YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
76 巻 , 1 号
選択された号の論文の35件中1~35を表示しています
  • 奥田 高千代
    1956 年 76 巻 1 号 p. 1-3
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    When boiled in morpholine, the Mannich bases obtained from paraformaldehyde, dimethylaniline hydrochloride, and acetophenones possessing nitro, chlorine, bromine, hydroxyl, methoxyl, or methyl as a substituent in the para-position, or unsubstituted, undergo substitution of the dimethylaxnino group with morpholino group. The yield of the reaction product, when the reaction was carried out under identical conditions, decreased in the order of methyl, methoxyl, unsub-stituted, bromine, chlorine, and nitro compounds.
  • 奥田 高千代
    1956 年 76 巻 1 号 p. 4-6
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    When boiled in pyridine, the Mannich bases obtained from paraformaldehyde, dimethylaniline hydrochloride, and acetophenones possessing nitro, chlorine, bromine, methyl, hydroxyl, or methoxyl as a substituent in the para-position, or unsubstituted, undergo substitution of the dimethylamino group with piperidino group. The yield of the reaction product, when the reaction was carried out under identical conditions, decreased in the order of methoxyl, hydroxyl, methyl, unsubstituted, chlorine, bromine, and nitro compounds. In general, ketonic Mannich bases possessing an electron donor group in the para-position of the benzene ring easily submit to amino exchange reaction but the reaction is difficult where there is an electron attracting group in such a position.
  • 山本 隆一, 高橋 智雄
    1956 年 76 巻 1 号 p. 7-10
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Relativity, if any, between the hygroscopic properties of drugs with moistureproof packaging and atmospheric conditions was examined, and some observations were made on the drugs having critical relative humidity. Results of critical humidity determinations of various drugs by the saturated solution method indicated that the rate of moisture absorption of a drug was alway proportional to the difference between the vapor pressure of the external atmosphere and vapor pressure at the critical humidity of the drug, within a certain range. The same relationship was found to hold for packaged drugs.
  • 大田 正樹, 木本 宏
    1956 年 76 巻 1 号 p. 10-12
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reactivity of the two methyl groups in 2, 5-dimethyl-1, 3, 4-thiadiazole (I) was examined. (I) reacts with benzaldehyde to form a mono- and distyryl derivatives but the methiodide of (I) only forms a mono derivative with benzaldehyde, p-nitrobenzaldehyde, p-dimethylaminobenzaldehyde, or p-nitrosodimethylaniline. Application of bromoacetophenone or p-nitrobromoacetophenone to (I) affords a quaternary base and its treatment with alkali failed to yield the expected thiadiazolylpyrrole derivative, affording crystals assumed from its various properties to be the pseude base.
  • 新谷 茂
    1956 年 76 巻 1 号 p. 13-15
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made as to whether the convulsant effect of 2-methyl-4-amino-5-hydroxymethylpyrimidine (OMP) in mice would be suppressed by the pyridoxines and it was found that the action is suppressed by the subcutaneous injection of a mixture of OMP and a minute amount of the pyridoxine group in intact mice. The suppressive effect became stronger in the order of pyridoxamine, pyridoxine, and pyridoxal, suppressing the action in an amount 1/5, 1/100, and 1/200, respectively, of that of OMP. Pyridoxal showed a 50% inhibitory effect even in 1/500 amount. The effect was observed in pyridoxine even on separate subcutaneous injection during 1 hour before to 30 minutes after administration of OMP, or even by oral administration. Such inhibitory effect was also observed by application on the abdominal skin but only when applied 1 hour before the administration of OMP. It was assumed from the similarity of the structures of the pyridoxine group and OMP that there would be a biological antagonism between these two kinds of substances.
