巻号一覧
102 巻, 2 号
選択された号の論文の13件中1～13を表示しています
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首藤 紘一1982 年 102 巻 2 号 p. 111-126
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーN-Arylhydroxylamines react with benzene in the presence of an acid. In the presence of trifluoroacetic acid (TFA), the reaction center is the nitrogen atom and nucleophilic attack by benzene proceeds at the nitrogen atom of the O-protonated N-phenylhydroxylamine. When TFA was replaced by trifluoromethanesulfonic acid (TFSA), the major products were aminobiphenyls. Together with the results obtained in the reaction of N, N-dimethylaniline N-oxide, it was demonstrated that the reactive intermediates are onium-benzenium ions which easily react with benzene and other aromatic compounds. Various iminium-benzenium ions were posturated in the reaction of nitroso-, azo-, azoxy-, and even nitrobenzenes with benzene. 1-Nitronaphthalene gave 1-(N, N-dihydroxyiminium)-benzenium ion in TFSA. The acid-catalyzed solvolytic reaction of O-aryl-N-acyl-or-N-sulfonylhydroxylamines formed highly delocalyzed phenoxenium ions, which react with nucleophiles such as benzene, phenol, anisole, alcohols, thiol, acetic acid, and acetonitrile. A few examples of synthetic application of these reactions were demonstrated : dibenzoazepines, aporysopine, aporphines, pyridocarbazole, orchinol and loroglossol were synthesized.抄録全体を表示PDF形式でダウンロード (1107K) -
北河 修治, 中垣 正幸1982 年 102 巻 2 号 p. 127-136
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーIn a mixed electrolyte solution, an ion can display characteristic transport phenomenon such as reverse permeation and overshooting under certain conditions, as we have already revealed theoretically and experimentally. In this report, we resolved the equation on ionic flux by approximating the distribution of ions in the membrane to be linear, and calculated ionic concentration change accompanied with membrane permeation by computer approximation. And we compared the estimation values with the experimental values about cellulose membrane for HCl-KCl-H2O and HCl-CaCl2-H2O ternary systems. As a result, these values almost agreed with each other, and could explain reverse permeation and overshooting phenomenon fairly well. About reverse permeation, as we also revealed by computer estimation, it proceeds remarkably when the concentration of the objective ion is low, and it proceeds rapidly and remarkably when the mobility of the objective ion is large. About overshooting, it proceeds rapidly and remarkably when the concentration of the objective ion is low or the difference of the mobilities of coexisting ions is large.抄録全体を表示PDF形式でダウンロード (857K) -
嶋林 三郎, 田村 知津子, 中垣 正幸1982 年 102 巻 2 号 p. 137-142
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーAdsorption of cetylpyridinium chloride (CPC) to hydroxyapatite (HAP) was studied. The amount of adsorbed CPC increased and decreased with the amount of added NaOH, and added NaCl or CaCl2, respectively. It was assumed that cetylpyridinium cation (CP+) is adsorbed to negatively charged sites on HAP surface by electrostatic force. Adsorption of anions such as OH- makes the number of adsorption sites for CP+ increase on the surface of HAP (cooperative adsorption). But the effect of Cl- anion, which may increase the amount of CP+ adsorption, was assumed to be smaller than that of Na+ cation, which decreases the amount of CP+ adsorption, because NaCl, as a whole, inhibits CP+ adsorption. Cations such as Na+ and Ca2+ compete with CP+ for the adsorption site charged negatively on HAP (competitive adsorption). The effect of Ca2+ was more remarkable than that of Na+, since Ca2+ is one of the lattice ions of HAP crystal. As the affinity of Ca2+ to HAP is stronger than that of CP+, the adsorption isotherm of Ca2+ became just one curve irrespective of concentration of CP+ added. The fact mentioned above may be one of the reasons why hard tissues and renal calculi adsorb Ca2+ selectively from body fluid containing many kinds of organic and inorganic ions, and grow up in our human body.抄録全体を表示PDF形式でダウンロード (632K) -
古家 義朗, 伊藤 和夫, 栗原 一郎, 上岡 龍一, 谷口 敏夫, 小杉 善雄1982 年 102 巻 2 号 p. 143-152
