YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
81 巻 , 2 号
選択された号の論文の37件中1~37を表示しています
  • 桜井 寛
    1961 年 81 巻 2 号 p. 155-159
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    A solution of morphine colors red when heated with 1-nitroso-2-naphthol in dil. nitric acid but the color is unstable (Reaction I). This coloration is not produced by codeine, thebaine, narcotine, and papaverine. The reaction of morphine with chloramine-T in dil. hydrochloric acid solution and addition of 4-aminoantipyrine into this solution results in red coloration (Reaction II ). This color is comparatively stable but codeine also exhibits this coloration and it must be separated from the opium alkaloids for separatory determination. Separation of codeine can be effected by extraction with chloroform in sodium hydroxide alkalinity. Limit of detection by a spot reaction is 5γ/0.05cc. by the Reaction I and 10γ/0.05cc. by the Reaction II. Determination of morphine by the Reaction II is carried out as follows: One cc. of the test solution (morphine, 150-600γ/cc.) and 1cc. of N hydrochloric acid are placed in a 10cc. measuring flask and the flask is immersed in water of 10-15° for 5minutes. The reagents, 0.4% chloramine-T solution (A) and 4% aminopyrine solution (B) are also similarly treated. One cc. of (A) is added to the test solution, maintained at the same temperature for 3minutes, 0.5cc. of (B) is added, and the mixture is maintained at the same temperature for 5minutes. To this mixture, 1cc. of 1.5% potassium ferrocyanate is added, flask is taken out, stood for 3minutes, 1cc. of 5% solution of 4-aminoantipyrine is added, followed by 1.5cc. of 5% ammonia water within 3minutes, and the mixture is diluted to 10cc. with water. This is shaken with 2cc. of chloroform (shaking vigorously about 100 times) and the mixture is cen-trifuged. Optical density of its aqueous layer at 505mμ is measured 20-30minutes after coloration. Blank test is carried out with 1cc. of water in place of the test solution.
  • 桜井 寛, 梅田 益雄
    1961 年 81 巻 2 号 p. 160-163
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of papaverine with chloramine-T in dil. hydrochloric acid solution and extraction with chloroform gives a red coloration in the chloroform layer. This coloration is not observed in morphine, codeine, thebaine, or narcotine. The limit of detection by a spot reaction is 0.75 γ/0.05cc. This reaction can be utilized for colorimetric determination of papaverine and the presence of one of the foregoing alkaloids in an amount equal to or less than papaverine does not affect this determination. When a larger amount of other alkaloids is present, chloramine-T is consumed and the determined value will be affected, so that the determination must be carried out after separation. The determination is carried out as follows:
    One cc. of the test solution (60-540 γ of papaverine) is placed in a centrifuge tube, 6cc. of 0.25N hydrochloric acid is added, and the mixture is maintained at 30°±1° for 5minutes. This is shaken with 1cc. of 0.5% chloramine-T solution and then maintained at the same temperature for 7minutes. The mixture is cooled in ice for 2minutes, 5cc. of accurately measured chloroform is added, and the mixture is shaken vigorously for 15minutes. The mixture is centrifuged for 5minutes, the aqueous layer is discarded, and the chloroform layer is dried by shaking with 0.1g. of anhydrous sodium sulfate. This is centrifuged for 5minutes and optical density of the solution at 505 mμ is measured. The blank test is carried out in exactly the same manner with 1cc. of water in place of the test solution.
    When in the presence of the same weight of morphine, codeine, thebaine, or narcotine, the alkaloid mixture is extracted with chloroform in tartaric acid solution to remove papaverine, treated with alkali to remove narcotine, and papaverine is extracted with chloroform. The residue obtained by evaporation of chloroform is mixed with 1cc. of water to be used as the test solution.
  • 桜井 寛
    1961 年 81 巻 2 号 p. 164-165
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Potentiometric titration of papaverine and narcotine was carried out by dissolving ca. 15mg. of the two alkaloids in acetone, methyl isobutyl ketone, or chloroform, and titrated with 0.005N p-toluenesulfonic acid in ethyleneglycol-isopropanol (1:1 mixture by volume). Jump in potential at the equivalence point was ca. 10mV./0.1cc. in chloroform and ca. 30mV./0.1cc. in acetone and methyl isobutyl ketone, from which it was learned that semimicro-potentiometric titration of papaverine and narcotine was possible by the use of the foregoing ketone solvent. Addition of phenol to the acetone solution makes it possible to carry out indicator titration by Methyl Orange. Good results were obtained by the use of this procedure for determination of the alkaloids in papaverine hydrochloride injection (4% solution) and narcotine powder (10% of narcotine).
