was calculated as 55Å2 and the ring plane was assumed to be oriented parallel to the mercury surface. Transition from alkalinity to acidity results in decrease of total wave height, lowering of the degree of fluores-cence, and increase of oxidation wave observed in rotating platinum electrode. It is assumed from these facts that 2-amino-4, 6-dihydroxypteridine takes the phenoxide form in alkaline medium and about one-half is present as 2-amino-7-hydroxy-7, 8-dihydropteridine-4(3H), 6(5H)-dione in acid medium. Velocity of transition from the former to the latter is proportional to the concentration of hydrogen ion and is calcul-ated as ΔH 11, 000 calories and ΔS -37 calories. Inverse reaction is proportional to [OH-].
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1565-1569
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Amino-4-hydroxypteridine-6-carboxaldehyde (I) shows three-step reduction waves and one-step anodic wave. The first and second reduction waves correspond to two electron-two proton reduction wave. The first wave is greater the higher the pH, the higher the temperature, and the lower the concentration of organic solvent. The wave height is proportional to the square root of mercury pressure and concentration of (I). The first and second waves are due to the reduction of pteridine to dihydropteridine, the first to that with non-hydrated aldehyde and the second to that of hydrated aldehyde. It was considered that the first wave is accompanied with kinetic current due to dehydration and adsorption of the reduction product. Third wave is thought to be the two electron-two proton reduction wave of the aldehyde at pH below 9. Electrolysis of (I) at the potential of the first wave results in the reaction of 2-amino-4-hydroxy-dihydropteridine-6-carboxaldehyde, formed on the electrode surface, and the unreacted substance in the solution and 1, 2-bis (2-amino-4-hydroxy-6-pteridyl) ethylene glycol is formed. Electrolysis of (I) at the potential of the third wave is considered to produce 1, 2-bis (2-amino-4-hydroxy-dihydro-6-pteridyl) ethylene glycol. 2-Amino-4-hydroxy-6-hydroxymethylpteridine shows one-step reduction wave near the potential of the second wave and this is considered to be due to its reduction to dihydropteridine.
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1570-1573
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Aminopterin (I), pteroic acid (II), 10-formylpteroylglutamic acid (III), and A-methopterin (IV), which have structure similar to that of pteroylglutamic acid (V), show three-step reduction waves in acid and 1-2 step reduction waves in alkaline state like (V). The first wave is a two electron-two proton reduction wave to dihydro-pteridine and this wave is split into two steps in (II) and (III) by dissociation of the hydroxyl. The second wave is due to reductive cleavage of -CH2-N=in 6-position and the third wave is due to reduction from 6-methyl-dihydropteridine to tetrahydro-pteridines. E1/2 of the first wave is similar in all these compounds and the value at pH 7 is around -0.72 to -0.76V. E1/2 of the second wave at pH 4 is -0.88 (V) and -0.98V (I, III, IV) and its wave height is the highest at around pH 4. Aminopterin shows post wave due to adsorption phenomenon.
  • 朝日 豊
    1959 年 79 巻 12 号 p. 1574-1578
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Polarographic behavior was examined in 2-amino-4-hydroxypteridine-6-carboxylic acid (I), 2-amino-4-hydroxypteridine-7-carboxylic acid (II), 2-amino-4-hydroxy-7-methylpteridine (IV), 2-amino-4-hydroxy-6-(D-arabo-tetrahydroxybutyl)-pteridine (III), leucopterin (V), lumazine (VI), and 6, 7-dimethyl-8-ribityllumazine (VII). These compounds all show two electron-two proton reduction wave to dihydropteridine. Compounds with dissociated hydroxyl also show reduction wave with -E1/2 and a kinetic current due to rebonding reaction with proton. The compounds (III) and (VI) show reduction wave to tetrahydropteridine in acid medium. As a result of comparing E1/2 of dozens of pteridine compound, it was found that CHO and COOH group rendered E1/2 into positive potential and OH, O-, CH3, and alkyl groups rendered it into negative potential, and that the effect of a substituent in 7-position is greater than that in 6-position.
