YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
94 巻, 12 号
選択された号の論文の23件中1~23を表示しています
  • 原野 一誠, 田口 胤三
    1974 年 94 巻 12 号 p. 1495-1502
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    In order to clarify the mechanism for the formation of trithiocarbonates by treatment of sodium xanthogenates, derived from allylic and benzylic alcohols, with methyl iodide in carbon disulfide-dimethyl sulfoxide mixture, 1b) the same experiments were made with sodium O-benzyl xanthogenate. Results of chemica1 reactions and ultraviolet spectral data supported the presumption that this reaction involved the following key steps : (a) Formation of sodium benzyl and methyldithiolcarbonates from sodium O-benzyl xanthogenate by reaction with methyl iodide, (b) transformation of the dithiolcarbonates to sodium benzyl and sodium methyltrithiocarbonates by the attack of carbon disulfide present in excess, and (c) alkylation of trithiocarbonates (monoester) with dibenzyl or benzyl S-methyl xanthates to their diester.
  • 梁井 光二, 武田 成子, 馬場 強三, 北川 浩一
    1974 年 94 巻 12 号 p. 1503-1514
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    2, 4-Dichloro- (Ia, b) or 4, 6-dichloropyrimidine (II) was treated with aminoalcohols to afford the 4-substituted compounds. When these compounds were treated with thionyl chloride in tetrahydrofuran, cyclized compounds (Va, b, VIb, XIa, b, XIIb, XVa, b, XVII, XIX, and XXI) were obtained. In this reaction, some of the compounds (VIb and XIIb) were substituted by chlorine atom at the 5-position of pyrimidine ring. By the reaction of compound XXI with alkaline solution under a mild condition, ring opening of the pyrimidine occurred to give imidazolidine derivatives (XXII and XXIII). The compounds Ia, b or II was treated with aminoacetal to afford 4-(2, 2-diethoxyethylamino) compounds, which were converted to imidazo[1, 2-c]pyrimidines (XXVIIa, b and XXXII) by the reaction with 6 N hydrochloric acid followed by cone. sulfuric acid. In this case, ring opened compound (XXXIII) was obtained as a minor product.
  • 小泉 京子, 三井 和子, 樋口 一恵
    1974 年 94 巻 12 号 p. 1515-1519
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Studies were made on the interaction of α- or β-cyclodextrin with seven kinds of barbituric acid derivatives and two kinds of analogous compounds, and it was found by solubility analysis that complexes were formed between both kinds of cyclodextrins and all of the barbiturates (including the analogous compounds) tested. The slopes of the solubilization isotherms were generally larger for β-cyclodextrin-barbiturate system than for α-cyclodextrin-barbiturate system. Barbiturates having a bulky substituent showed especially small interaction with α-cyclodextrin. Solubility analysis, and composition analysis of crystalline complexes showed that 2 : 1 complexes were formed between α-cyclodextrin and the barbiturates, and 1 : 1 complexes between β-cyclodextrin and the barbiturates. A possible explanation for such a difference was given. Deposition of free thiopental from aqueous preparation of sodium thiopental by absorption of atmospheric carbon dioxide was retarded to a large extent in the presence of α-cyclodextrin.
  • 亀谷 哲治, 高橋 喜美男, 鈴木 敏夫, 福本 圭一郎
    1974 年 94 巻 12 号 p. 1520-1523
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Treatment of N-furoyltryptophan with polyphosphate ester in chloroform afforded 2-furoylamino-4-methy1cyc1opent[b]indol-3-one (VIII), but not 3, 4-dihydro-β-carboline derivatives (VII). The structure of VIII was confirmed from infrared, nuclear magnetic resonance and mass spectral data. Catalytic hydrogenation of VIII in acetic acid in the presence of platinum oxide as a catalyst gave a diastereoisomeric mixture of the tetrahydrofuran derivatives, whose spectral data supported the structure (IX), and the ring closure by way of route c was found to have occurred.
  • 小澤 光, 池田 實
    1974 年 94 巻 12 号 p. 1524-1530
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Pharmacological drug interaction of nonsteroidal anti-inflammatory drugs was tested from the standpoint of their inhibitory effect on capillary permeability and analgesic action in mice by oral administration, and the following results were obtained. 1) The inhibitory effect of the combined use of naproxen with indomethacin on capillary permeability was weak, partial, and antagonistic. On the other hand, the combined effect of indomethacin with phenylbutazone and of naproxen with aminopyrine was additive. 2) The combined use of (a) aminopyrine with naproxen, (b) aminopyrine with phenylbutazone, and (c) aminopyrine with indomethacin action showed a slightly potentiating action on analgesis, and the degree of potentiation of the combination is decreased, in the order of a, b, and c. On the other hand, the combined effect of phenylbutazone with indomethacin and phenylbutazone with naproxen was additive, but the acute toxicity was potentiated in the latter combination. These results suggest that the potentiation of analgesic action may result from the combined use of a weak basic drug, aminopyrine, with weak acidic nonsteroidal antiinflammatory drugs.
