YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
83 巻 , 5 号
選択された号の論文の22件中1~22を表示しています
  • 後藤 茂, 井口 定男
    1963 年 83 巻 5 号 p. 435-439
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The solubility aiding action of pyrone derivatives regarding adrenochrome monosemicarbazone (AD) and riboflavin (RF) has been studied by the solubility method. The results are: (1) the aiding action of pyrone ring itself is weak, (2) the action is remarkably increased when the carbonyl and carboxylic groups are introduced into pyrone ring in the case of AD and the mechanism in which the carbonyl and carboxylic groups are participating directly has been considered, (3) any interrelation such as observed in the case of AD has not been found in the case of RF and (4) meconic acid is found to show the strongest action.
  • 赤塚 政美
    1963 年 83 巻 5 号 p. 440-444
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    By the reaction of aniline in alkaline media, 2, 3-dichloro-α-naphthoquinone (I) afforded 2-hydroxy-3-chloro-α-naphthoquinoline (III) dominantly, besides 2-anilino-3-chloro-α-naphthoquinoline (II), and 3, 4-dichloro-β-naphthoquinoline (IV) gave 3-chioro-4-anilino-β-naphthoquinone (V). The reaction of acid hydrazide in alkali gave blue salt from I and red from IV respectively, being followed by hydrolyzing to the free condensates of the salt with acid. The hydrolysis of each condensate with acids identified that 2-acylhydrazino-3-chloro-α-naphthoquinone (VI) was derived from I and 3-chloro-4-acylhydrazino-β-naphthoquinone (VII) from N in the respective condensation.
  • 黒田 耕司
    1963 年 83 巻 5 号 p. 445-454
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Critical relative humidity (CRH) of the mixture which form double salt, except Na2SO4-(NH4)2SO4 mixture, by the pre-equilibrium method, coincided almost with the saturation method when measured under a similar condition to that in the previous report. The X-ray diffraction analysis showed that, at the beginning of moistening, the thermodynamic equilibrium was not maintained between the components in the Na2SO4-(NH4)2SO4 mixture.
    CRH of the mixture which form solid solution (mixed crystal) of KBr-KCl and NH4Cl-KCl, by the pre-equilibrium method, coincided with that by the saturation method.
    CRH of NaCl-Na2SO4 and NaCl-Na2CO3 mixtures by both method is not always coincided. The change of solid phase by moistening of 4 kinds of tautomeric double pair salt and CRH by pre-equilibrium method generally correspond with the report by Merz and the calculation equation of CRH in the tautometric double pair salt was examined.
  • 黒田 耕司
    1963 年 83 巻 5 号 p. 455-462
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nicotinamide (NAA)-tartaric acid (TA) and NAA-urea mixture are considered to form least hygroscopic compound, and CRH was calculated even by the pre-equilibrium method under the experimental conditions by author. This value almost coincided with that by the saturation method. With NAA-L-ascorbic acid (LAA) mixture, CRH is coincident by both methods. The LAA-urea mixture is considered to form a compound but the X-ray diffraction analysis showed that it was simply a mixture. According to the X-ray diffraction of the solid phase, even when CRH by both method may coincident, it was found that the thermodynamic equilibrium is not always maintained between the component. The calculation equation of CRH in the IV report, is applicable to the mixture of forming complex. A decline in Vitamin C potency by moistening in NAA-LAA mixture, is considered to be prevented by forming complex beforehand but the experiment by the author was not the case.
  • 黒田 耕司
    1963 年 83 巻 5 号 p. 463-466
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Though H3BO3-mannit and caffeine-sodium benzoate (BNA) systems were considered to interact between the components in aqueous solution. The relation of reciprocal humidity (H)-mixing ratio of solute (y), molar ratio (x1)-y, the activity coefficient of water (f1)-y was the same, when interaction between the components was not taken place and equation (1) was found to be formed. CRH of caffeine-BNA by the pre-equilibrium method was the same when any interaction between the components was not taken place and any changes of the solid phase by moistning, has not been recognized. Therefore the behavior of such a mixture has been concluded to be the same as CRH of having no interaction.
