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151.
Summary A new micro bromination method is proposed for the determination of oxygen in titanium. The sample is mixed with carbon and treated with bromine at 825° C in a quartz boat, using argon as a carrier gas. The oxygen in the sample combines with the carbon to form carbon monoxide, which is then oxidized to carbon dioxide with hot copper oxide. The carbon dioxide is absorbed by a weighed absorption tube containing soda-asbestos. The bromine and titanium tetrabromide are removed by a cold trap cooled by dry ice and alcohol. To remove the last traces of bromine or bromine compounds, a soda tube and silvergauze heated to 650° are used. The method has been satisfactorily applied to the determination of oxygen in commercial titanium.
Zusammenfassung Eine neue Mikromet-hode zur Bestimmung von Sauerstoff in Titan durch Bromierung wird vorgeschlagen. Die Probe wird mit Kohlenstoff gemischt und bei 825° C in einem Quarzschiffchen mit Brom behandelt, wobei Argon als Trägergas dient. Der in der Probe enthaltene Sauerstoff reagiert mit dem Kohlenstoff zu Kohlenmonoxyd, das dann über erhitztem Kupferoxyd zu Kohlendioxyd oxydiert wird. Dieses wird in einem gewogenen Absorptionsröhrchen an Natronasbest gebunden. Brom und Titantetrabromid werden in einer Falle mit Trockeneis und Alkohol ausgefroren. Zur Entfernung der letzten Spuren Brom oder Bromverbindungen dient ein auf 650° erhitztes Röhrchen mit Natron und Silberdrahtnetz. Das Verfahren hat sich zur Bestimmung von Sauerstoff in handelsüblichem Titan zufriedenstellend bewährt.
Résumé Les auteurs proposent une nouvelle microméthode de bromuration pour le dosage de l'oxygène dans le titane. L'échantillon mélangé avec du carbone est traité par le brome à 825° C dans une nacelle de quartz sous courant d'argon utilisé comme gaz de transport. L'oxygène de l'échantillon se combine au carbone sous forme d'oxyde de carbone qui est oxydé en anhydride carbonique sur oxyde de cuivre à chaud. L'anhydride carbonique est absorbé et pesé dans un tube absorbeur rempli d'amiante sodé. Le brome et le tétrabromure de titane sont retenus dans un piège refroidi par le système glace carbonique-alcool. Les dernières traces de brome et de composés bromés sont éliminées à l'aide d'un tube à soude et d'une toile d'argent chauffée à 650°. La méthode a été appliquée avec succès au dosage de l'oxygène dans le titane commercial.相似文献
152.
Treatment of N-(o-alkynylphenyl)imine derivatives with W(CO)(5)(L) induces the 5-endo-mode of cyclization of the imine nitrogen onto the electrophilically activated alkyne moiety to afford a novel reactive species, a metal-containing azomethine ylide. [3 + 2] cycloaddition of this ylide species with various electron-rich alkenes proceeds smoothly to give unstable carbene complexes, which in turn undergo 1,2-hydrogen-, alkyl-, and aryl-migration to afford in good yield 6-5-5 tricyclic indole skeletons having an alkyl or an aryl substituent at the 3-position of the indole nucleus. 相似文献
153.
A triphenylphosphine-catalyzed cyclization of alpha-keto esters, alpha-keto nitriles, or alpha,alpha,alpha-trifluoroacetophenone with dimethyl acetylenedicarboxylate is reported to produce highly functionalized alpha,beta-unsaturated gamma-butyrolactones in moderate yields. Thus treating a mixture of methyl 4-nitrophenylglyoxylate and dimethyl acetylenedicarboxylate with 20 mol % of triphenylphosphine afforded 5,5'-disubstituted 3-methoxy-4-(methoxycarbonyl)-2(3H)-furanone in 94% yield. In the reaction of alpha-keto esters R(1)COCOOMe, an electron-withdrawing R(1) substituent is required for satisfactory reactivity. On the other hand, electron-donating R(1) substituents give higher yields with alpha-keto nitriles R(1)COCN. Another electron-deficient carbonyl compound, alpha,alpha,alpha-trifluoroacetophenone, gave the corresponding lactone in good yield. The use of an alpha-hydroxy ketone as an electrophilic carbonyl compound with more than 1 equiv of triphenylphosphine produced dihydrofuran derivatives. One equivalent of triphenylphosphine oxide was obtained as a major product. An intramolecular Wittig reaction is proposed as a reaction mechanism. 相似文献
154.