  • 滝野 吉雄, 沢西 直美, 入谷 信彦
    1974 年 94 巻 12 号 p. 1531-1533
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    The reaction of tetracyanonickelate with benzenediazonium salt which gave benzonitrile was studied. After the reaction free nickel ion, remaining total cyanide ion, and benzonitrile produced were determined and yield of benzonitrile was estimated (Table I). The estimated values were no different with one another and showed that four cyanide ions in a tetracyanonickelate ion, which takes part in the reaction, are used only to form benzonitrile. The reaction was affected by pH of the solution and a high yield was obtained in alkaline solutions and none in acidic solutions (Fig. 1). The reason for this effect is the decrease of tetracyanonickelate ions by their dissociation. It may be concluded that the cyanide ion which forms benzonitrile reacts only in a form of tetracyanonickelate ion and a chemical formula for the reaction can be written as follows : 4C6H5N2++ Ni (CN)42-→ 4C6H5CN+N2+Ni2+
  • 榊原 仁作, 猪飼 勝重, 安江 政一
    1974 年 94 巻 12 号 p. 1534-1540
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Along with previously reported lyoniol-A and -B, the toxic principles of Lyonia ovalifolia var. elliptica, a new toxic diterpene named lyoniol-D was isolated and the structure (I) has been proposed on the basis of spectral data, chemical reactions, and correlation with lyoniol-A. Lyoniol-A (II) was chemically correlated with grayanotoxin-I (XI) through the conversion of both to a common substance, 3, 6-dioxo-5, 10, 16-trihydroxygrayanane (XX=XXII). Therefore, the structures of lyoniol-A and -D have been unambiguosly established as II and I, respectively, since the structure of grayanotoxin-I was already determined as XI by the X-ray structural study. Several hitherto undescribed derivatives of were also prepared in the course of the attempted correlation of above described lyoniols.
  • 桑島 淳二, 坪井 俊紀, 藤谷 武一, 石川 幸作, 中村 恵二, 大沢 淑子, 金子 博美, 吉田 耕一, 清水 当尚
    1974 年 94 巻 12 号 p. 1541-1549
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    CG-635, a new thyroxine analog, was examined for its lipid-lowering effect and influence on basal metabolic rate (BMR), heart and thyroid gland in comparison with L-thyroxine (LT4) and D-thyroxine (DT4) . With daily doses of 3-30 mg/kg, CG-635 markedly reduced plasma cholesterol level in rats and rabbits fed a high cholesterol diet. The potency of these compounds in cholesterol-lowering activity was as follows : LT4=DT4> CG-635> clofibrate. In normal rats, CG-635 with a daily dose of 100 mg/kg showed no effect on BMR, heart rate, heart weight and thyroid gland weight, though LT4 showed considerable effect even with the daily dose of 1.0 mg/kg. The effect of CG-635 on BMR, heart rate and heart weight in thiouracil- or methimazole-treated rats was 700 -3500 times less than that of LT4, and 200-275 times less than that of DT4. The relative activity of CG-635, DT4 and LT4 on BMR, heart rate and heart weight compared at the dose showing the same cholesterol-lowering potency was 1 : 4 : 12-60. These results suggested that CG-635 had a marked cholesterol-lowering activity without corresponding effect on BMR, heart and thyroid gland.
  • 志野木 正樹, 村井 康子, 森 五彦, 武内 孝之
    1974 年 94 巻 12 号 p. 1550-1559
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Examinations were made on optimal experimental conditions for instrumental determination of various elements in cannabis by neutron activation analysis, without any radiochemical separation, and the following conditions were found to be useful. Irradiation samples to be used are about 300 mg of the leaves or stem bark, and about 100 mg of the root. For soil sample, about 50 mg is used for the determination of short half-life nuclides and about 300 mg for long half-life nuclides. For short half-life nuclides, the samples are irradiated for 1 min, activity is measured for 200 sec after a decay of 3 min, and for 400 sec after a decay of 10 min. For long half-life nuclides, the samples are irradiated for 60 min and the activities are measured for 4 K sec after 1 week and for 10 K sec after 1 month. Use of supersonic waves is also convenient for cleansing of the samples. Thirty-five kinds of interesting elements were determined by this method from cannabis cultivated in Maizuru area.