  • 近藤 嘉和
    1963 年 83 巻 5 号 p. 467-471
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Lithium aluminum hydride reduction of 8-(2-oxopropyl)dihydroberberine (I) gave diastereoisomers of 8-(2-hydroxypropyl)dihydroberberine (II and III) which on sodium borohydride reduction afforded three stereoisomers of 8-(2-hydroxypropyl)-2, 3-methylenedioxy-9, 10-dimethoxydibenzo[a, g]quinolizidine (IV, V and VI). On the basis of their ultraviolet, infrared and nuclear magnetic resonance spectra and their reaction behavior, it was assumed that the orientation of C-8 substituent and juncture at C-14 of IV, V and VI are e′ and trans, a′ and cis and e′ and trans, respectively.
  • 浅井 篤
    1963 年 83 巻 5 号 p. 471-479
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    When 5-(p-aminobenzamido)-3, 4-dimethylisoxazole was shaken in hydrogen, in the presence of palladium-carbon, absorption of one mole of hydrogen was observed. The structure (II) was assigned to the product, C12H15O2N3, on the basis of ultraviolet and infrared spectra. In confirmation of this structure, the product was converted into 2-(p-aminophenyl)-4, 5-dimethyl-6-pyrimidinol (VI) by heating with ethanolic potassium hydroxide, aqueous ammonia, hydrazine hydrate, or 33% acetic acid. In some of these reactions, hydrolysis of the compound (II) took place simultaneously, giving ammonia, carbon dioxide, p-aminobenzamide, and methyl ethyl ketone as the end products.
    Lithium aluminum hydride reduction of the compound (II) afforded 3-methyl-4-(p-aminobenzylamino)-2-butanol (VII), as shown by synthesis.
    Thus it was found that the catalytic reduction of 5-(p-aminobenzamido)-3, 4-dimethylisoxazole over palladium-carbon led to cleavage of the ring rather than formation of an isoxazoline derivative.
  • 松尾 義治
    1963 年 83 巻 5 号 p. 480-487
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the previous report, the synthesis of N-substituted amino acid amide derivatives, a remarkable pharmacological effect, as well as the greater water-solubility, were described on the studies of the antipyretics and the analgesics. In this report, in order to investigate the pharmacological action of the urea-type derivatives as a related compound, with a comparatively low toxicity, the N-substituted amino acids urea derivatives of antipyrine and aryl compounds were synthesized. In this synthetic process of acylation of 1-methyl-1-phenylurea, an unusual reaction was observed and the structure of the products, as well as the productive procedure was studied.
  • 高橋 智雄, 山本 恵津子
    1963 年 83 巻 5 号 p. 487-491
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Riboflavin crystals irradiated with 4 to 8×107r. of γ-rays from 60Co are more stable than non-irradiated riboflavin when compounded in powdered preparations with calcium carbonate, the same as in the case of thiamine hydrochloride.*1 The density of the irradiated crystals was higher, hygroscopicity was lower, and a difference was noted in relative intensity in X-ray diffraction pattern from those of the non-irradiated crystals.
    Comparison of γ-ray decomposition and photodecomposition of the aqueous solution of riboflavin under four kinds of condition showed difference in their ultraviolet spectra and paper chromatographic changes. In γ-ray decomposition, lumichrome is not formed, differing from the case of photodecomposition in neutral and acidd reactions. It was also found that a substance is formed by this γ-ray decomposition, which shows up as a fluorescent spot on paper chromatogram not found after photodecomposition.
  • 藤沢 正計
    1963 年 83 巻 5 号 p. 492-497
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Photodecomposition of thioproperazine 5-oxide (IV) was found to take place by irradiation of fluorescent light (twelve 20-W cool white light tubes, ca. 5000 luces) in acid aqueous solution under anaerobic condition. Thioproperazine (I) and dimethylamine were isolated and identified as the decomposition products. The fact that 10-[3-(4-methyl-1-piperazinyl)propyl]-2-phenothiazinesulfonic acid 5-oxide (V) was not formed during the process of this photodecomposition was proved by paper partition chromatography, which endorsed the assumption that photoreduction of IV produces I which undergoes the decomposition previously reported. V and 10-[3-(4-methyl-1-pipera-zinyl)propyl]phenothiazine 5-oxide (VI) were also found to undergo photoreduction. In general, the sulf oxide group in N-substituted phenothiazine 5-oxides easily undergoes photoreduction which is accelerated by the presence of a reducing agent. Photoreduction of IV was quantitatively evaluated by the colorimetric determination using palladium chloride. Ascorbic acid and sodium sulfite accelerate this photodecomposition, while maleic acid and picolinic acid inhibit this reaction.