  • 新谷 茂
    1956 年 76 巻 1 号 p. 15-17
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Toxicity increase of OMP by DK feed, discovered by Abderhalden, was observed with synthetic pyridoxine-deficient diet and effect of further addition of pyridoxines was examined. When intact mice are fed synthetic pyridoxine-deficient diet for 1 week, the 50% convulsant dose of OMP becomes about 1/7 that of the mice fed on ordinary diet and the effect becomes greater than in the case of DK diet. Addition of pyridoxines to the deficient diet effects gradual increase of the 50% convulsant dose of OMP, in proportion to the amount added, the effect becoming almost the same as that of DK diet by the addition of 5 γ of pyridoxines per mouse. These effects are also observed by the oral administration of isonicotinic acid hydrazide, but not the increase in the effect by the concurrent use of the deficient diet or rather, the effect of pyridoxine seems to be weakened. Mechanism of the convulsant action of OMP is discussed.
  • 新谷 茂
    1956 年 76 巻 1 号 p. 18-20
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antipyridoxine action of 2-methyl-4-amino-5-hydroxymethylpyrimidine (OMP) was observed in a rat. Feeding of young rats with pyridoxine-deficient diet containing 2-5mg. of OMP per rat results in pyridoxine-deficiency symptoms (acrodynia) in 2-3 weeks with stoppage of growth. Pyridoxine-deficient rat, fed on deficiency diet for 4 weeks, begins normal growth by the administration of pyridoxine but such growth is suppressed when OMP is added to the diet in an amount 200-250 times that of pyridoxine, again showing deficiency symptoms after 3-4 weeks.
  • 新谷 茂
    1956 年 76 巻 1 号 p. 21-23
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Effect of 2-methyl-4-amino-5-hydroxymethylpyrimidine (OMP) on the tryptophan metabolism was observed. It was found that OMP possessed antipyridoxine action characterized by the abnormal metabolism of tryptophan. Xanthurenic acid in the 24-hour urine of a rat administered orally with L-tryptophan was determined by the method of Rosen, Huff, and Perlzweig. Administration of 5mg. of OMP with L-tryptophan to intact mice resulted in the increase of xanthurenic acid in the urine. It was further found that abnormal tryptophan metabolism had occurred in the experimental rat whose growth had been inhibited by the addition of 5mg. of OMP to 25 γ of pyridoxine, as shown in the previous paper.
  • 新谷 茂, 川島 實
    1956 年 76 巻 1 号 p. 23-25
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antipyridoxine action of 2-methyl-4-amino-5-hydroxymethylpyrimidine (OMP) was observed with microörganisms. Growth inhibition of S. carlsbergensis (IFO 0565) in Atkin medium by OMP was examined by turbidimetry and it was found that its minimum inhibitory concentration was 16 γ/cc. when pyridoxine was added to the medium and 400 γ/cc. when such addition was not made. This has made it clear that the growth inhibitory action of OMP is competitively antagonized by pyridoxine in a certain range of concentrations. It was concluded that OMP was responsible for the allergic side-effects caused by the continuous administration of thiamine.
  • 森本 浩, 中守 律夫
    1956 年 76 巻 1 号 p. 26-30
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was shown in the previous paper that β-kainic acid (III) obtained by the so-called “kainic inversion” of α-kainic acid (I) was a stereoisomer of (I) in which the steric configuration of the carboxyl group attached to C2 in the pyrrolidine ring was different from that of (I). Further, it had been shown that α-allokainic acid (IV) was also a stereoisomer of (I) in which the steric configuration of the isopropenyl group alone was different from that in (I). In the present series of experiments, (IV) was submitted to the “kainic inversion” to form β-allokainic acid (VII) which is a stereoisomer of (IV) in which the steric configuration of the carboxyl at C2 in the pyrrolidine ring alone differs from that bf (IV). (VII) so obtained undergoes “retrokainic inversion” to (IV) by high temperatures. (I), (III), (IV), and (VII) are diastereoisomers and constitute four of the eight theoretically possible stereoisomers of kainic acid. The remaining four should be their respective antipodes.
