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991.
Otani T Takayama J Sugihara Y Ishii A Nakayama J 《Journal of the American Chemical Society》2003,125(27):8255-8263
3,4-Di-tert-butylthiophene 1-oxide (1a) reacted with a series of electron-deficient alkenic dienophiles at its syn-pi-face relating to the S=O bond to give [4+2] adducts in excellent yields. The 1-oxide 1a also reacted even with angle-strained dienophiles acenaphthylene and norbornene at its syn-pi-face to afford [4+2] adducts; in the latter case, norbornene reacted exclusively at its exo-pi-face. The oxide 1a reacted with dimethyl acetylenedicarboxylate to produce dimethyl 4,5-di-tert-butylphthalate in high yield with spontaneous extrusion of SO from the initial adduct even at room temperature. Similarly, 3,4-di-tert-butylthiophene 1-(p-toluenesulfonyl)imide (3a) reacted with alkenic dienophiles at its syn-pi-face relating to the S=N bond to give [4+2] adducts in good yields. The reaction of 3a with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) afforded a 1,2-thiazetidine 12a, the first example of S-unoxidized 1,2-thiazetidine, in good yield, through rearrangement of the initial [4+2] adduct. The molecular structure of 12a is discussed on the basis of the X-ray crystallographic analysis. Comparison of the foregoing reactions leads to the conclusion that the 1-oxide 1a is more reactive as a diene than the 1-imide 3a, which is more reactive than 3,4-di-tert-butylthiophene 1,1-dioxide. The origin of the syn-pi-face selectivities of 1a and 3a in Diels-Alder reactions is discussed in terms of the orbital mixing rule and steric effect and also based on B3LYP/6-31G(d) calculations. 相似文献
992.
Wen Wei Lai Teh Chou Chang 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1075-1083
A series of crosslinkable thermotropic liquid crystalline poly(ether-ester)s and copoly(ether-ester)s was prepared. All of the polymers were crosslinked by thermal treatment or photo-irradiation upon heating. The thermal stability and thermal crosslinking reaction of these polymers were investigated. These polymers also could be crosslinked by copolymerization with vinyl monomers, such as styrene or methyl methacrylate. The crosslinked polymers exhibited thermotropic liquid crystalline behavior after softening by heating. The phase behavior of linear polymers and crosslinked polymers was studied by differential scanning calorimetry (DSC) and an optical polarizing microscope equipped with a heating stage. © 1995 John Wiley & Sons, Inc. 相似文献
993.
气动雾化进样微波等离子体炬(MPT)原子荧光光谱法测定锌的研究 总被引:5,自引:0,他引:5
本文将水溶液雾化进样与微波等离子体炬原子荧光光谱法联用,建立了HCL-MPT-AFS测定Zn的新方法。讨论了实验条件的选择问题以及溶液中共存离子对测定Zn的影响,本文所推荐的方法具有较高的灵敏度和精密度,并将其用于实际样品分析。 相似文献
994.
Bernd GüNTHER 《中国科学B辑(英文版)》2007,50(6)
The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe3O4 core with single domain and the average grain size around 8-12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers ad- sorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case. 相似文献
995.
Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2,6-diformyl-4-methyl-phenol with 4′,5′-diaminobenzo-12-C-4 promoted by proton. The compound was characterized by MS,IR ^1HNMR spectroscopy and elemental analysis. 相似文献
996.
傅里叶变换红外光谱和傅里叶变换拉曼光谱法无损鉴别药材的真伪 总被引:19,自引:0,他引:19
利用傅里叶变换红外(FT-IR)和近红外傅里叶变换拉曼(NIR FT-aman)光谱法对大黄(西宁大黄)与伪品大黄(华北大黄、山大黄、水根大黄)进行了无损快速的鉴别。结果表明:尽管正品大黄与伪品大黄差别较小,有大部分的化学成分有很大的相同之处,但在红外、拉曼谱图中各自的特征峰较突出,根据谱峰的强度和位置可容易地将它们区别开来。红外和拉曼光谱法相互印证,相互补充,具有快速、准确、操作简单、重复性好、不需对样品进行分离提取,可直接鉴别等特点。 相似文献
997.
本文制备了一系列富勒烯及其衍生物,并利用多种质谱技术进行了鉴定、表征、揭示了它们在离子源条件下的稳定性及解规律。这些富勒烯及其省生物在FDMS、ISMS中均得到了较强的准分子离子峰且碎片峰很少。结果表昨FDMS,LSIMS技术均适于富勒烯及其衍生物的定性分析,是目前富勒烯分析鉴定中较好的方法。 相似文献
998.
Haas P Hempstead M Jensen T Kagan H Kass R Behrends S Gentile T Guida JM Guida JA Morrow F Poling R Rosenfeld C Thorndike EH Tipton P Besson D Green J Namjoshi R Sannes F Skubic P Stone R Bortoletto D Chen A Goldberg M Horwitz N Jawahery A Lubrano P Moneti GC Trahern CG van Hecke H Csorna SE Garren L Mestayer MD Panvini RS Word GB Yi X Alam MS Bean A Ferguson T Avery P Bebek C Berkelman K Blucher E Cassel DG Copie T DeSalvo R DeWire JW Ehrlich R Galik RS Gilchriese MG Gittelman B Gray SW 《Physical review letters》1985,55(12):1248-1251
999.
An all-atom dimethyl sulfoxide (DMSO) model and a TIP5P water model have been adopted for molecular dynamics simulation. Two new qualities ηrelE and ηrel are introduced to describe the anomalous nonideal behaviors of DMSO–water mixtures. The simulation is compared with chemical shift and excess enthalpy of mixing, which shows good concentration dependences. In addition, our all-atom simulation also indicates that the C–H groups of DMSO may interact with the oxygen atoms of water and DMSO. The weak C–HO contacts and the strong O–HO hydrogen bonds represent the consistent concentration dependences, which exhibits the cooperation effect. 相似文献
1000.
离子注入修饰电极检测硝基苯 总被引:9,自引:0,他引:9
离子注入是一种新技术,可按人们的意愿和需要,将不同的离子注入不同的基本电极表面,制成具有催化活性强,稳定性高,重现性好等特点的修饰电极。作者研究了离子注入钴和注入镍的玻碳电极在0.1mol/LHAc-NaAc缓冲溶液中硝基苯的行为及测定。 相似文献