  • 郡 定文, 河野 通文
    1961 年 81 巻 2 号 p. 166-169
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separatory determination of Ephedra alkaloids has not been established as yet. By the application of partition column chromatography or adsorption chromatography, Separatory determination of l-methylephedrine from l-ephedrine or d-pseudoephedrine was successfully carried out. In the case of partition chromatography, Celite 545 was used as the carrier, buffer solution of pH 6.4 as the stationary phase, and chloroform as the moving phase to separate l-methylephedrine from the sample of alkaloid mixture. The use of chloroform-ethanol mixture (5:1 by volume) as the moving phase then separated l-ephedrine or d-pseudoephedrine. In adsorption chromatography, Brockmann's alumina was used as the adsorbent and the mixture sample was developed with 85% butanol-ether mixture (1:50 by volume) to separate l-methyl-ephedrine. Development with 85% ethanol-ether mixture (1:1 by volume) eluted the remaining l-ephedrine or d-pseudoephedrine. Each of the alkaloids separated by chromatography was determined by nonaqueous or neutralization titration.
  • 郡 定之, 河野 通文
    1961 年 81 巻 2 号 p. 170-172
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Although separately determination of l-methylephedrine from l-ephedrine or d-pseudoephedrine was found possible by the use of partition or adsorption chromatography, l-ephedrine and d-pseudoephedrine could not be separated by these procedures. Their separation was successfully effected by the use of salting-out chromatography. A column (20×500mm.) of Dowex-50 X 2 (200-400 mesh) carrying the sample was developed with 0.1M tripotassium phosphate to separate the two alkaloids and each alkaloid was determined by nonaqueous titration after extraction with chloroform.
    Combination of the method described in the preceding paper and the present one enables separatory determination of l-methylephedrine, l-ephedrine, and d-pseudoephedrine.
  • 掛見 喜一郎, 有田 隆一, 小泉 保
    1961 年 81 巻 2 号 p. 172-178
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Attempts were made to prolong the action of sulfaethylthiadiazole (N1-(5-ethyl-1, 3, 4-thiadiazol-2-yl)-sulfanilamide) by granulation with tristearin as the binder. Blood level of the drug was tested after administration in a rabbit and the lowering rate was found to be decreased. Blood level formula, which agreed well with observed values, was derived by the consideration of the fact that the in vitro erosion is represented by a primary reaction formula and that this erosion rate affected blood level.
  • 山口 一孝, 伊藤 巳代子
    1961 年 81 巻 2 号 p. 179-181
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Atropine and scopolamine were detected quantitatively by paper electrophoresis using 0.1N ammonia solution as the electrolyte. The alkaloids separated on the filter paper were detected as brown spots when exposed to iodine vapor. After elution of these spots, the solvent was evaporated, the alkaloidal residue was nitrated, dissolved in dimethylformamide, and tetraethylammonium hydroxide was added, according to the method of Freeman. The absorbancy (y) of each solution at 545mμ was measured and concentration (x in γ/cc.) of each alkaloid was calculated from the following equations:
    For atropine: x=113y+0.8
    For scopolamine: x=131y+1.3
    Assay results from this method were compared with that of the official method, using scopolia extract and scopolia root as samples.
  • 谷 英郎
    1961 年 81 巻 2 号 p. 182-185
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ethyl 6-methylnicotinate 1-oxide was prepared by oxidation of the ethyl group alone in 2-methyl-5-ethylpyridine by treatment with conc. nitric acid and selenium dioxide, followed by esterification and oxidation with hydrogen peroxide in glacial acetic acid. The nicotinate oxide was derived to 1-methoxylated quaternary salt by treatment with dimethyl sulfate and reacted with potassium cyanide in ethanol-water mixture to form ethyl 4-cyano-6-methylnicotinate, which was derived to dimethyl 6-methylcinchomeronate 1-oxide by hydrolysis, esterification, and oxidation with hydrogen peroxide in glacial acetic acid. This oxide was reacted with phosphoryl chloride at 120° to form dimethyl 2-chloro-6-methylcinchomeronate, which was hydrolyzed with acetic acid-sodium acetate and esterified to form dimethyl 2-oxo-6-methyl-1, 2-dihydrocinchomeronate. Reaction of this salt with ammonia in methanol and reaction of its product diamide with phosphoryl chloride in pyridine finally afforded 3, 4-dicyano-6-methyl-2(1H)-pyridone, an intermediate material for the synthesis of cobalamine.