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーThe acid-catalyzed reversible etherification of the allelotrope of p-nitrosophenol (PNP) with ethanol in dioxane was studied kinetically togather with its reverse reaction, the acid-catalyzed reversible hydrolysis of p-nitrosophenetole (PNPT) in dioxane. Both reactions have another rate equation at more or less than 0.4 M water as follows : In the case of CH2O⪈0.4M and CH2SO4=0.1N ; Rateforward=(k2-kf-3hCH2O+k3CPNP)CPNPCEtOH Ratereverse=(k-2-kf3hCH2O+k-3CPNPT)CPNPTCH2O In the case of CH2O≨0.4 M and CH2SO4=0.1N ; Rate'forward={k2-0.4kf-3h+kf3h(CH2O-0.4)+k3CPNP-k-4hCPNP(CH2O-0.4)}CPNPCEtOH Rate'reverse={k-2-0.4kr3h+kr-3h(CH2O-0.4)+k3CPNPT-k4hCPNPT(CH2O-0.4)}CPNPTCH2O When the concentration of water is constant, the rate equation of the forward reaction was simplified in the following way. Rateforward=(k2'+k3'CPNP)CPNPCEtOH Isotope Effects on these rate constants were k2'H/k2'D=0.83 and k3'H/k3'D=2.58, respectively. Apparent activation parameters, ΔEa and ΔS&bne; were obtained to be 2.1 kcal/mol, -72.4 e.u. for the forward reaction expressed by k2' and 27.0 kcal/mol, 4.4 e.u. for the forward one expressed by k3', respectively. Nucleophilic attack of oxygen atom of ethanol on the ring carbon attached to hydroxyl group of the allelotrope, is discussed as a probable mechanism.抄録全体を表示PDF形式でダウンロード (716K) -
高野 誠一, 伊藤 文隆, 小笠原 国郎1982 年 102 巻 2 号 p. 153-161
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーDiels-Alder reaction between furan derivatives (1, 15a-d, and 21) and dienophiles (2 and 14) was examined with the intention of constructing the non-tryptamine moiety of yohimbine.抄録全体を表示PDF形式でダウンロード (937K) -
大塚 紘司, 藤岡 章二, 小宮 威彌, 水田 栄治, 高本 正幸1982 年 102 巻 2 号 p. 162-172
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーThe crude drug"Cinnamomi Cortex"the bark of Cinnamomum cassia BLUME and other plants of the same genus (Lauraceae) is well described in herbals or medicinal books of Chinese medicine, and has been used medicinally from old times. This important crude drug is clinically prescribed for sweating, anti-pyretic, and analgesic effects in many Chinese medicine and widely used for aromatic stomachics as folk remedy or spice in the world. In the course of search for active anti-inflammatory constituents in the crude drugs and plants, an aqueous methanolic (1 : 1, v/v) extract from the bark of Cinnamomum sieboldii MEISSN. was found to have the potent inhibitory activity of the formation of granulation tissue through the screening by the fertile egg method. Exploration on the bark of this plant resulted in the isolation of the known (-)-epicatechin (1), (+)-catechin (2), procyanidin B2 (5), and procyanidin B4 (6), and new compounds named cinnamonol D1 (9), and cinnamonol D2 (10) as their acetates, respectively. The activity increased in the order of monomers, dimers, and trimers.抄録全体を表示PDF形式でダウンロード (1015K) -
亀谷 哲治, 気賀沢 和雄, 柊木 峯治, 我妻 永利, 小萩沢 利孝, 瓜生 恒夫, 中村 俊久1982 年 102 巻 2 号 p. 173-181
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーWith the expectation of the synthesis of the compounds having both agonist and antagonist properties, novel decahydrocinnoline derivatives (IIa-i), (IIIa-g) and (IVa-f) were synthesized as analgetics. In order to prepare N-2-propenyl derivatives, the reduction of N-acryloyl compounds (IIf) and (IIg) with various reducing agents (lithium aluminum hydride, sodium borohydride and sodium bis (2-methoxyethoxy) aluminum hydride was examined. In addition, it was found that N-acryloyl derivative (IIf) cyclized to give 2, 3, 4, 5, 6, 6a, 7, 8, 9, 10, 10a, 11-dodecahydro-1H-pyrazolo [1, 2-a] cinnoline derivative (VII) by heating with phosphorus pentasulfide and potassium sulfide in xylene. Among these decahydrocinnoline derivatives (IVa), (IVb) and (IVc) were found to have a potent analgesic effect with antagonistic effect for morphine analgesia.抄録全体を表示PDF形式でダウンロード (758K) -
石井 永, 陳 益昇, 赤池 美砂子, 石川 勉, 盧 盛徳1982 年 102 巻 2 号 p. 182-195
