著者
市川 正孝 高木 康 一番ケ瀬 尚
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.768-771, 1961-05-25 (Released:2010-02-19)
参考文献数
4

Nitration of ethyl 8-hydroxycoumarin-3-carboxylate (I) in glacial acetic acid solution affords ethyl 5-nitro-8-hydroxycoumari-3-carboxylate (III), m.p. 203.5-204°, and ethyl 7-nitro-8-hydroxycoumarin-3-carboxylate (IV), m.p. 201-202°. Methylation of (III) and (IV) with methyl iodide respectively gives 8-methoxy compounds, (VII) of m.p. 184-186°, and (VIII) of m.p. 152°, respectively. On the other hand, nitration of 3-methoxy-salicylaldehyde acetate (XVI) affords 4-nitro (IX), m.p. 92-93°, 5-nitro (X), m.p. 142°, and 6-nitro (XI), m.p. 104°, compounds. By condensation of (IX) and (XI) with ethyl malonate, in the presence of piperidine, the position of the nitro group in the foregoing (III) and (IV) was determined.Hydrolysis of (I), (III), and (IV) with hydrochloric acid respectively afforded 8-hydroxycoumarin-3-carboxylic acid, m.p. 292-293° (decomp.), 5-nitro-8-hydroxycoumarin-3-carboxylic acid, m.p. 292-293° (decomp.), 5-nitro-8-hydroxycoumarin-3-carboxylic acid (V), 257-258°, and 7-nitro-8-hydroxycoumarin-3-carboxylic acid (VI), m.p. 246-248°.
著者
桑野 晴光 田村 千尋
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.764-767, 1961-05-25 (Released:2010-02-19)
参考文献数
5
被引用文献数
2 2

Polymorphism of chloramphenicol was examined by the X-ray diffraction method and quantitative relationship between the two crystal forms was examined. In general, proportionation of concentration to diffraction intensity can be quantitated in polymorphs but the method was inconvenient for use with organic compounds due to strict packing conditions. In the binary system (α- and β-forms) of chloramphenicol palmitate, specific intensity and specific concentration of the component were in proportion and quantitative straight line independent of packing codition was obtained. This was found to be effective in the range of over 3% of the β-form and precision is within 1%. As the quantitative linear equation: the following was obtained: xβ/xα=(0.347±0.005)⋅Iβ/Iα, where x is the concentration of the component and I is the intensity of reflection.
著者
田村 千尋 桑野 晴光
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.759-764, 1961-05-25 (Released:2010-02-19)
参考文献数
6
被引用文献数
1 1

From the consideration of X-ray diffraction, infrared absorption spectra, and various transition conditions of long-chain esters of chloramphenicol, and some assumptions were made on their crystal structure.1) According to X-ray diffraction, all-trans configuration for the long-chain portion of the β-form molecule results in good agreement between the molecular models and the long axis by X-ray measurement. In the case of α-form, the long axis of the crystal cannot be explained unless the molecule is assumed to have some cis linkages or the long chain part is a trans structure but deeply twined with each other.2) Infrared absorption spectra suggest that the α-form is closely resembled to a solution state and crystals with a cis configuration, having distorted molecule, may be assumed. The β-form is considered to have a higher order molecular arrangement as a crystal and it is convenient to assume an all-trans configuration by X-ray measurement.3) Stability of the β-form can be assumed form the measurement of melting point and specific gravity. On the other hand, similarity to the α-form and solution state (or amorphous state) as found from transition conditions and these agree well with the above two measurements.
著者
田村 千尋 桑野 晴光
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.755-759, 1961-05-25 (Released:2010-02-19)
参考文献数
6
被引用文献数
13 19