  • 久保田 和彦, 加来 天民
    1961 年 81 巻 2 号 p. 186-191
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Comparative examinations were made on the pharmacological action of ethyl d- and l-1, 1-diphenyl-3-piperidinobutyl sulfones. Toxicity of the levorotatory compound by intraperitoneal injection in mice was ca. 3 times that of the dextro compound, probably 2-4 times considering respiration and blood pressure tests in rabbits. However, AD50 and AtD50 of the levo compound was ca. 8 and 7 times that of the dextro compound and it is interesting that analgesic and antitussive activity is 2-3 times greater than toxicity. There was no difference between dextro and levo compound in their effect against excised intestine. In antihistamine effect, the levo compound is somewhat stronger than the dextro compound, while the order is reversed in anti-acetylcholine effect, the dextro compound being stronger than levo compound. This compound causes transitory increase in number of drops in aural vessel perfusion test in a rabbit, though the action is weak, and there was no difference in this action between the dextro and levo compounds.
  • 宇野 豊三, 河野 昌雄, 古谷 素子
    1961 年 81 巻 2 号 p. 192-194
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    A method was devised to isolate and determine sulfisoxazole alone from various metabolic products formed after administration of sulfisoxazole. The procedure is as follows:
    A chromatographic column is prepared with 1g. of powdered cellulose, filled in a glass tube (5.5mm.×20cm.) with a solvent mixture of butanol-propanol-water (2:1:1). The sample solution is diluted five fold with butanol-propanol mixture (1:1) and 0.5cc. of its supernatant is passed through the foregoing column. The column is eluted with a solvent mixture of butanol-propanol-water (2:1:1) and 3.5cc. of the initial eluate is discarded. The next 2cc. of the effluent is diluted with ethanol to 5cc. and 1cc. of this solution is added with 0.3cc. of 2N hydrochloric acid and 5cc. of 2% ethanolic solution of p-(dimethylamino)benzaldehyde. The mixture is allowed to stand at 30° for 7minutes, diluted to 10cc. with ethanol, and its optical density at 453mμ is measured. Concentration of sulfisoxazole is calculated from the calibration curve prepared preliminarily.
    The amount of unchanged sulfisoxazole excreted into urine after oral administration of this sulfa drug was determined. Comparative examination was also made on the present method and that of Bratton-Marshall, and the amount of sulfisoxazole changed in the body was measured.
  • 小林 忠之
    1961 年 81 巻 2 号 p. 195-199
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the effect of 2-phenylbutyric acid, its derivatives, and related compounds, quantitative determination of cholesterol was examined. The colorimetric determination by the digitonin method, petroleum ether method, and ferric chloride method did not show any significant difference in procedural effect. Blood cholesterol level in rats was examined and there was no significant difference according to their age, sex, and strain. Examinations were also made on hyper-cholesterolemia in a rat cawed by administration of Triton WR-1339. No change occurred on continuous subcutaneous injection of 50mg./kg./day for 2 weeks or single intravenous injection of 100mg./kg. and a linear dose-response curve was obtained up to 500mg./kg. The blood cholesterol level reached the maximum 18hours after intravenous injection of 200mg./kg. and 22hours after intraperitoneal injection of the same dose, and the level fell to the normal after 120hours.
  • 小林 忠之
    1961 年 81 巻 2 号 p. 200-203
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the effect of 2-phenylbutyric acid, 2-(p-biphenyl)butyric acid, their derivatives, and related compounds which had been found to inhibit endogenous cholesterol synthesis, as reported by Cottet, et al. and by Garattini, et al. Of the 10 kinds of related compounds, water-soluble sodium 2-(p-biphenyl)butyrate had the strongest effect. The effect of the sodium salt of N-(2-p-biphenylylbutyryl)taurine and sodium 2-(p-biphenyl)butyrate showed no significant difference in intraperitoneal and oral administration.