  • 小沢 樹夫, 渋谷 茂雄
    1963 年 83 巻 5 号 p. 498-502
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    8-Quinolinol series compounds, when heated with formaldehyde in dilute ethanol in potassium carbonate alkalinity, form the so-called “joint reaction” products and the methyl group in 2-position of 2-methyl-8-quinolinol does not react with formaldehyde.
    1) 8-Quinolinol forms 7, 7′-methylene-bis-8-quinolinol.
    2) 5-Chloro-8-quinolinol forms 7, 7′-methylene-bis[5-chloro-8-quinolinol] (IVa) but the reaction does not progress in sodium hydroxide alkalinity.
    3) 2-Methyl-8-quinolinol forms 7, 7′-methylene-bis[2-methyl-8-quinolinol] (VIa) and the methyl group does not take part in the reaction.
    4) 2-Methyl-8-quinolinols with halogen groups in the position para to the hydroxyl, such as 2-methyl-3-(2-chloroethyl)-4-chloro-5-bromo-8-quinolinol (X) and 4-methyl-9-chloro-2, 3-dihydrofuro [3, 2-c] quinolin-6-ol (Xa), do not undergo this reaction.
    5) with 2-methyl-4-chloro-5, 7-dibromo-8-quinolinol (XII) and 2-methyl-3-(2-chloro-ethyl)-4-chloro-5, 7-dibromo-8-quinolinol (XIII), one bromine atom is lose and compounds (XIV and XV) forming a methylene bonding at that position are obtained.
  • 小沢 樹夫, 渋谷 茂雄
    1963 年 83 巻 5 号 p. 503-506
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to determine the position of the bromine atom lost in the reaction of 2-methyl-3-R-4-chloro-5, 7-dibromo-8-quinolinol (I: R=CH2CH2Cl; Ia: R=H) in its reaction with formaldehyde in potassium carbonate alkalinity, the reaction outlined in Chart 1 was carried out. Heating of 2-methyl-3-R-4-chloro-5-bromo-7-[N-(2-hydroxy-ethyl)aminomethyl]-8-quinolinol (VII: R=CH2CH2Cl; VIIa: R=H) with paraformaldehyde in potassium carbonate alkalinity results in the liberation of bromine to form VIII and VIIIa. Application of 1 molar ratio of bromine to VIII and VIIIa results in the formation of II and IIa, which agreed with the products obtained by debromination of I and Ia by heating with paraformaldehyde in potassium carbonate alkalinity. It is concluded from these experimental results that VIII and VIIIa are 5, 5′-methylene-bis [7-quinolinemethanol] type compounds and that II and IIa are 5, 5′-methylene-bis [7-bromo-8-quinolinol] type compounds, debromination of I and II having taken place at 5-position.
  • 甘露寺 泰雄
    1963 年 83 巻 5 号 p. 507-513
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The relationship between absorption spectra and ferric complexes in acidic iron springs was examined.
    (1) The absorbance in the range of 220-340mμ increases on exposure to the air. The relationship between absorbance, D, and formal concentration of ferric ion, CFe3+, is linear at all pH.
    (2) The absorption at wave lengths longer than 270mμ increases by decreasing acidity or increasing concentration of sulfate ion. The relationship between absorbance and concentration of hydrogen ion, and of sulfate ion is given by the following equation.
    1/D=a+b[H+]=a′+b′/(CSO42-)
    where a, b, a′, and, b′ are experimentally constant.
    The absorption at wave lengths longer than 270mμ mainly due to FeSO4+. This result is in good agreement with studies on oxidation-reduction potential of iron springs by Mashiko. Many kinds of ferric complexes (Fe3+, FeSO4+, FeCl2+, Fe(OH)2+, Fe(OH)2+, etc.) are present in iron springs, but among these complexes, ferric sulfate complex, FeSO4+, plays a leading part in the absorption spectra and oxidation-reduction potentials of the springs.
  • 甘露寺 泰雄
    1963 年 83 巻 5 号 p. 513-518
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The relationship between absorption spectra and sulfur compounds, such as hydrosulfide, polysulfide, and thiosulfate ions, contained in sulfur springs were examined.
    (1) The maximum absorption at 230mμ, which is due to hydrosulfide ion, is observed in neutral and weak alkaline sulfur springs. The absorption curve changes its shape markedly on exposure to the air. The change is caused by the oxidation of hydrosulfide ion to polysulfide and thiosulfate ions. The absorption in the region of 220-260mμ, which is due to hydrosulfide ion, decreases with time, but when hydrosulfide ion is oxidized to polysulfide ion, the absorption at wave length longer than 260mμ, which is due to polysulfide ion, increases for a short time and then it decreases.