It was found that chloramphenicol palmitate, myristate, and caprylate come in two kinds of crystalline form and one amorphous form. These compounds were prepared and their transition conditions were examined.1) When the crystals is dissolved in a solvent and crystallized out, optional form of crystals can be obtained by controlling crystallization rate and this form is not affected by polarity or pH of the solvent. Crystals of α-form is obtained by rapid crystallization while the β-form is obtained by gradual crystallization. When a small amount is fused and cooled rapidly in a refrigerator, a vitrious substance is obtained.2) Transition between the solids occur only in the direction of amorphous to α-form to β-form, and there is no reverse progress. The transition rate is faster, the nearer the melting point. The mechanism of such a transition is thought to be the transition to a stable form by the heat motion of the molecule itself. The transition rate becomes suddenly rapid after formation of β-form crystal and this is considered to be due to added effect of catalytic transition.
著者
関口 慶二
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.664-669, 1961-05-25 (Released:2010-02-19)
参考文献数
9

Solubilizing action of the sodium salt of benzoic acid, o-, m-, and p-hydroxy-, methoxy-, amino-, nitro-, and chloro-benzoic acid, and nicotinic acid on caffeine was determined and the effect of the kind and position on the solubilization was examined. The solubilizing action was found to be in the descending order, in molar equivalent of the salt, of salicylate≅m-chloro-, p-chloro-, m-hydroxy-≅p-hydroxy-≅m-methoxy-≅p-methoxy-, m-nitro-, p-nitro-, o-amino-, and p-amino-benzoate, benzoate, m-aminobenzoate, nicotinate, and o-chloro-, o-methoxy-, and o-nitro-benzoate. The solubilizing action of these benzoates is assumed to be not due to formation of a complex of established composition but due to the formation of a hydrogen bond between caffeine and benzoate, with the water molecule of the solvent acting as the hydrogen-bond donor.
著者
掛見 喜一郎 有田 隆一 大橋 貞
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.748-750, 1961-05-25 (Released:2010-02-19)
参考文献数
2
被引用文献数
1 1

Potency determination of kanamycin solution was carried out as follows: To 5cc. of kanamycin solution in water, 0.5cc. of 20% sodium carbonate solution is added, followed by 0.5cc. of 1% solution of sodium 1, 2-naphthoquinone-4-sulfonate with cooling in ice water, and the mixture is allowed to stand at 0° to 2° for 20 minutes, protected from light. To this solution, 1.0cc. of acetone and 0.5cc. of 50% acetic acid are added and optical density of this solution, is measured at 420 mμ. As a control, the same procedure is carried out with distilled water in place of the sample solution. The potency of the sample solution is read from the calibration curve prepared with kanamycin of known potency.The same determination was carried on samples boiled with acid or alkali, and samples left at various temperatures. Comparison of the values so obtained with the values determined by the cup method, stipulated in the antibiotics standard, showed good agreement.
著者
加瀬 佳年 由井薗 倫一
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.740-747, 1961-05-25 (Released:2010-02-19)
参考文献数
30
被引用文献数
3

The pharmacology of d-N, N, 1-trimethyl-3-(ethylsulfonyl)-3, 3-diphenylpropylamine hydrochloride (A-5) was described in detail. A-5 showed a long-acting antitussive activity, duration of the effect being 18.9 times that of codeine (intravenous) and 13.5 times that of codeine (oral), though 50% antitussive dose is only 1.4 and 1.7 times that of codeine in dogs and cats, respectively. The site of action seemed to be the cough center per se. Toxicity in mice (subcutaneous) is 1.5 times that of codeine and 30% that of Methadone. No tendency to establish tolerance, cumulative action, or addiction liability was found by long-term administration. Analgesic action and other actions were discussed.
著者
堀川 諭 Satoru Horikawa
出版者
大手前大学
雑誌
大手前大学社会文化学部論集 = Otemae journal of socio-cultural studies (ISSN:13462113)
巻号頁・発行日
vol.1, pp.21-33, 2000-03-25