  • 橋本 忠, 関 道子
    1961 年 81 巻 2 号 p. 204-209
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of 1 and 2 moles of bromine to N, N-dirnethyl-3-trirethylsilylaniline (I) respectively affords 4-bromo (III) and 2, 4-dibromo (IV) compounds. Application of nitrous acid to (I) gives the 4-nitroso compound (V) whose catalytic reduction over palladium-carbon affords the 4-amino compound (VI), which can be acetylated to the 4-acetamido compound (VII). The reaction of (I) with benzenediazonium chloride, p-nitrobenzenediazonium chloride, and p-azobenzenesulfonic acid respectively produces 4-phenylazo compound (VIII), 4-(p-nitrophenyl)azo compound (IX), and 4-(4-dimethylamino-2-trimethyisilylphenylazo)benzenesulfonic acid (X). Reduction of (X) with sodium dithionite gives (VI). Nitration of (I) with acetyl nitrate gives the 4-nitro compound (XI) which also forms (VI) by catalytic reduction over palladium-carbon. Reaction of (I) with dimethylformamide, in the presence of phosphoryl chloride, gives 2-trimethylsilyl-4-dimethylaninobenzaldehyde (XII).
    These reaction sequences have revealed that the application of cationoid reagent to (I) results in substitution in the position para to the dimethylamino group, that. the bond between silicon and aromatic ring is stable, and that the stability of this bond is increased by bromine substitution.
  • 亀山 勉
    1961 年 81 巻 2 号 p. 209-214
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Using the pain reaction recording apparatus, which can record pain reaction of a mouse on the hot plate, and the pressure pain apparatus, attempt was made to assay quantitatively some antipyretic analgesics, which have been thought comparatively difficult to detect.
    1) In general, the antipyretic analgesics did not inhibit the primary pain reaction of mice on the hot plate, but prolonged the secondary reaction time to jump out of the hot plate. The narcotic analgesics inhibit both pain reactions completely when large quantities are applied.
    2) All the pyrazolone derivatives used elevated the threshold of the secondary pain reaction of mice on the hot plate and this response increases linearly with the increasing dose of pharmaceutics.
    3) It was found that the range of the effective dose of aniline and p-aminophenol derivatives was very limited and that the side effect appeared when a higher dosages were used.
    4) The salicylates have only a slight analgesic activity to pain stimuli. N-Methyl-salicylamide has a higher analgesic effect than salicylamide.
    5) The analgesic effect of pyrabital was comparatively high and the primary pain reaction on the hot plate was also inhibited by it.
  • 亀山 勉
    1961 年 81 巻 2 号 p. 215-221
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The analgesic activity of some sympathomimetic amines and related substances was tested by means of the hot-plate method and the pressure pain method, which were reported in the previous papers. Motor activity of mice on the hot plate was recorded and compared at the same time. The mice, given 1mg./kg. of methamphetamine subcutaneously, became sensitive to heat pain and the secondary reaction time to jump out of the hot plate was reduced. Although larger doses of methamphetamine increased the motor activity on the hot plate, it prolonged the secondary reaction time, which was considered to be the analgesic effect of the drug.
    In general, the analgesic activity of sympathomimetics increased along with their stimulatory action, which is clearly shown in the comparison between d- and l-methamphetamine. Adrenaline and ephedrine exhibited a slight analgesic activity. Central stimulants, such as methyl phenidate and caffeine, also showed some analgesic action.
    The analgesic action of morphine (2mg./kg.) and methamphetamine (5mg./kg.) was significantly potentiated and the excitatory action of methamphetamine was diminished on combined use.
  • 浮田 忠之進, 鈴木 茂生
    1961 年 81 巻 2 号 p. 222-224
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to synthesize the glycine ester of D-glucose, attempt was made to obtain the starting material, 6-O-(N-benzyloxycarbonylglycyl)-D-glucopyranose, by esterification of N-benzyloxycarbonylglycine with glucose derivative and it was found that dicyclohexylcarbodiimide is a good condensation agent. Compared to the ester condensation of N-benzyloxycabonylglycine and glucose derivative with mixed anhydride of other acids, the use of dicyclohexylcarbodiimide as the condensation agent was found to have the advantage of not forming a large amount of by-products. Further, the latter reagent was found to have entirely no effect on the urethan bond like N-benzyloxycarbonyl group. This process was used to obtain N-benzyloxycarbonylglycine ester of four kinds of glucose derivatives whose hydroxyls other than that at 6-position were protected, and three of them easily afforded 6-O-(N-benzyloxycarbonylglycyl)-α-D-glucopyranose.
