The weak base type anion exchange adsorbent was prepared by introducing the amino group to the cotton yarn. The adsorbent was for the water recycle model system in order to remove reactive dyes in the rinsing water. The chemical treatments were carried out in aqueous solutions for introducing the ion exchange group into the inside of the fiber matrix. Cotton yarns were graft-copolymerized with 5% acrylamide using cerium salt as an initiator at 50°C. The maximum grafting ratio was 23.3%. The grafted amide group was transformed into the amino group through Hofmann-degradation using sodium-hypochloride. The nitrogen content of the sample was 1.5%. The breaking strength of the ion exchangeable cotton yarn decreased to 75% of the original cotton yarn through the above chemical treatments. The colour removal from rinsing waste water used in the model system was examined with the treated yarn. It was found that the capacity of this yarn for adsorbing hydrolyzed reactive dyes increased in acidic solution and at a high temperature. The colour removal of this yarn was the same as that of activated carbon powder according to the results of the batch method. In contrast, the colour removal with this yarn was ten times higher than that with activated carbon granules in the column method.

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Our previous study showed that an anion exchangeable cotton yarn was capable of adsorbing hydrolyzed reactive dyes in waste water, This yarn was prepared by Hofmann-degradative treatment of poly (acrylamide) -cotton graft copolymers by using hypochlorite. In this paper we report on the improvement of the preparation of anion-exchangeable cotton yarns. For enhancing grafting ratio and conversion ratio of the graft copolymerization of acrylamide onto cotton yarns, a Fe⁺²-H₂O₂ redox system was used as an initiator. The ferrous salt was adsorbed on cotton yarns and then added to a monomer solution containing H₂O₂. This redox system as an initiator gave three times higher grafting ratio than the cerium salt system. The conversion ratio of graft copolymerization was dependent on the monomer concentration and the bath ratio. The maximum conversion ratio (78%) was obtained with 10% acrylamide at bath ratio, 1:8 by using this redox system. The capacity of yarns for adsorbing hydrolyzed reactive dyes was dependent on the conditions of Hofmann-degradative treatment. The maximum capacity of dye adsorption (230mg/g) was attained when the grafted yarn was treated at room temperature for 6h in the solution containing a large excess of NaOH and hypochlorite, where the active chlorite was 1.4 times as much as the molar quantities of the grafted acrylamide. The adsorbed dye on the cotton yarn was easily eluted with dilute NaOH solution and the maximum desorption of dyes (96.3%) was attained with 0.05% NaOH solution. This yarn adsorbed the dye more effectively even at a high flow rate (SV 215) than the activated carbon in the column method.

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5-メチル-3-アミノイソオキザゾールは分解反応によって製造される。すでに確立されている反応機構にもとづいて反応速度論的解析を行ない,回分法による実験から反応速度定数を決定した。その結果,この反応は連続反応装置を用いる流通系反応操作によって有利に行なわれることを知った。典型的連続反応装置の一つである多段槽型反応装置に対して,ディジタル電子計算機を用いて,種々の操作変数の組合わせについて理論計算を行なって合理的操作条件を予知し,実際に3段槽型連続反応装置により実験した結果は予期したとおりの好成績をおさめた。