日々報道される少年事件の背景はさまざまであり、一様に論ずることができないことはいうまでもない。また、少年法の規制の中でわれわれの知りうる情報はきわめて限られたものであるから、個々の事件をあれこれ論ずることには慎議でなければならない。しかし、こうした少年事件にしばしば衝動的で短絡的なクレッチマーのいう「短絡反応」(short circuit reaction) ともいえる心珊機制がみられることも事実である。そこで、この小文では、少年による短絡反応の事例と考えられるニつの有名な事件、一つは、事件後三百数十年もの問語り継がれてきた「八百燦お七」の物語、いま一つは、昨今の短絡的な少年事件の現代的嚆矢ともいえる高島忠夫氏氏長男の「道夫ちゃん事件」を取り上げ、それに若干の精神病理学的な検討を加えた。いみじくも両者はともに17 歳の少年による犯行であり、前者はわが国を代表する古典作品として怯承され、後者は報道規制の緩やかであった時代の、それゆえ比較的詳細に事件の本質に迫ることのできる事件として興味深いものがある。
著者
角 保男
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.652-655, 1961-05-25 (Released:2010-02-19)
参考文献数
5

Leucoriboflavin 5′-phosphate derivatives were prepared by reductive acylation of riboflavin 5′-phosphate. These compounds were rather unstable and were easily hydrolyzed to riboflavin 5′-phosphate derivatives, regaining the yellow color. On heating with 17% hydrochloric acid, leucoriboflavin 5′-phosphate tetraacetate and monoethylformate yielded riboflavin 2′, 5′-anhydride, m.p. 300-302°. This substance was sensitive to light and formed lumichrome as the photo-decomposition product on exposure to light.
著者
角 保男
出版者
公益社団法人 日本薬学会
雑誌
YAKUGAKU ZASSHI (ISSN:00316903)
巻号頁・発行日
vol.81, no.5, pp.647-651, 1961-05-25 (Released:2010-02-19)
参考文献数
3

Leucoriboflavin, reduced form of riboflavin, is easily oxidized to riboflavin when shaken with air. To retain the leuco state, riboflavin was reduced with sodium dithionite or with zinc in acid solution to the leuco compound and its acylation with acetic anhydride or benzoyl chloride gave leucoriboflavin acylate. These compounds were stable in solid state but were easily decomposed to riboflavin acylate on exposure to sunlight or by heating, regaining the yellow color. Several decomposition products of leucoriboflavin acylate are described.
著者
室伏 良信 木村 美佐子 桑野 晴光 飯島 康輝 山崎 光郎 金子 正勝
出版者
公益社団法人日本薬学会
雑誌
Chemical & pharmaceutical bulletin (ISSN:00092363)
巻号頁・発行日
vol.36, no.10, pp.3760-3769, 1988-10-25

Addition reactions of the C^<4′>-C^<5′> double bond of griseolic acid were investigated. C^<4′>-C^<5′>Dihydrogrisiolic acid was obtained by reduction of the adduct having halogen at the 4′-position.The ring juncture of the two five-membered rings of the C^<4′>-C^<5′> dihydro derivaticves was of all-"cis"configuration. Acetolysis of the protected dihydrogriseolic acid gave the corresponding 1′-acetoxy sugar derivative. Reaction of this sugar derivative with silylated bases gave guanine and uracil derivatives of the dihydrogriseolic acid. The cyclic nucleotide phosphodiesterase (PDE)-inhibitory activity of the C^<4′>-C^<5′> cis dihydrogriseolic acid derivative was weaker than that of griseolic acid.The uracil derivative of C^<4′>-C^<5′> cis dihydrogriseolic acid completely lost the inhibitory activity against both adenosine 3′, 5′-cyclic monophosphate (cAMP) and guanosine 3′, 5′-cyclic monophosphate (cGMP) PDE, whereas the guanine derivative showed reduced inhibitory activity against cAMP PDE, but retained its activity against cGMP PDE. It was also apparent that the C^<4′>-C^<5′>trans dihydro derivative which was obtained as a minor product from the same culture broth of griseolic acid had almost the same inhibitory activity as griseolic acid.
著者
金子 正勝
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.49, no.11, pp.989-1001, 1991
被引用文献数
8

Recent development in the synthetic chemistry of the antitumor antimetabolites of nucleic acid related compounds has been reviewed. In addition to the methodology of the synthesis of antimetabolites from the point of synthetic chemistry, the antitumor activities and the mechanisms of them have also been mentioned.