The allylic-type diindium reagents A and B were prepared from 3-bromo-1-iodopropene (1a) and 4-bromo-2-iodobut-2-ene (1b), respectively, and their reactions with electrophiles were investigated. The diindium reagents A and B were initially reacted with imines and the resulting vinylindium compounds were then treated with organic halides in the presence of Pd(PPh(3))(4) to give linear N-aryl and N-tosyl homoallylic amines. Diindium A is stable in a small amount of water in solvent, whereas B is easily protonated to give a crotylindium reagent. The reaction of B with benzaldehyde gives mainly the 1,3- and 1,5-diols via a spontaneous coupling with two molecules of the aldehyde, in contrast to A, which reacts with one molecule of carbonyl compounds to give the vinylindium compounds. 相似文献
155.
156.
Fujio Suganuma Sueo Machi Hiroshi Mitsui Miyuki Hagiwara Tsutomu Kagiya 《Journal of polymer science. Part A, Polymer chemistry》1968,6(8):2069-2078
Gamma-radiation-induced polymerization of ethylene in alcohols such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl alcohols was carried out under a pressure of 400 kg./cm.2at 30°C. at a dose rate of 1.4 × 105 rad/hr. in a batch reactor of 100 ml. capacity. The yield and molecular weight of polymer formed in the alcohols (except tert-butyl alcohol) were much lower than those of the bulk polymerization under the same conditions, whereas the addition of tert-butyl alcohol increased the yield and reduced the molecular weight. From the infrared spectra of the polymers and those of the bromination products it was concluded that only primary OH exists in the polymer formed in methyl alcohol and that both primary and secondary OH are in the polymer formed in other primary alcohols. Both secondary and tertiary OH were observed in the polymer when the secondary alcohols were used, and only tertiary OH in the case of tert-butyl alcohol. These polymers were found to contain small amounts of vinylidene unsaturation and methyl group. On the basis of these results the roles of the alcohols in the polymerization are discussed. 相似文献
157.
Bond IA Budding E Conway MJ Fenton KB Fujii H Fujii Z Hasegawa H Hayashida N Honda M Hotta N Humble JE Kabe S Kasahara K Kifune T Masaike A Matsubara Y Mitsui K Miura Y Mori M Murakami K Muraki Y Nagano M Nakamura K Nakamura T Norris PM Ohashi Y Okada A Saito T Sakata M Sato H Shibata S Shima M Storey JR Tanimori T Teshima M Torii S Uchino K Watase Y Woodhams MD Yamamoto Y Yock PC Yuda T 《Physical review letters》1988,60(12):1110-1113
158.
Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β‐Ketonitrile Derivatives
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Dr. Kensuke Kiyokawa Takaya Nagata Prof. Dr. Satoshi Minakata 《Angewandte Chemie (International ed. in English)》2016,55(35):10458-10462
The highly efficient electrophilic cyanation of boron enolates using readily available cyanating reagents, N‐cyano‐N‐phenyl‐p‐toluenesulfonamide (NCTS) and p‐toluenesulfonyl cyanide (TsCN), is reported. Various β‐ketonitriles were prepared by this new protocol, which has a remarkably broad substrate scope compared to existing methods. The present method also allowed efficient synthesis of β‐ketonitriles containing a quaternary α‐carbon center. In addition, a preliminary result with the use of a chiral boron enolate for the enantioselective cyanation reaction is described. 相似文献
159.
160.
Kazunari Takaya Yuya Hasegawa Tetsuo Koizumi Hajime Tanuma 《International Journal for Ion Mobility Spectrometry》2016,19(4):183-187
The mobilities of polyatomic molecular ions in He gas, measured at 83 and 306 K using a low-temperature drift tube, were smaller than the polarization limit K pol. The mobilities of atomic or small molecular ions tended to show a bump at intermediate reduced field, and then approach the polarization limit at low reduced field; however, the measured mobilities of polyatomic molecular ions were different. We compared the experimental mobilities with values calculated using the MOBCAL program, and found that they agreed well. 相似文献