  • 吉岡 一郎, 池田 辰雄, 米谷 晃一
    1956 年 76 巻 1 号 p. 30-33
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    1-Hydroxy-6, 7- and -8, 9-benzophenazines were prepared by the condensation of 1-methoxy-2, 3-phenylenediarine and β-naphthoquinone or by the improved Wohl-Aue reaction followed by denethylation. 2-Methoxy-6, 7- and -8, 9-benzophenazines were also prepared by the improved Wohl-Aue reaction. 1-Hydroxy-6, 7, 8, 9-dibenzophenazine was prepared by the condensation of phenanthrenequinone and 1-hydroxy-2, 3-phenylenediamine.
  • 赤澤 彌三郎, 井上 正敏, 八木 千鶴子, 宮嶋 鼎
    1956 年 76 巻 1 号 p. 33-36
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the discoloration test of activated carbon, the use of titanous solution for the determination of residual methylene blue was examined, and a simple, industrially applicable discoloration test by the use of titanium sesquisulfate Ti2(SO4)3 was devised. This method differs from the Merck method in that the excess Ti3+ is back titrated and the reaction of the colored solution and titanous solution is maintained at 60° to prevent the oxidation of the titanium ion, by which a low concentration of the methylene blue solution could be determined. A calibration curve of the consumption of ammonium ferric sulfate used for the back titration of titanium and the concentration of the methylene blue solution was prepared and its use facilitated calculation of the discoloration rate of the activated carbon. Titanous solution was prepared from high purity sponge titanium by dissolving it in dilute hydrochloric or sulfuric acid in carbon dioxide stream, easily affording a high concentration of titanium chloride or sesquisulfate. The comparatively stable crystals of the sesquisulfate were obtained in a good yield by bringing the sulfate concentration to approximately 50% by the addition of conc. sulfuric acid to the solution of sesquisulfate obtained.
  • 藤田 穆, 廣瀬 良男, 小柳 尚行, 吉廣 由彌
    1956 年 76 巻 1 号 p. 37-40
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Compounds in which the substituted phenyl ring is bonded to undecanoic acid in the ω-position through ether or amine linkage, and another in which the phenyl ring possessing two hydroxyls or one hydroxyl and one methoxyl, is bonded to one of the acid groups in sebacic acid were prepared, as well as several products of the Clemmensen reduction of the latter. Antibacterial tests of these compounds revealed that they possessed antibacterial efficacy toward tubercle bacilli.
  • 朝比奈 菊雄
    1956 年 76 巻 1 号 p. 41-46
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    The present paper describes some observations on the forming pressure in tabletting. With the tabletting machine used in the present series of experiments, in which the lower die is fixed and upper die alone moves, the lower die received the maximum pressure after that received by the upper die during tabletting, the upper die receives negative pressure during its rise, and there is a great difference in the pressure received by the upper and lower dies. The difference in the pressure received by the tablet itself is far smaller but the tablet swells somewhat when the tabletting pressure is removed. It was found that the higher the forming pressure and shorter the time in which the forming pressure is applied, the longer it took for disintegration of the tablets.
  • 朝比奈 菊雄
    1956 年 76 巻 1 号 p. 47-49
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the variation of tablet weights in one lot and it was concluded that the difference in the volume of the die was the largest cause of the variation. The next great cause for the variation seemed to be the accidental error, while that due to the passage of time seemed far smaller than was expected. There was, however, no tendency for the variation to increase with prolongation of working time. Variation coefficients obtained were about 3.1 for the total variation, 2.4 for that by the dies, 0.7 for that by passage of time, and 1.9 for that by accidental error.
  • 鹿島 哲, 加納 宏一郎
    1956 年 76 巻 1 号 p. 50-53
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    The effect of the combined acid on the direct titration of the salts of organic bases and inorganic or organic acids with perchioric acid in glacial acetic acid was comparatively examined by the titration curves obtained by the potentiometric titration of the salt of diphenhydramine and various acids with glass-calomel electrode. It was thereby found that the order of the strength of the acids in glacial acetic acid was almost equal to their strength in aqueous solution. It may be concluded that weak acids with dissociation constants below 10-3 would be almost without effect on the titration but stronger acids would lower the measurement accuracy.