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーChemical constituents of the root wood of X. integrifoliolum (MERR.) MERR. (F. integrifoliola MERR.), Rutaceae, were examined. Two new alkaloids, integriamide (25), mp 302-304°C, and integriquinolone (43), mp 257-260°C, were isolated with ten known alkaloids [Dictamnine (7), skimmianine (11), 4-methoxy-1-methyl-2-quinolone (12), arnottianamide (13), haplopine (14), rutaecarpine (16), (+)-platydesmine (29), myrtopsine (30), α-allocryptopine (32), and robustine (33)]. Other than alkaloids four known coumarins [6, 7, 8-trimethoxycoumarin (8), 5, 6, 7-trimethoxycoumarin (9), aesculetin dimethyl ether (10), and fraxinol (19)], and six known components [acid mixture, lupeol (5), β-sitosterol (6), d-sesamin (15), dl-syringaresinol (34), and 2, 6-dimethoxy-p-benzoquinone (35)], were isolated.抄録全体を表示PDF形式でダウンロード (1395K) -
山本 智子, 山本 緑, 中江 裕子, 高田 寛治, 浅田 昌三, 横山 照由, 黒田 耕司1982 年 102 巻 2 号 p. 196-201
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーThe gastrointestinal absorption of indomethacin polymorphs (α-or γ-form) was studied in rabbits and their absorption kinetics was analyzed. There was no significant difference between the bioavailabilities of the two polymorphs after oral administration. The absorption kinetics was found to be satisfactorily explained by a two-compartment model with two consecutive first order input steps.抄録全体を表示PDF形式でダウンロード (536K) -
上野 雅晴, 堀越 勇, 高橋 薫, 桜川 信男1982 年 102 巻 2 号 p. 202-206
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーFor the oral administration of factor IX, (1) the stability of factor IX, (2) the encapsulation of factor IX in liposome preparations, (3) the transformation of prothrombin (factor II) into thrombin, and (4) the absorption of factor II, VII, IX and X from the intestine were studied. The following results were obtained : factor IX was stable from 4°C to 25°C and in a mild alkaline solution. Factor IX was the most effectively encapsulated in liposome preparations with stearylamine or Ca2+. The transformation of prothrombin into thrombin was inhibited by adding lecithin or aprotinine. Oral administration of factor IX entrapped in liposomes tended to shorten clotting time in beagle dogs.抄録全体を表示PDF形式でダウンロード (581K) -
吉柳 節夫, 立山 正, 井口 定男1982 年 102 巻 2 号 p. 207-210
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーThe effect of complex formation on the water-benzene interfacial transfer rate of barbital was studied. The transfer rate of barbital from aqueous to benzene phase was much accelerated by the addition of aminopyrine. The association constants of 1 : 1 barbital-aminopyrine complex in both phases were determined by solubility method. The constants in benzene and aqueous solutions at 30°C were 22.1 and 2.24 M-1, respectively. The best fitting equations for transfer data were numerically analyzed and it was clarified that the time course of the transfer rate of the complex was similar to that of free barbital and that the large value of the association constant in benzene solution resulted in the large transfer rate constant of the complex.抄録全体を表示PDF形式でダウンロード (464K) -
石黒 義信, 沢田 勝, 大眉 和代, 河部 靖1982 年 102 巻 2 号 p. 211-214
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーThe volatility of ethylenediamine from aminophylline preparations was studied. Ethylenediamine liberated from aminophylline tablets was characterized as dibenzo [f, h] quinoxaline. The liberation of ethylenediamine from aminophylline JP and aminophylline tablets could be regarded as a pseudo first-order reaction at 60°C, 70°C, 80°C, 90°C and 100°C. The Arrhenius plots of log kobs. vs. 1/T were almost linear in the temperature range of 70-100°C.抄録全体を表示PDF形式でダウンロード (421K) -
森田 秀行, 小西 徹也1982 年 102 巻 2 号 p. 215-220
発行日: 1982/02/25
公開日: 2008/05/30
ジャーナル フリーHigh performance liquid chromatography (HPLC) by use of a reverse phase column (TSK LS410K) was applied to determine the residual dithiothreitol, iodoacetamide and oxidized dithiothreitol in the alkylated human immunoglobulin (AHIG). After extraction by ethyl acetate, the above compounds were separated by HPLC with MeOH-H2O (60 : 40 v/v) as solvent. Determination was completed within 5 min with high reproducibility. Less than 0.5 ppm for each residual substance could be quantitated. The method was quite suitable for the routine analysis of the residual contaminants in AHIG.抄録全体を表示PDF形式でダウンロード (555K)
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