    (2) The absorption of hydrosulfide ion changes with deviation of pH value and the relationship between absorbance, D, and concentration of hydrogen ion is given by the following equation:
    1/D=1/ε1CH2S+[H+]/ε1CH2S⋅KH2S
    where ε1 is the absorption coefficient of HS-, CH2S is the total concentration of H2S, and KH2S=[H+][HS-]/[H2S]. Plots of the reciprocal of absorbance against concentration of hydrogen ion is experimentally linear under constant total concentration of H2S. Formal dissociation constant, KH2S, is calculated from the equation.
  • 松尾 市郎, 高橋 通, 大木 貞雄
    1963 年 83 巻 5 号 p. 518-522
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    By Bischler-Napieralski ring closure reaction with N, N′-diphenethyloxamides (IIc, d, e), the tetrahydro-1, 1′-biisoquinolines (IIIc, d, e) were obtained in the yields of 61.5, 32.3 and 8.2%, respectively. Catalytic reduction of IIIc and IIId afforded corresponding octahydro-derivatives (VIIc, d). 1-(Phenethylcarbamoyl)-3, 4-dihydrolsoquinolines (IVc, f) were synthesized from ethyl 3, 4-dihydro-1-isoquinolinecarboxylates (VIa, b) and phenethylamine.
    Compounds (IIIc, d), (VIIc) and (IVf) did not exhibit strong blood pressure lowering and pain alleviating activities.
  • 川添 豊, 夏目 幸子
    1963 年 83 巻 5 号 p. 523-526
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Through the investigation of nuclear magnetic resonance spectra of pyridazines and their N-oxides, ring π-electron structure of pyridazines N-oxides were discussed. In case of N-oxides it was assumed that π-electron density at α and γ-position to the N-oxide group would be increased whilst the π-electron density at β-position would be decreased. It follows, therefore, that the position of N-oxide group in the assymetrically substituted pyridazine N-oxides can be determined from their nuclear magnetic resonance spectra.
  • 吉武 寛人
    1963 年 83 巻 5 号 p. 527-531
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Phenylphenol is obtained on industrial as well as laboratory scale by the purification of distillation residue of synthetic phenol or from the dehydrogeneous condensation of phenol. These procedures are superior to others because of an inexpensive and steady large scale supply of starting material. Since 2- and 4-phenylphenol both exist in these starting materials and form a solid mixture in all proportions, their isolation becomes difficult. The reexamination of the various known procedures of their purification indicated that inspite of troublesome methods, the purity and the yields of the products are not satisfactory. During our studies concerning the isolation of pure 2-phenylphenol, which is required for hydrogenation, from the distillation residue, we found the solubility ratio of two isomers of phenylphenol in aliphatic alcohol to be much larger than those in petroleum type solvents such as petroleum benzin. Using this property we succeeded in isolating pure 2- and 4-phenylphenols in high yields by the comparatively simple procedure. In this case, the sudden change in solubility of 2-phenylphenol, which results by its transformation into its m. p. 23° crystalline form, was observed. The sulfur containing impurity in the 2-phenylphenol fraction of synthetic crude phenol obtained by sulfonation method, is presumed to be a cause of troublesome purification of 2-phenylphenol. Desulf urisation of impure 2-phenylphenol (m. p. 58-59°, S, 0.3%) with 5% Raney nickel by weight of starting material, at initial hydrogen pressure, 70kg./cm2, temperature, 120° and time, 50 min., gave 2-phenylphenol, m. p. 57-57.5°, S, 0.0007%. When 10% of Raney nickel at atmospheric hydrogen pressure, temperature, 120°, time, 3 hours was used, 2-phenylphenol m. p. 57.5-58°, S, 0.01% was obtained.