  • 森本 武男, 山元 正昭, 丸山 成和, 鶴水 隆
    1974 年 94 巻 12 号 p. 1560-1565
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Cholera crisis-inhibiting factors (CCIF) and immunoglobulines were isolated from the intestines of rabbits immunized with inactivated vibrio cholerae and also from non-immunized intestines, and they were purified. From the immunized intestines, four fractions possessing cholera crisis inhibiting activity, PL, PS, IgA, and IgM were obtained. The cholea crisis-inhibiting activity of fraction PL appeared at a dose of 0.05 μg/mouse, the specific activity of which was the same as those of fractions IgA and IgM, but the cholera-crisis inhibiting activity of fraction PS appeared at a dose of 0.005 μg/head and the activity of fraction PS was the highest. From non-immunized intestines, three fractions possessing cholera crisis-inhibiting activity, NL, IgA, and IgM, were obtained. Activity of each of these fractions was lower than those obtained from the immunized intestines, and especially, fraction NS did not show any activity. A thin-layer electrophoresis of fraction PL showed a wide band. The fraction PL was found to be a high molecular glycoprotein containing IgA, IgM, and IgG. The activity of fraction PL seems to be due to the non-specific activity of immunoglobulin, the activity of which may be strengthened by further immunization. A thin-layer electrophoresis of fraction PS showed almost a single band, but its disc electrophoresis did not prove it to be a single component. This product is a novel active substance produced by immunization and is a low molecular glycoprotein, which contains hexose, hexosamine, and methylpentose, but does not contain sialic acid and immunoglobulin. The property of this product is different from that of fraction PL. Cholera crisis-inhibiting factors are produced by immunization of pigs as well as rabbits with vibrio cholerae or crude exotoxin.
  • 加藤 日出男, 越中 栄一, 荒田 義雄, 花岡 美代次
    1974 年 94 巻 12 号 p. 1566-1573
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Reduction of the methiodides (VI and XV) with sodium amalgam gave the medium ring aminolactams (VII and XVI respectively) in an excellent yield. Treatment of VI and XV with phenyllithium resulted in the rearrangement to afford the spiroaminolactams (XI and XX), which were reduced with lithium aluminum hydride to the spirodiamines (XII and XXI, respectively). The spirodiamine (XII) was also obtained directly from VI on treatment with lithium aluminum hydride.
  • 遠藤 次郎, 長沢 元夫
    1974 年 94 巻 12 号 p. 1574-1579
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Five new sesquiterpenoids, caulesyl acetate (II), 4-hydroxy-β-bulnesene (III), selina-3, 7(11)-dien-8-one (IV), selina-4(14), 7(11)-dien-8-one (V), and germacrone 4, 5-epoxide (VI), and four known sesquiterpenoids, germacratriene (VIII), β-selinene (IX), selina-3, 7(11)-dien (X), and germacrone (VII), were isolated from the essential oil of the subterranean part of Asarum caulescens (Aristolochiaceae). Structures of these substances were determined by chemical and spectroscopic evidences.
  • 高村 綱一, 金庭 延慶, 今川 歓二
    1974 年 94 巻 12 号 p. 1580-1584
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Adsorption of the cationic surfactant, hexadecyltrimethylammonium bromide, on sulfadiazine, sulfaphenazole, and sulfisomidine in aqueous solution were determined at pH 5.0 and at a constant ionic strength and temperature. The ζ-potentials of these sulfonamides and porosities of the sedimentation bed of the suspensions were also measured under the same conditions. It was found that both the adsorption isotherms and ζ-potential curves for these three sulfonamides are divided into four distinct regions and the surfactant molecules adsorbed form hemimicelles at water-solid interface in the third region for all sulfonamides. The estimation of hydrophobic energy for the adsorption of the surfactant was made by the application of Grahame's equation to each adsorption isotherm and the results indicate that the hydrophobic energy between the surface of uncharged sulfonamide and hydrocarbon chains of the surfactant is important in the same way as the cohesive energy between hydrocarbon chains of adsorbed surfactants. The flocculation-deflocculation properties of the suspension may be explained by the orientation of adsorbed surfactant molecules at the water-solid interface.