  • 萩庭 丈寿, 村越 勇, 大部 順久
    1959 年 79 巻 12 号 p. 1578-1581
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    The acylated compound (III) of o-aminomethylphenylacetic acid (II) was distilled with equal amount of soda lime and formed 3-R 1, 2-dihydroisoquinoline (IV) which was labile and was gradually oxidized to 3-substituted isoquinoline (VI) but this is not a disproportionation of the dihydro base (IV). The picrate and perchlorate of (IV) were also easily oxidized and formed the picrate and perchlorate of (VI). This kind of cyclization reaction is not limited to the methylene-carbon of a carboxylic acid but occurs also in a cyano compound (I) to form 3-substituted isoquinoline, though in poor yield.
  • 大熊 誠一
    1959 年 79 巻 12 号 p. 1582-1585
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    For separation of colored iron complex salts formed from pentacyano-iron complex, such as sodium nitroprusside and sodium pentacyanoammineferroate, and various organic compounds by paper chromatography, better result can be obtained by the use of a more polar solvent for development. Non-polar solvents cannot be used. Increased polarity of the developing solvent improves the reproducibility of Rf values but separation becomes poor. On the contrary, less polar solvent increases separation but reproducibility of Rf values becomes poor. The solvent systems having both suitable reproducibility of Rf values and separative ability were found to be the following: Sodium hydrogen carbonate (2g.)-ammonia water (40cc.)-acetone (60cc.); ammonium sulfate (10g.)-ammonia water (40cc.)-acetone (60cc.); sodium hydrogen carbonate (1.5g.)-ammonia water (30cc.)-methanol (70cc.), and ammonium sulfate (10g.)-ammonia water (30cc.)-methanol (70cc.).
  • 大熊 誠一
    1959 年 79 巻 12 号 p. 1586-1590
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    In paper electrophoresis using 0.05N sodium carbonate or 1% sodium hydrogen carbonate solution as the electrolytic solution, sodium pentacyanoammineferroate, pentacyanoaquoferroate, and the colored pentacyano-iron complex salts migrate as anions, and this process can be utilized for separatory identification and estimation of the original organic compounds in the colored pentacyano-iron complex salts formed by the reaction of sodium pentacyanoammineferroate and organic compounds. Similar complex salts formed by reaction of sodium nitroprusside and organic compounds are unstable and cannot be separatory determined by this paper electrophoretic method. The migration value of a sample is inversely proportional to the concentration of electrolytic solution at a constant voltage gradient, while the value is proportional to voltage gradient and current density under constant concentration.
  • 大熊 誠一
    1959 年 79 巻 12 号 p. 1590-1595
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction ratio of sodium pentacyanoammineferroate and aromatic primary amines was examined by the method of continuous variation and the ratio was confirmed to be 1:1. After reacting such primary amines with sodium pentacyano-ammineferroate in 1:1 ratio, the colored solution thereby produced was submitted to the ultraviolet absorption spectra. Such solutions show absorption maxima in the range of 620-735mμ and this absorption maximum can be utilized to distinguish between isomers of aminophenols, phenylenediamines, naphthylamines, and chloroanilines. The colored solution of 1, 4-aminophenol compounds such as p-aminophenol, 2, 4-diaminophenol, 5-aminosalicylic acid, and 1, 4-aminonaphthol shows absorption maximum in the range of 690-710mμ, and color of the solution is very intense and stable. The electron-releasing group (OH, NH2, CH3) indicates hyperchromic effect while electron-attracting group (NO2, HOOC, CH3CO, Cl) shows hypochromic effect. The hydroxyl group in para-position, amino group in ortho-position, and electronattracting group show bathochromic effect.