  • 浮田 忠之進, 鈴木 茂生
    1961 年 81 巻 2 号 p. 225-226
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The bonding of the benzylidene group in the 2, 3:4, 5-di-O-benzylidene-aldehydo-D-glucose derivative, obtained by benzylidenation followed by demercaptolization of 6-O-benzoyl-D-glucose diethyl mercaptal, was determined as 2, 4:3, 5 and not 2, 3:4, 5. The Meerwein-Ponndorf reduction of 2, 3:4, 5-di-O-benzylidene-aldehydo-D-glucose 6-benzoate gave the corresponding alcohol, which was debenzoylated to the known 2, 4:3, 5-di-O-benzylidene-D-glucitol.
  • 百瀬 勉, 向井 良子
    1961 年 81 巻 2 号 p. 227-230
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    A rapid determination of lactose in milk and powdered milk, and of lactose and sucrose in condensed milk, using 3, 6-dinitrophthalic acid was established. Diluted solution of milk or its products is deproteinized by heating for a short time with basic zinc carbonate and colored by 3, 6-dinitrophthalic acid in the previously established method for reducing sugars. The lactose content is read from the calibration curve. The sucrose in condensed milk is inverted and colored by the same reagent.
    To deproteinize the solution, the sample is diluted with water to 1% solution for milk, 0.1% solution for powdered milk, and 0.25% solution for condensed milk. Two cc. of this solution is diluted with 3cc. of water, deproteinized with about 150mg. of basic zinc carbonate, and diluted to 20cc., except for condensed milk, which solution is diluted to 100cc. The lactose is determined by developing 2cc. of the diluted solution.
    For the determination of sucrose in condensed milk, 2cc. of 10% solution is deproteinized with about 300mg. of basic zinc carbonate, hydrolysed with hydrochloric acid, neutralized, and diluted to 2000cc. Two cc. of this solution is developed and total sugar is read from the calibration curve of glucose. Lactose gives the coefficient of 0.785 when it is read on the curve of glucose and sucrose is calculated from the following equation:
    Sucrose(%)={total sugar(%)-lactose(%)×0.785}×0.95
    This method of determination is simple and rapid for treating a larger number of sample, and the determined value agrees with the macro methods within the largest deviation of ±3%.
  • 村井 好之助
    1961 年 81 巻 2 号 p. 231-235
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In general, the indophenol reaction is thought to be positive in phenols only when there is a substituent in the position para to the hydroxyl group. However, recent reports have shown that the reaction becomes positive even when there is a substituent in the position para to the hydroxyl if such a substituent is liberated by this reaction. It was considered that the similar liberation of the para-substituent might also take place in the indophenol reaction using dimethyl-p-phenylenediamine as the reagent. In order to prove the liberation of such a substituent from the para-position, indophenol pigments were prepared from phenol and 2, 6-xylenol substituted in the para-position with halogen, carboxyl, or sulfonic acid. The pigments were examined by paper chromatography, ultraviolet and infrared absorption spectra, and elemental analysis, and they were all found to be entirely identical with those chemically synthesized from phenol and 2, 6-xylenol. It was thereby confirmed that these substituents present in the position para to the hydroxyl are liberated by this reaction.
  • 伊藤 徳三
    1961 年 81 巻 2 号 p. 236-238
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Methanolic extract of the leaves of Picea bicolor MAYR afforded benzoic acid, 3, 4-dihydroxyacetophenone, resveratrol, and a kind of new stilbene derivative, m. p. 222°(decomp.), C14H12O4. Examination of the leaves from the plants of Omorica section showed that there is a marked difference in components of the leaves from the plants of Eupicea and Omorica sections. Correlation was found to exist between componental distribusion and plant classification.
  • 石井 永, 原田 謹爾
    1961 年 81 巻 2 号 p. 238-242
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In continuation of the previous work, bases contained in Xanthoxylum planispium SIEB. et ZUCC. (Rutaceae) (Japanese name “Fuyuzansho”) were examined and γ-fagarine (III) was newly isolated from its root. Terrestrial portion yielded manoflorine (IV) and xanthoplanine (XPQR-base I), The kind and content ratio of the bases contained in the root and terrestrial portion are listed in Table I.