  • 柴崎 利雄, 吉岡 澄江
    1974 年 94 巻 12 号 p. 1585-1592
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Fluorescence was examined for the chelates of alkyl and aryl salicylates with boric acid. A significant difference was found in fluorescence intensities and also in fluorescence lifetime between alkyl and aryl esters. This difference was interpreted in terms of the electronic energy levels and the electron distributions in the salicylates calculated with semi-empirical LCAO-SCF-CI method and the method of composite molecule. It was found that in the case of alkyl esters charge-transfer configuration contributes predominantly in the first excited state, whereas in the case of aryl esters locally excited configuration contributes predominantly. The difference in the fluorescence intensities is concluded to be due to the difference in the rates of the non-radiative transition.
  • 竹本 常松, 草野 源次郎, 青田 恵太郎, 兼島 瑞枝 /, N.A.EL. EMARY
    1974 年 94 巻 12 号 p. 1593-1596
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Three new sesquiterpenes, namely, O-methylcacaldienol (I), mp 76 -78°, C16H16O2, O-methyldehydronorcacalol (II), mp 168°, C15H18O3, and cacalonol (III), mp 201 -203°, C15H14O3, were isolated from Cacalia auriculata DC. var. kamtschatica (MAXIM.) MATSUMURA (Japanese name, "Mimikohmori") (Compositae) and their structures were elucidated. O-Methyldehydrocacalol (IV), β-amyrin (V), and phytol (VI) were also isolated, and β-sitosterol (VII), stigmasterol (VIII), and campesterol were detected by gas chromatography and mass spectrometry.
  • 竹本 常松, 宮瀬 敏男
    1974 年 94 巻 12 号 p. 1597-1602
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    A new flavonol glycoside, named boehmerin, was isolated from the roots of Boehmeria tricuspis MAKINO (Urticaceae) together with quercetin, taxifolin and avicularin. The structure of boehmerin was determined as quercetin 3-(3"-O-acetyl)-α-L-arabinofuranoside on the basis of its spectrometrical and chemical data.
  • 山根 靖弘, 坂井 和男, 吹野 秀亀, 大多和 昌克, 飯郷 正明, 森田 育男
    1974 年 94 巻 12 号 p. 1603-1606
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Following the previous report on the determination of 4-nitroquinoline 1-oxide (4-NQO), which is a chemical carcinogen, and its metabolites, 4-hydroxyaminoquinoline 1-oxide (4-HAQO), 4-aminoquinoline 1-oxide (4-AQO), and 4-hydroxyquinoline 1-oxide (4-(OH)QO) in biological materials, fluorimetric determination of 4-aminoquinoline (4-AQ), which is the last reduced metabolite of 4-NQO, was established. After the development on a silica gel thin-layer chromatography, a single band of Rf 0.15, corresponding to 4-AQ, was extracted with HCl-MeOH (Rfs of 4-HAQO 0.60, 4-AQO and 4-(OH)QO 0.45) and the fluorescence intensity was measured with excitation at 300 nm and emission at 355 nm. In addition a further modification of the determination of 4-NQO and its metabolites was attempted and a more rapid and more reliable determination was established.
  • 金庭 延慶, 高村 綱一
    1974 年 94 巻 12 号 p. 1607-1611
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Adsorption isotherms of hexadecyltrimethylammonium bromide on sulfaphenazole and sulfadiazine in aqueous solution were determined at pH 4.0 and 6.0, and at constant ionic strength and temperature. The ζ-potentials of these sulfonamides and porosity of the sedimentation bed of their suspension were also measured under the same conditions. It was found that ζ-potentials of both sulfaphenazole and sulfadiazine decrease as pH of suspensions increases. Changes in the surface charge of sulfaphenazole affect the adsorption of the surfactant on it and therefore the orientation of the surfactant molecules at water-sulfaphenazole interface and dispersibility of the suspensions vary with the pH change of the suspensions. In the case of adsorption on sulfadiazine, however, almost the same adsorption isotherms are obtained in the suspensions of pH 4.0 and 6.0. Some effects of the specific adsorption of anions have to be considered in addition to the effect of dissociating ions at the surface of both sulfonamides for their surface charge.
  • 高村 綱一, 金庭 延慶
    1974 年 94 巻 12 号 p. 1612-1615
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    The adsorption isotherms of hexadecyltrimethylammonium bromide on sulfadiazine, sulfaphenazole, and sulfisomidine in the presence of 10-3, 10-2, and 10-1M KBr were determined and comparison of these isotherms with isotherms in the absence of KBr was made. It is clear from this comparison that with increasing concentrations of KBr the adsorption isotherms move toward lower equilibrium concentrations and the saturated amount of adsorption increases for these three sulfonamides. This movement of isotherms and increase in the saturated amount of adsorption by addition of KBr vary with the kind of sulfonamides and these variations may be explained by both hydrophobic and hydrophilic characters of the surface of each sulfonamide. It is found that these variations of the adsorption isotherms influence the flocculation-deflocculation property of the suspensions.