  • 富永 敏夫, 仲田 富士徳
    1956 年 76 巻 1 号 p. 54-56
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Paper chromatography of the glycoside A from Engelhardtia formosana with 20% methanol as the developing solvent gives two spots (cf. Table I). Isolation of the two substances was attempted by the chromatopile method by which they were separated into engelitin (I) and kaempferol 3-L-rhamnoside (II) as yellow plates, m.p. 172-174°, C21H20O10⋅2H2O, which agreed with the properties of afzelin except for the water of crystallization. Recrystallization of a mixture of (I) and (II) afforded a substance completely identical with the glycoside A, which was thereby confirmed as a mixed crystal.
  • 高橋 酉藏, 堀 幹夫, 鶴羽 肇
    1956 年 76 巻 1 号 p. 56-60
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    A series of 1-alkyl (or aryl)-2-dialkylaminocyclohexanones (III to X) were prepared by the reaction of the Grignard reagents of methyl, ethyl, propyl, butyl, benzyl, and phenyl halides with 2-dialkylaminocyclohexanones (I and II) obtained from 2-halocyclohexanone and dialkylamines. (X) gives 1-phenyl-1-benzoyloxy-2-dimethylaminocyclohexane hydrochloride (XI) on the application of benzoyl chloride but (IV), (VI), and (VII) only afford their own hydrochlorides. Treatment of (X) with formic acid or dry hydrogen chloride gas affords 1-phenyl-2-dimethylaminocyclohex-1- or -6-ene (XII). The use of sodium as the condensation agent in the reaction of 2-ethoxycarbonylcylohexanone and dialkylamino-ethyl chloride gives 2-β-dialkylaminoethyl-2-ethoxycarbonylcyclohexanones (XI and XII). Further treatment of these with barium hydroxide to 2-β-dialkyl-aminoethylcyclohexanones (XIII and XIV) and application of the Grignard reagents of methyl, ethyl, butyl, and phenyl halides afford the corresponding 2-β-dialkyl-aminoethyl-1-alkyl (or aryl) cyclohexanols (XV to XXI).
  • 桶田 秀雄, 谷口 幹二, 榎 吉二, 谷口 卓藏, 加治 有恒, 阿部 一夫, 先本 礼二
    1956 年 76 巻 1 号 p. 60-62
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new synthetic method for sulfisoxazole (VI), starting with methyl ethyl ketone (VII), was established and the present paper reports the course leading to the intermediate α-acetylpropionitrile (III). Chlorination of methyl ethyl ketone (VII) by the passage of chlorine gas through the hydrochloric acid solution of (VII) at a low temperature gives methyl α-chloroethyl ketone (VIII) in far smoother and faster rate than the existing method, with twice the reaction rate. Application of alkali cyanide to (VIII) affords α, β-dimethylglycidonitrile (IX) which undergoes conversion to α-acetylpropionitrile (III) on heating with alkali cyanides, carbonates, hydrogen carbonates, alkali earth hydroxides, or pyridine.
  • 桶田 秀雄, 谷口 幹二, 谷口 卓藏, 加治 有恒
    1956 年 76 巻 1 号 p. 63-66
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    On heating with sodium cyanide in aqueous or ethanolic solution α, β-dimethyl-glycidonitrile (I) affords α-acetylpropionitrile. In order to elucidate this reaction mechanism α-ethyl-β-methylglycidonitrile (VI) was boiled with sodium cyanide in aqueous solution and only 2-cyanopentan-3-one (VIII) was obtained and not its isomer, 3-cyanopentan-2-one (VII). (I) was boiled with a labelled sodium cyanide, Na14CN, in aqueous or methanolic solution and a radioactive α-acetylpropionitrile (IX) was obtained. The specific activity of its 2, 4-dinitrophenylhydrazone (X) was equal to that of Na14CN used as the starting material. From these facts, the mechanism of this reaction was clarified to be the initial addition of sodium cyanide to (I) to form cyanohydrin of (II) which underwent decomposition to form (II), and not the rearrangement of a proton or -CN group of (I).