    The new quaternary base, xanthoplanine, is an aporphine-type phenolic base represented by the empirical formula C16H10(OCH3)3(OH)(=N+(CH3)2). Examinations were also made on the reineckate and phenol methods for separation of water-soluble quaternary base and it was proved that the reineckate method is better in easily affording a base of high purity.
  • 石井 永
    1961 年 81 巻 2 号 p. 243-248
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Structural examinations were made on xanthoplanine, a new water-soluble quaternary base contained in Xanthoxylum planispium SIEB. et ZUCC. (Japanese name “Fuyuzansho”) (Rutaceae), and O-methylxanthoplanine iodide was found to be entirely identical with O, O-dimethyllaurifoline iodide (I:R1-4=CH3). It was further confirmed that O-ethylxanthoplanine iodide showed the same infrared spectrum (in chloroform) as that of synthesized dl-O-ethyl-N-methyllaurotetanine methiodide (VII) and that O-ethylxanthoplanine methine methiodide showed the same infrared curve (KBr) as that of synthesized O-ethyl-N-methyllaurotetanine methine methiodide (IX). It follows, therefore, that the new base, xanthoplanine, is N, N-dimethyllaurotetanine, an aporphine-type quaternary base indicated by formula (X).
  • 石井 永
    1961 年 81 巻 2 号 p. 248-253
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to obtain ultraviolet and infrared spectra of the reduction products of skimmianine, syntheses were carried out according to the route shown in Charts 1-3 for isoskimmianine (II), dihydroskimmianine (III), tetrahydroskimmianine (IV), tetrahydroisoskimmianine (V), tetrahydronorskimmianine (VI), norskimmianine (VII), tridemnethyltetrahydroskimmianine (VIII), isodictamnine (XIII), and dihydrodictamnine (XIV). New compounds prepared in the present series of work included dihydroisoskimmianine (IX), dihydronorskimmianine (X), N-methyltetrahydroskimmianine (XV), and N-methylhexahydroskimmianine methiodide (XIX). Absorption of these compounds, which lacked the lactam and carbonyl bands in their infrared spectra, in the range of 1700 to 1600cm-1 was examined (Table I).
  • 北村 為男, 菅本 もと子
    1961 年 81 巻 2 号 p. 254-261
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Cleavage reaction of O-methyldomesticine (I) with lithium in liquid ammonia afforded two kinds of decomposition bases, A and B. The base A was obtained as its hydrochloride of needles, m.p. 256°(decomp.), and the base was found to be identical with the hydrochloride of 2-methoxy-10-hydroxyaporphine (II) obtained by the action of sodium on (I) in liquid ammonia. Consequently, this reaction was also found to effect complete liberation of the methoxyl group in 1-position, indicating a rather interesting abnormal reaction to take place.
    The base B (needles, m.p. 239°; C17H21O2N) was found to be a monohydroxy-oxohexahydroaporphine. Wolff-Kischner reduction of this base gave a reduction product of the ketone (C17H23ON; [α]D19+161.7°(MeOH), m.p. 210-212°) and its O-methyl ether (m.p. 57-59°; [α]D20+148°(MeOH)). These substances were found to be identical with the synthesized (+)-10-hydroxy-1, 2, 3, 3a, 11b, 11c-hexahydroaporphine (VIIIa), m.p. 206-207°; [α]D25+160.7°, and its O-methyl ether (IXa), m.p. 65-66°; [α]D18.6+158.6°, by mixed melting point determination and infrared absorption spectrum (in Nujol or chloroform). The base B was therefore determined as 2-oxo-10-hydroxy-1, 2, 3, 3a, 11b, 11c-hexahydroaporphine (VI).
    The same lithium-liquid ammonia reaction was carried out on the base A (II) and formation of the ketone compound (VI) was also noticed in this case. This has revealed that this cleavage reaction of O-methyldomesticine (I) first produces the intermediate compound (II) which undergoes reduction to form (VI).
    As one of the model experiments of this reaction, lithium-liquid ammonia reaction was carried out on 2-methoxybiphenyl (X) and it was found that the benzene ring carrying the methoxyl group submitted to partial hydrogenation.