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2, 6-ジフルオルアニリンの誘導体のなかには生物学的に活性をもつと期待される化合物があるが, その合成1ま容易でない。かって著者らの1人は, 発ガン性物質の合成研究の-環として3, 5-ジフルオルアニリンの4-位にp-ニトロフェニルジアゾニウムクロリドをカップルさせ, 得られたアゾ色素を還元分解して2, 6-ジフルオル-1, 4-フェニレンジアミンを得, さらに4-アミノ-2, 6-ジフルオルアセトアニリドの脱アミノ化により2, 6-ジフルオルアセトアニリドをはじめて合成した。
いっぽう, きわめて最近Roeらは2, 6-ジフルオルアニリンの新しい合成ルートを報告している2) 。これはm-ジフルオルベンゼンを原料とし, そのリチウム化物である2, 6-ジフルオルフェニルリチウムを炭酸化して2, 6-ジフルオル安息香酸とし, クルチウス反応を適用してそのアジドを硫酸中で分解してアミンに変えるものである。
著者らはこれと別個に, 2, 6-ジクロルベンゾニトリルを原料とし, そのフッ素化, ついで部分的加水分解による2, 6-ジフルオル安息香酸アミドの合成, さらにその反応による2, 6-ジフルオルアニリンの合成について検討し, よい結果をえた。
Cl-CN-Cl→F-CN-F→F-CO₂H-F→F-CONH₂→F-NHCO₂CH₃→F-NH₂-F
原料の2, 6-ジクロルベンゾニトリルは除草剤として工業的に製造されており3), またそめハロゲン交換によるフッ素化も知られている4) 。著者らは2, 6-ジフルオルベンゾニトリルを60%硫酸と煮沸するとカルボン酸にまで加水分解されるが, 90%硫酸と70℃に加温するだけでは加水分解は部分的にとどまり, 定量的にアミドが得られることを知った。またこのアミドの反応も常法によって円滑に進行して収率よくアミンがえられ, このルートによる2, 6-ジクロルベンゾニトリルから2, 6-ジフルオルアニリンの通算収率は55～60%であった。なおをメタノール中でおこなわせると, 2, 6-ジフルオルフェニルカルバミン酸メチルがこれもよい収率でえられた。

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3,5-ジ-t-ブチル安息香酸アミド(I)のホフマン分解における中間体3,5-ジ-t-ブチルフェニル・カルバミン酸メチル(II)を,3,5-ジ-t-ブチルアニリン(III)とクロル炭酸メチルから別途合成し,構造の確認を行なった。
III+ClCO₂Me→II
また,Iのホフマン分解における副生成物を単離・確認した。
(1)Iのの際得られる副生成物は4-(3,5-ジ-t-ブチルフェニル)-1-(3,5-ジ-t-ブチルベンゾイル)セミカルバジド(VII)であった。
(2)IIの加水分解反応の際副生する生成物はN,N′-ジ-(3,5-ジ-t-ブチルフェニル)尿素(V)であった。Vは次の反応でIIより生成することがわかった。2II→V+2MeOH+CO₂
(3)Vを,構造確認のためIIIとホスゲンから別途合成した。
2III+COCl₂→V

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L-α, β-Diaminopropionic acid was obtained in 92% yield from L-aspartic acid by the Schmidt reaction using 30% fuming sulfuric acid and sodium azide.

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Sphingolipids have been known as lipid second messengers in mammalian cells and cell membranes, and a great deal of attention has been devoted to the studies of the biological process regulated by sphingolipids. Now, it has been well accepted that the sphingolipids play key roles in the cellular signal transmission pathway. Sphingomyelin, which is one of the key sphingolipids, is a ubiquitous constituent in animal tissue and has been known to occur in virtually every cell and in cell membranes. Ceramide and phosphoryl choline, which are the primary catabolites of sphingomyelin, are generated through the action of sphingomyelinase; ceramide is believed to display key roles as a signal transduction factor in cell differentiation and in programmed cell death (apoptosis) derivation (Figure 1). Although the significance of the sphingomyelin pathway, which is initiated by hydrolysis of sphingomyelin by SMase, has been well recognized, none of the tertiary-dimensional structures of these important enzymes have been determined and their hydrolytic mechanism has not been well-defined. It is, therefore, a very attractive challenge to reveal the catalytic mechanism of action of this important enzyme. Strong and selective sphingomyelinase inhibitors would contribute to a better understanding both of the roles of these enzymes and of ceramide in signal transduction. In order to elucidate the detailed catalytic mechanism of SMase, the development of the methods for supplying the sphingomyelin analogues, which competitively act at the catalytic site and strongly inhibit the hydrolytic ability of the enzyme, have strongly been desired. We then designed the substrate analogues 1, 2, 3, 4, 5 and 6 as inhibitor candidates on the basis of our previous results obtained on sphingomyelin analogues. In theses analogues, one of the oxygen atoms of the phosphoester, at which sphingomyelin is hydrolyzed by the enzyme, is replaced by either methylene, ethylene, difluoromethylene, nitrogen, or sulfur group, and the relative configuration of the asymmetric centers is (D)-erythro (3S, 4R) form (Figure 2). We will describe in detail the highly efficient stereocontrolled syntheses of the short chain substrate analogues 1, 2, 4, and 6 and their inhibitory activities toward B. cereus SMase.