  • 菊池 徹, 横井 利夫, 梅本 和子, 新宮 徹朗
    1974 年 94 巻 12 号 p. 1616-1619
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Constituents of Scaevola frutescens (MIILER) KRAUSE were investigated and several known triterpenes and xanthyletin (VIII) were obtained. In addition, two kinds of coumarins (IX and XI) were isolated and their structures were examined by means of nuclear magnetic double resonance methods.
  • 篠田 雅人, 太田(清水) 節子, 日野 亨, 赤星 三弥
    1974 年 94 巻 12 号 p. 1620-1626
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    Relationship between the chemical structure of 43 kinds of compounds, having indole and indoline as their fundamental skeleton, and their effect in protecting radiation damage was examined in mice irradiated with 800 R of X-rays, and the following facts were learned. 1) Tryptamine and many of its derivatives proved to have a radioprotective activity. 2) Compounds having acetonitrile, thioacetamide, or 2-aminothiazoline as the side chain in the 3-position were effective. 3) Some of the derivatives with 2-mercaptoethylamine side chain and 2-indolinethione-type compounds were effective as protectors. 4) Derivation of the side chain in the indole ring to the effective sulfur-containing group resulted in retardation of the appearance of the protective effect.
  • 梅本 光一郎
    1974 年 94 巻 12 号 p. 1627-1633
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    It has become quite clear from past studies that the composition and appearance of crystalline inorganic components in plants form an important character index in plant taxonomy. Taxonomic system of Japanese plants of the Saxifragaceae was reexamined from the componental and morphological relation of the crystals contained in the leaves of these plants. Crystal observations were made by the "low-temperature plasma ashing method for biological tissues" that the author had devised. The plants of the Saxifragaceae examined were among those in Ohwi's "Flora of Japan" and comprised 20 genera. Results of this examination are summarized below. Saxifragaceae plants can be divided roughly into three groups from their crystalline components but the majority contain crystals of calcium oxalate[Ca(COO)2-H2O]crystals. Therefore, it may be said that the Saxifragaceae plants are a fairly coherent group of plants when looked from their crystalline component. The most interesting fact is that Mitella acerina MAKINO (Japanese name, Momiji-Charumeruso) alone contains calcium carbonate crystals in addition to calcium oxalate crystals. Crystal form in Saxifragaceae plants can be divided into 14 types, and the plants can be classified into 8 groups from interrlationship among these types. Looked from the crystal form, Engler's syllabus classification system, which dose not make a distinction between herbaceous and woody plants, is less of a taxonomical problem than the classification of Hutchinson, Huber, and Takhtajan, which distinguishes the herbaceous and woody plants as different lines. Nevertheless, both classification systems seem to have several problematical points which must fully be discussed in future. The result of the present examinations failed to show any evidence which of these classification systems more closely follows the natural trend, and a concerted and careful conclusion must be drawn after further examination of other characteristics in addition to that of crystalline inorganic components.
  • 安江 政一, 榊原 仁作, 伊奈 郊二, 柳澤 いく子
    1974 年 94 巻 12 号 p. 1634-1638
    発行日: 1974/12/25
    公開日: 2008/05/30
    ジャーナル フリー
    The flowers of Tripetaleia paniculata were extracted with methanol and the extract was treated (Chart 1). Compounds detected are higher aliphatic saturated hydrocarbons, ester, alcohols, epifriedelinol, β-sitosterol, ursolic acid, oleanolic acid, maslinic acid, β-sitosteryl β-D-glucoside, quercetin, avicularin, hyperoside, 6-hydroxy-7-methoxycoumarin, monotropein, arabinose, xylose, glucose, sucrose, and toxic diterpene, rhodojaponin-III. From the wood extract of the same plant were detected hydrocarbons, esters, taraxerol, taraxeryl acetate, friedelin, epifriedelinol, β-sitosterol, ursolic acid, oleanolic acid, acetyloleanolic acid, 3-O-(p-hydroxy-trans-cinnamoyl)-ursolic acid, β-sitosteryl β-D-glucoside, monotropein, monotropein methyl ester, lyonisidem, and 2, 6-dimethoxy-p-benzoquinone.
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