  • 高木 敬次郎, 福田 英臣, 藤江 恭, 松井 賢一郎, 佐藤 道子
    1961 年 81 巻 2 号 p. 261-265
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antitussive activity of several drugs, including antispasmodics, sympathomimetics, antihistamines, and some ω-(diphenylmethoxy)alkylamines, was examined against coughing produced in guinea pigs by mechanical stimulation. A certain relationship was found to exist between chemical structure and antitussive activity of the compounds derived from ω-(diphenylmethoxy)alkylamines. In these compounds, the highest antitussive activity was found in 1-[2-(4-chloro-α-phenylbenzyloxy)ethyl]-piperidine and 4-[2-(4-chloro-α-phenylbenzyloxy)ethyl]-1-piperazineëthanol, which were far more effective than codeine. Pharmacological properties of these two compounds were briefly examined.
  • 高木 敬次郎, 福田 英臣, 佐藤 道子
    1961 年 81 巻 2 号 p. 266-270
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antitussive activity and other pharmacological properties of narcotise and its N-oxide were investigated. Employing the two methods of assay for antitussive activity, it was found that the activity of narcotine N-oxide is a little stronger than narcotine (Table I). The constipating action and inhibition of gastrointestinal propulsion of these drugs could not be observed. Further, their action on blood pressure, respiration, papaverine-like antispasmodic action, and acute and subacute toxicity were examined.
  • 福田 英臣
    1961 年 81 巻 2 号 p. 271-274
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Combined use of pharmaceutics of similar effect is expected to give additive effect if the site of action is the same and pontentiative effect if the site of action is different. This point was examined by the combined use of codeine with other antitussives, tested by the mechanical stimulation method. It was thereby found that the combined use of hydrocodeine and codeine N-oxide, which are considered to have the same site of action, resulted in additive effect while the combined use of chlorpromazine and diphenhydramine showed potentiative effect. Narcotine potentiated the effect of codeine to some extent.
  • 松本 昌次
    1961 年 81 巻 2 号 p. 274-277
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    As a preliminary experiment for elucidation of the reaction mechanism of quinone-activated carbon treatment, reaction was carried out of p-benzoquinone, α-naphtho-quinone, and chloranil with 25 kinds of nitrogen-containing organic compounds, including aliphatic and aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, and proteins. Examinations were made on the isolation of products by adsorption on actuated carbon and ddsorption from this activated carbon. As indicated in Table I, the results of these experiments showed that nitrogen-containing organic compounds in general, with the exception of a few, reacted easily with quinones and that the reaction products are separated by adsorption on activated carbon. It was found that a nitrogen-containing organic compounds are liberated from the adsorbed carbon according to the nature of such compounds or to reaction conditions with a quinone. The appropriateness of this quinone-activated carbon treatment was confirmed and the experiments made some important suggestions for elucidation of this reaction mechanism.
  • 松本 昌次
    1961 年 81 巻 2 号 p. 277-281
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Elucidation of the reaction mechanism of quinone-activated carbon treatment was attempted in order to establish fundamental conditions for complete elimination of pyrogen by such a treatment.
    Reaction of pyrogen and quinone, and experiments on adsorption and desorption of the reaction product by activated carbon were carried out with ribonucleic acid, having similar nature to pyrogen, and pyrogenic sodium alginate injection as test samples. It was thereby revealed that pyrogen (P) and quinone (Q) formed a reversible compound (PQ) like a molecular compound at the initial stage of the reaction and that this compound changed into an irreversible compound PQ like a condensation compound. This was confirmed mainly through the adsorption-desorption curve of these compounds on activated carbon and a reaction sequence illustrated in Chart 1 was presumed.
  • 松本 昌次
    1961 年 81 巻 2 号 p. 282-286
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In accordance with the reaction mechanism for removal of pyrogen by quinone-activated carbon treatment described in the preceding report, examinations were made on the practical operational conditions for complete removal of pyrogen. Several injections of various substances containing pyrogen were submitted to the experiments under the conditions described below. In the quinone-treatment reaction, it is fundamentally essential to have all the pyrogen (P) present in the sample form the irreversible compound, PQ. The conditions for this reaction are the finely pulverized α-naphthoquinone as the quinone, in approx. 0.3g./100cc. of the injection, the solution to be maintained at neutral or slightly alkaline state, and the heating to be effected at 100° for 1-3 hours. Practical injection to be used as a sample for removal of pyrogen are glucose, pyrogenic glucose, fructose, invertose, Ringer solution, sodium alginate, dextran, and sodium citrate. Evaporated tap water was also used as a sample.
    It was thereby found that this treatment was able to reduce pyrogen to the extent undetectable by the modified TBP coloration, i.e. below 0.257γ/cc., in all the samples examined in which the original content of pyrogen was 0.63-7.5γ/cc. calculated as egg albumin.