  • 桶田 秀雄, 谷口 幹二, 榎 吉二, 山田 幸元, 荒木 正雄
    1956 年 76 巻 1 号 p. 66-69
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Imidoetherification of α-acetylpropionitrile (I) with carbon tetrachloride in solvents other than ether afforded propioimido ether hydrochloride (II) which formed α-acetylpropioimido ether (III) with cold alkali and α-methylacetoacetic ester (VI) with dilute mineral acids or water. (III) reverted to (II) on application of hydrochloric acid gas, to (VI) by mineral acids or ammonium chloride, and to (I) with alkali. (III) formed 3, 4-dimethyl-5-aminoisoxazole (VIII) and 1-carbamido-3, 4-dimethyl-5-aminopyrazole (VII) by the respective action of hydroxylamine or semicarbazide hydrochloride. In general, imido ethers form amidines by ammonia but (II) and (III) failed to form amidines by ammonia but formed substances of m. p. 170° and 200°, respectively. (I) easily formed an unstable substance assumed to be α-acetylpropioimide hydrochloride (IV) by hydrochloric acid gas and (IV) formed (II) on the addition of ethanol. These facts suggest that the formation of (II) from (I) occurs through the intermediate formation of (IV) and (III). In accordance with this theory, imidoetherification and neutralization of α, β-dimethylglycidonitrile (XI) was carried out from which a substance corresponding to β-chloro-α-hydroxy-α-methylbutyroimido ether (XIV) was obtaind through its hydrochloride (XIII).
  • 川城 巖
    1956 年 76 巻 1 号 p. 70-73
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Contrary to expectations, p-nitro-N-methylaniline-N-glucoside consumed 5 moles of periodic acid in oxidation. Since α-amino alcohol, which does not possess free hydrogen in the nitrogen, does not react with periodic acid, the foregoing result was assumed to be due to a secondary reaction by the clialdehyde compound, the primary oxidation product, which had received hydrolysis and consumed more periodic acid than was expected. This was proved by the comparison of the rate of periodic acid consumption and of hydrolysis in piperidine-N-glucosioe 3, 4, 6-triacetate. These facts suggested that it would be impossible to make structural determination of the lactol ring in arylamine-N-glucosides by periodic acid oxidation.
  • 石館 守三, 橋本 嘉幸
    1956 年 76 巻 1 号 p. 73-77
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction of mercaptoacetamide or cysteine with trans-π-oxocamphor, a respiratory and cardiac stimulant, was studied together with comparative examination with some other aliphatic and aromatic aldehydes. trans-π-Oxocamphor, 10-oxocamphor, formaldehyde, and acetaldehyde mixed with mercaptoacetamide in their alcoholic solution gave 2-substituted thiazolidone derivatives (formula C) under dehydrative ring formation. On the other hand, the aromatic aldehydes, benzaldehyde, p-nitrobenzaldehyde, and p-dimethylaminobenzaldehyde, under the same mild conditions, formed only hemimercaptal compounds (formula A), which were however transformed into the corresponding thiazolidones on treatment with anhydrous zinc chloride. 2-(trans-π-Apocamphoryl)-4-carboxythiazolidine (XI) obtained from d-trans-π-oxocamphor and l-cysteine considerably dissociates in the aqueous solution into its components, and no noticeable formation of the addition product was observed in the solution of 2×10-4 M of both components (Fig. 2).