  • 大熊 誠一
    1959 年 79 巻 12 号 p. 1596-1600
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    The blue or green pigment produced by the color reaction of phenols between pentacyano-iron complex salts, such as sodium nitroprusside, pentacyanoammineferroate, and pentacyanoaquoferroate, and hydroxylamine, was examined by paper chromatography and paper electrophoresis. The phenols possessing electron-releasing group produce two kinds of anionoid pigment. From their behavior to alkalis, Rf value, and migration value, one of the pigments was assumed to be an organic pigment and the other, a complex anion. Phenols possessing electron-attracting group produce only one kind of comparatively labile complex anion. It was concluded that the identification of the pigment produced and original phenols can be made by utilization of paper chromatography and paper electrophoresis.
  • 人見 弘
    1959 年 79 巻 12 号 p. 1600-1606
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Decomposition of procaine benzylpenicillin by warming its aqueous solution to 37° results in six kinds of decomposition reactions: (1) Formation of benzylpenicilloic acid by hydrolysis, (2) formation of benzylpenilloic acid by decarboxylation of benzylpenicilloic acid, (3) initial formation of benzylpenicilloic acid and its hydrolysis to form N-formyl-d-penicillamine and phenaceturic acid, (4) formation of benzylpenillic acid by intramolecular rearrangement, (5) formation of d-penicillamine and benzylpenilloaldehyde by hydrolysis of benzylpenilloic acid, and (6) formation of the disulfide of d-penicillamine and N-formyl-d-penicillamine by their oxidation.
  • 人見 弘
    1959 年 79 巻 12 号 p. 1606-1610
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Decomposition of benzylpenicillin in aqueous solution with aniline and ring-substituted aniline results in the formation of benzylpenicilloic acid, benzylpenilloic acid, N-formyl-d-penicillamine, and benzylpenillic acid. With some kinds of amines, benzylpenicilloic acid-α-amide and phenaceturamide were formed. Some considerations were made on the relationship between the yield of benzylpenillic acid and pK'a value of the amine.
  • 人見 弘
    1959 年 79 巻 12 号 p. 1611-1614
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Decomposition of benzylpenicillin in aqueous solution with N-substituted aniline or alkylamine results in the formation of benzylpenicilloic acid, N-formyl-d-penicillamine, and benzylpenillic acid. Benzylisopenilloic acid is formed by the application of N-disubstituted anilines and alkylamines. Some considerations were made on the relationship between the yield of benzylpenillic acid and pKa' value, and the mode of decomposition of procaine benzylpenicillin.
  • 富野 耕一
    1959 年 79 巻 12 号 p. 1615-1617
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaline catalytic reduction of N, N-dimethyl-2, 6-dihydrobenzamide was attempted in order to obtain 2-dimethylcarbamoylcyclohexane-1, 3-dione but the cleavage of the ring occurred to form 6-dimethylcarbamoyl-5-oxohexanoic acid. This was identified by ketonic decomposition to 5-oxohexanoic acid semicarbazone.
  • 佐々木 豊作, 三上 雅章
    1959 年 79 巻 12 号 p. 1618-1619
    発行日: 1959/12/25
    公開日: 2010/02/19
    ジャーナル フリー
    Components of the fruit of Stephania cepharantha HAYATA (Menispermaceae), in parts other than seeds, were examined and the presence of a carotenoid, considered to be lycopene, was found in the ether-soluble portion. The carotenoid melted at 172° (corr.) and exhibited ultraviolet absorption maxima (in benzene) at 455, 487, and 522 mμ. A mixture of fatty acids, consisting of 73.8% of liquid acid and 26.2% of solid acid, was also obtained. Since the liquid fatty acid afforded elaidic acid in comparatively good yield by elaidination reaction, majority of it was considered to be oleic acid. Palmitic acid was identified from solid fatty acid. Water-soluble portion was found to contain tyrosine and glycerol.
  • 1959 年 79 巻 12 号 p. e3aa
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ab
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ac
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ad
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ae
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3af
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ag
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3ah
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e3b-e4
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4a
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4b
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4c
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4d
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4e
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4f
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1959 年 79 巻 12 号 p. e4g
    発行日: 1959年
    公開日: 2010/02/19
    ジャーナル フリー
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