  • 吉武 寛人
    1963 年 83 巻 5 号 p. 532-541
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    When 2-phenylphenol, 4-phenylphenol and biphenyl were hydrogenated with Raney nickel (initial hydrogen pressure, over 90kg./cm2), the reaction proceeded according to temperature-pressure relation curve, constituting two well defined valleys. The first valley showed the completion of hydrogenation of phenol part in the two benzene rings while the second, that of phenyl part. It follows therefore, that the selective hydrogenation can be carried out effectively using this phenomenon. The similar results were obtained in the case of medium pressure hydrogenation reaction (initial hydrogen pressure 50-90kg./cm2). The higher pressure hydrogenation product of 2-phenylphenol obtained by this procedure was analysed by gas chromatography. The all components characterized by gas chromatography were further identified chemically. Besides the six compounds which are known to form, 2-phenylcyclohexanone, 2-cyclohexylcyclo-hexanone and 2-cyclohexenylcyclohexanone were also detected. The retention times of these nine compounds and their infrared spectra were examined.
  • 吉武 寛人
    1963 年 83 巻 5 号 p. 542-548
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the previous paper, the high pressure liquid-phase hydrogenation of 2-phenylphenol (initial hydrogen pressure, 100-130kg./cm2) was reported. It has been observed that these harsh conditions are not suitable to examine the course of reaction since the hydrogenation proceeds further in such case. Therefore, in this paper medium pressure liquid-phase hydrogenation (initial hydrogen pressure 50-90kg./cm2, hydrogen mole ratio, 6.8-12) was investigated and the important factors which influence the reaction and the products obtained were examined. Among eighteen tested catalysts, three nickel type reduction catalysts were found to be suitable. Copper-zinc catalyst showed less hydrogenation activity and among the reduction products, large amounts of 2-phenylcyclohexanone and 2-cyclohexylcyclohexanone were found. The following relationship between solvent used and hydrogenation speed were established: tert-butanol; propanol; iso-butanol; butanol; sec-butanol; methanol=259; 182; 129; 113; 108; 100, respectively. In the case of hydrogenation of 2-phenylphenol and its related compounds the reaction was proceeded more by the pressure than the temperature. The hydrogenation began from a pressure of about 80kg./cm2, irrespective of the kind of solvent and compound used. The formation of stereoisomers during the reaction was also studied. Similar to that of high pressure liquid-phase hydrogenation, in medium hydrogen pressure liquid-phase, cis-isomer rearranged into trans-isomer (DL-trans-2-cyclohexylcyclohexanol), depending upon the stage of hydrogenation.
  • 吉武 寛人
    1963 年 83 巻 5 号 p. 549-551
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The gas-phase hydrogenation of 2-phenylphenol (nickel-aluminium catalyst, hydrogen pressure, 1-11kg./cm2, oil bath temperature, 200°, catalyst temperature, 200-270°), gave bicyclohexyl, phenylcyclohexane and 2-cyclohexylcyclohexanone, which are derived from 2-phenylphenol by hydrogenation, dehydrogenation and dehydration. This result differs from that of the liquid-phase hydrogenation in which alcohol and ketone were formed. In this case when space velocity of hydrogen is greater and pressure is lower, i.e. the period of contact with catalyst and 2-phenylphenol is shorter, the yield of phenylcyclohexane and 2-cyclohexylcyclohexanone is increased. In contrary conditions the yield of bicyclohexyl is increased. When catalyst temperature is over 270° hydrogenolysis of 2-phenylphenol and its hydrogenation product occurs.
  • 上田 伸一, 寺岡 章雄
    1963 年 83 巻 5 号 p. 552-554
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    A dibromide of 1, 6-dimethoxydibenzo-p-dioxin (I) was obtained by its brominati on in glacial acetic acid. This dibromide is identical with the dimethoxy derivative which is synthesized by the procedure of Chart 1 from a dinitro compound obtained by nitration of 1, 6-dibromodibenzo-p-dioxin (III) with fuming nitric acid in glacial acetic acid. Hence dibromi de of I is revealed to be 1, 6-dimethoxy-4, 9-dibromodibenzo-p-dioxin (II) and dinitro derivative of III, 1, 6-dibromo-4, 9-dinitrodibenzo-p-dioxin (IV). Also, mononitro and dinitro derivatives were prepared by a similar nitration of I with fuming nitric acid in glacial acetic acid. These compounds are assumed to be 1, 6-dimethoxy-4-nitrodibenzo-p-dioxin (VII) and 1, 6-dimethoxy-4, 9-dinitrodibenzo-p-dioxin (VIII), respectively.
  • ヒキノ ヒロシ, 曳野 靖子, 竹下 保義, 岩動 淑子, 竹本 常松, 赤堀 昭, 安田 郁夫
    1963 年 83 巻 5 号 p. 555-558
    発行日: 1963/05/25
    公開日: 2010/02/19
    ジャーナル フリー
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