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脳循環改善薬KB-2796の生体内動態を研究するため, ¹⁴C標識体の合成を行った。中間体として2, 3, 4-trimethoxybromobenzene (II) をリチウム化後, ¹⁴C-二酸化炭素と反応させcarboxy-¹⁴C-2, 3, 4-trimethoxybenzoicacid (IV) を合成した。VIをエステル化後, 還元しformy1体 (VI) とした。VIとbis (4-fluorophenyl) methylpiperazineを縮合し, ¹⁴C-KB-2796 (I) を得た。¹⁴C-炭酸バリウムからの全収率は39%, 放射化学的純度は99%, 比放射能は1816.7MBq/mmol (49.1mCi/mmol) であった。

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In recent years, halogen bonding (XB) interaction has attracted much attention in organic synthesis, especially for the activation of substrates. On the other hand, the use of XB interaction for the “stabilization” of molecules has been less explored. In this manuscript, the authors described our recent work on the development of new class of N-acyliminoiodinanes and iodonium ylides, which can be used as nitrene and carbene equivalents, respectively. The intramolecular XB interactions were confirmed by X-ray structure and natural bond orbital (NBO) analyses. The synthesized N-acyliminoiodinanes were found to be activated by photo-irradiation to react with silyl enol ethers, glycals, alkynes, and(hetero)aromatic compounds to afford the corresponding aminated adducts. In addition, the iodonium ylides baring intramolecular XB interaction underwent additive-free chemoselective coupling reaction of thioamides, even in protic polar solvents. The intramolecular XB could also control the coordination mode of the nucleophile via σ-holes, suppressing undesired side reactions. These findings would pave new avenues chemoselective coupling reactions using hypervalent iodine compounds.

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3,5-ジ-t-ブチル安息香酸アミドは通常法によるホフマン分解によってはほとんど反応せず,Burgersらも.Rec.trav.chim.75,1327(1956)で成功しなかったと報告しているが,著者らの考案した変法によれば極めて容易に反応し,中間体たる3,5-ジ-t-ブチルフェニル・カルバミン酸メチル(新化合物)を経て,82%の高収率で3,5-ジ-t-ブチルアニリンを生成することを知った。この変法は, 通常の臭素・金属ナトリウム・メタノール法における臭素の代りに, 臭素のメタノール溶液を用いるものである。

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An analytical curve fitting technique, the least square method, is described and applied to infrared spectrophotometric analysis of caffeine, ethoxybenzamide and dibenzoylthiamine in mixed pharmaceutical preparations. These components were extracted from the pharmaceutical preparations with chloroform, and the transmittance of the chloroform solution was determined at six points of 5.86, 8.70, 8.90, 9.15, 10.23, and 11.13 μ. The conversion of transmittance into absorbance and the calculation by the least square method were carried out by an electronic computer (NEAC 2206). Interferences of the component, which has absorbances at the selected wavelengths, were eliminated by regarding the ratio of these absorbances as constants. This method provides a rapid quantitative analysis of the complex mixtures, can be applied to a wide variety of samples, and is useful as a rapid industrial analysis.

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