  • 武田 健一, 徳山 幹治
    1956 年 76 巻 1 号 p. 77-79
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of nitriles of acetonitrile and benzonitrile series with alkali hydroxides was carried out in liquid ammonia. It was thereby found that the reaction occured either with the active hydrogen or with the nitrite in accordance with the strength of the reactivity or the presence or absence of the hydrogen attached to the α-carbon of the nitrile. The alkali hydroxide had been considered to be present as a salt but it is assumed that the reaction took place because the alkali hydroxides in liquid ammonia underwent dissociation at higher temperatures.
  • 徳山 幹治
    1956 年 76 巻 1 号 p. 80-82
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    When diphenyl ethers or anisole possessing a nitro group in the ortho- or para-position is reacted with alkali hydroxides in liquid ammonia, they undergo cleavage to a phenol. This may be considered an anionoid substitution with a hydroxyl anion and may indicate the dissociation of alkali hydroxides in liquid ammonia to be a fact. On the other hand, cleavage of anisole to a certain extent suggests that alkali hydroxides act as a catalyst to cause reductive cleavage and such a possibility is further furnished by the formation of an amine compound during the cleavage of o- or p-nitroanisole but not in the case of anisole.
  • 伊藤 四十二, 青沼 繁, 瀧川 泱男, 篠田 雅人
    1956 年 76 巻 1 号 p. 83-86
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    A substance was obtained from a bovine submaxillary gland, designated as S-parotin, which lowered the serum calcium level in rabbits. S-Parotin (purity: 93.8%) was found to be very similar to parotid in its ultraviolet absorption maxima, polarogram, changes in the circulating leucocyte counts, and calcium deposition in the rabbit dentin.
  • 伊藤 四十二, 青沼 繁
    1956 年 76 巻 1 号 p. 87-91
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Physiological saline, ether, acid ethanolic extracts, and an extract by the Best method were prepared from bovine submaxllary gland but none possessed the action of lowering blood sugar level in a rabbit. The pH 4.5-precipitate, and the fractions which lowered the serum phosphate level and serum calcium level, all obtained from the bovine submaxillary gland were devoid of the action of lowering blood sugar level in rabbits by intravenous injection, as in the case of parotin. The fraction which lowers serum phosphate level in rabbits significantly increased the blood sugar level at a 5% danger rate by subcutaneous injection.
  • 青沼 繁
    1956 年 76 巻 1 号 p. 91-94
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Equine submaxillary gland also afforded a substance, as the bovine gland, which lowered the serum calcium and inorganic phosphate level in rabbits. Precipitates at pH 5.4 and 4.5 were obtained by dilute alkali extraction of the equine submaxillary gland and were submitted to fractional precipitation with ammonium sulfate. The principle which lowers rabbit serum calcium level was obtained in the fraction of 12.5% ammonium sulfate from the pH 5.4-precipitate, while the principle effective for the serum phosphate was obtained from the fraction of 25% ammonium sulfate from the pH 4.5-precipitate.
  • 安江 政一
    1956 年 76 巻 1 号 p. 95-98
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    R-CO-COOH (II), obtained by the oxidation of R-CH (OH)-COOH (I), (R=5-acetamino-2-methylphenyl) gives R-CN (IV) on application of hydroxylamine on heating, and an oxime (III) at room temperature. The semicarbazone is stable and can be recrystallized from water. The hydrolysis product (V) of (II) possesses securely bound water of hydration and its dehydration results in the formation of a condensate, (C8H7N)xH2O (VI), which is soluble in organic solvents, insoluble in alkalis, and soluble in acids. When its hydrochloric acid solution is basified, a substance soluble in ether is obtained but attempted recrystallization causes reversion to (VI). Application of acetic anhydride to the ether solution gives R-CHO (VII) which is also obtained on warming (I) and conc. sulfuric acid at 40°. The crude acid (II) containing chlorine forms R-CH (NH2)-COOH (IX) on the application of ammonia but the product returns to (I) by the action of nitrous acid. (IX) gives a hydrolysis product (X) of m. p. 210° (decomp.), and an oxidation product of m. p. 242° (decomp.). It is certain, therefore, that R-CHCl-COOH (VIII) is present in the crude acid. It is assumed that (VIII) alone was present during the reaction and formed (I) by hydrolysis during the procedure. Another acid obtained must be R2CH-COOH (XI), which was confirmed by synthesis from (I) and RH. Liberation of nitrogen from (XI) gave di (o-tolyl) acetic acid (XII) which was also obtained from o-tolyl iodide and methyl formate.