  • 稲垣 勲, 久田 末雄, 野呂 征男
    1961 年 81 巻 2 号 p. 287-290
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Phloroglucinol derivatives of Extractum Aspidii deposit colloidal precipitate by aqueous cupric acetate in petroleum benzin solution. This reaction can be applied as qualitative test for effective constituents in Aspidium. By this test 111 species of Japanese ferns were examined, in which only Dryopteris genus (24 species) was positive.
  • 北原 一太
    1961 年 81 巻 2 号 p. 291-293
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    An ozonizer was devised in which a lead wire, as the electrode, is passed through the center of an insulator tube, such as glass and synthetic resin tubes, this central electrode is wound with a spiralling insulator so as to make the space between the central electrode and inner wall of the tube uniform. Amount of ozone produced per unit time was compared between this ozonizer and the Siemens tube. It was thereby found that the new apparatus is 1/10 of the Siemens tube in total volume, lower in discharge voltage, about five times greater in electric power per unit discharge area, and the rate is 70% to around 55% in the Siemens tube. Moreover, this new tube is easier to make and a long one of 1-2m. can be made, so that ozone of low to high concentrations can be produced freely.
  • 深間内 久雄, 榎原 竜子, 上原 みつ子
    1961 年 81 巻 2 号 p. 294-296
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Following previously reported iodination of resorcinol and resorcylic acid derivatives, iodination of p-orsellinic acid, one of the carboxylic acids of orcinol, was carried out. For the iodination of p-orsellinic acid, iodine-potassium iodide solution was added at ordinary temperature to the phosphoric acid disodium phosphate solution (pH 2.50) of p-orsellinic acid and the mixture was allowed to stand for two hours. Diiodo-p-orsellinic acid was obtained in quantitative yield as slightly yellowish white crystals, m.p. 179-180° (decomp.). Its diacetate formed white needles, m.p. 157-160° (decomp.). Both these substances are new compounds.
  • 由比 顕之介
    1961 年 81 巻 2 号 p. 297-298
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The conditions under which 3, 5-dibromosalicylaldehyde undergoes coloration with amino acid were examined and the aldehyde was found to be utilizable as a reagent for determination of amino acid. Determination conditions were established for lysine, arginine, serine, and glycine and the determination was carried out on standard amino acid solution. Determinable limit was 5-100γ in neutral and basic amino acids. Acidic amino acids, proline, and hydroxyproline do not undergo this coloration.
  • 万木 庄次郎, 沼田 光雄, 伏見 富吉
    1961 年 81 巻 2 号 p. 299-301
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Methyl 8-formyl-6-oxoöxyoctanoate (III), obtained by application of formic acid to methyl 8-chloro-6-oxoöctanoate (I) or methyl 6-oxo-7-octenoate (II), was submitted to high-pressure reduction, followed by bromination and esterification, to form ethyl 6, 8-dibromoöctanoate (VI). α-Lipoic acid (XI) was prepared by the reaction of alkyl 6, 8-dihaloöctanoate (VI and VII) with sodium trithiocarbonate (VIII).
  • 久田 末雄
    1961 年 81 巻 2 号 p. 301-302
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Phloroglucinol derivative was isolated from ether extract of the rhizome of Dryopteris erythrosora (EAT.) O. KTZE. and it was identified as aspidin. This is the first time that aspidin was isolated from Japanese ferns. Later, aspidin was also isolated from the rhizome of Dryopteris nipponensis KOIDZ., D. fuscipes C. CHR., D. decipiesns (HOOK.) O. KTZE., D. hondoensis KOIDZ., D. championi (BENTH.) C. CHR., and D. kinkiensis KOIDZ.
  • 久田 末雄
    1961 年 81 巻 2 号 p. 303-305
    発行日: 1961/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    A crystalline phlorolucinol derivative was isolated from crude filicin of the ether extract of the rhizome of Dryopteris bissetiana (BAK.) C. CHR. and it was identified as aspidinol. Its yield was 0.17% of the dried rhizome. This substance was also obtained in the same yield from D. pacifica (NAKAI) TAGAWA. The chief component of the ether extract of rhizomes of these two kinds of ferns is considered to be aspidinol but this is the first time that it was found from Japanese ferns. Aspidinol was also obtained from D. sacrosancta KOIDZ. and D. varia (L.) O. KTZE.
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