  • 名川 方敏, 進藤 英世
    1956 年 76 巻 1 号 p. 99-100
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Determination of chloramphenicol was effected by heating it with 4% hydrochloric acid for 1 hour in a boiling water bath to decompose it completely to the l-base and determined by azotometry using the principles of the Van Slyke method. Good results were obtained by the use of saturated saline solution for the sealing, supply, and washing solutions. The minimum determinable range was up to 50 γ of chloramphenicol and the determination was found possible up to 20 γ of chloramphenicol with a slight error.
  • 名川 方敏, 進藤 英世
    1956 年 76 巻 1 号 p. 101-102
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Determination of penicillin was attempted by warming penicillin with N sodium hydroxide, acidified with 5% hydrochloric acid, heated for 1 hour in a boiling water bath to quantitatively liberate the two primary amino groups, which were determined by azotometry using the principles of Van Slyke method, The minimum determinable range is up to 30 γ of penicillin G-K in 1cc. of the final test solution.
  • 橋本 徳二
    1956 年 76 巻 1 号 p. 103-104
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    The product (II) obtained by the reaction of 3-acetamrnohydrocarbostyril (I) and chlorosulfonic acid at 50° was converted to the 6-sulfonamide (III) of (I) by ammonia and to 6-sulfonic acid (V) by boiling it with a large amount of water. Both (III) and (V) were deacetylated with dilute acids to the 3-amino compounds (IV) and (VI). The substituent position was confirmed by the oxidation of (III) with potassium permanganate, boiling with 5% sodium hydroxide, followed by diazotization and decomposition with water to 5-sulfonamidosalicylic acid. Animal tests with the hydrochloride of (IV) and sodium salt of (VI) revealed that neither of them possessed pharmacodynamic action of amyostatic poisons in mice.
  • 橋本 徳二
    1956 年 76 巻 1 号 p. 105-106
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    6-Iodo-3-aminohydrocarbostyril (II) was prepared from 3-acetaminohydrocarbostyril by the application of iodine monochloride to its glacial acetic acid solution to form (I) which was deacetylated with dilute hydriodic acid. The position of the iodine in (II) was confirmed by oxidation with potassium permanganate followed by boiling with N sodium hydroxide to 5-iodoanthranilic acid. Administration of the aqueous solution of the hydrochloride of (II) to mice showed that it possessed the pharmacodynamic action of amyostatic poison, almost similar to that of 3-aminohydrocarbostyril.
  • 安江 政一
    1956 年 76 巻 1 号 p. 106-108
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of 0.5 equivalent of methyl formate to diphenylcarbinolmagnesium iodide formed by the Grignard reaction results in the formation of diphenylmethyl ether, (C6H5)2CH-O-CH(C6H5)2. Use of an excess of methyl formate affords diphenylmethyl iodide, which was proved indirectly by the formation of sym-tetraphenylethane with magnesium. Formation of diarylacetic acid from the diarylmethyl iodide here formed was attempted. Application of magnesium would give a hydrocarbon and will not form a Grignard reagent. Therefore, carbon dioxide gas was passed through during the addition of magnesium and the objective acid was obtained in a small amount.
  • 醍醐 晧二
    1956 年 76 巻 1 号 p. 109-110
    発行日: 1956/01/25
    公開日: 2010/02/19
    ジャーナル フリー
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