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141.
Carlo Carlini Marco Di Girolamo Alessandro Macinai Mario Marchionna Marilena Noviello Anna Maria Raspolli Galletti Glauco Sbrana 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):137-146
The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst. 相似文献
142.
Di Bussolo V Caselli M Romano MR Pineschi M Crotti P 《The Journal of organic chemistry》2004,69(21):7383-7386
The reaction of alpha vinyl oxirane 5, prepared through a new route to the d-gulal system, with O-nucleophiles (alcohols and di-O-isopropylidene-alpha-d-monosaccharides) and C-nucleophiles (lithium alkyls) affords, in a completely stereoselective way, the corresponding 2-unsaturated alpha O- and C-glycosides having the same configuration as the starting epoxide. 相似文献
143.
氢化物发生—分光光度法测定染发剂中的微量铅 总被引:1,自引:0,他引:1
本文提出了用铁氰化钾将铅氧化至高价,再用氢化物发生-分光光度法测定铅的一种新方法。该法灵敏度高,简便快速,用于分析染发剂中的铅,取得了较好的效果。 相似文献
144.
一种分离抗凝血酶Ⅲ的高效亲和色谱填料的制备及表征 总被引:6,自引:0,他引:6
以聚甲基丙烯酸环氧丙酯微球 ( PGMA)为基质 ,利用还原氨化方法将肝素键合在其表面上 ,得到一种以肝素为配基的高效亲和色谱填料 ,该填料对抗凝血酶 的亲和容量为 1 .2 mg/g,对抗凝血酶 和人血清白蛋白的回收率分别为 96.9%和 94 .4 % .利用前沿色谱法测定了肝素与抗凝血酶 之间的表观解离常数为 1 .96× 1 0 - 5mol/L.利用该填料可直接从人血浆中分离出抗凝血酶 相似文献
145.
R. CurciF. Di Furia 《Tetrahedron》1972,28(14):3905-3913
The influence of OH− concentration, in the solvent medium dioxane-water 40:60 at 25·0, on the oxidation rates of diphenylphosphine oxide (DPPO) by t-BuOOH, H2O2 and p-nitroperoxybenzoic acid, and of bis-p-tolylphosphine oxide by t-BuOOH has been investigated. For the oxidation of the phosphorus substrates by the hydroperoxides above, the rate law found (R = k2″[Ar2PHO] [ROO−]) differs from the rate law confirmed to hold for the oxidation of DPPO by peroxyacids in alkaline media, i.e.: R = (k2″ + k3[OH−])[Ar2PHO] [RCO3−]. This is interpreted on the basis of one common reaction mechanism involving formation of an intermediate of similar structure, wherein a change in the rate controlling step is likely to occur on passing from p-O2N·C6H4CO3− to t-BuOO−. In the same solvent medium, pKa′ values for t-BuOOH and H2O2 have been estimated. 相似文献
146.
Albano VG Di Serio M Monari M Orabona I Panunzi A Ruffo F 《Inorganic chemistry》2002,41(10):2672-2677
The silver-assisted ligand metathesis reaction involving a platinum(II) complex of formula [PtClMe(N,N-chelate)] with acetonitrile has been investigated. By using a suitably hindered N,N-chelate, an otherwise hardly detectable trinuclear species has been isolated and characterized through X-ray diffractometry. The trinuclear cation consists of two nearly orthogonal [PtCl(Me)(N,N-chelate)] square-planar units entrapping an Ag(+) cation through the chloride ligands that, acting as bidentate, form a linear AgCl(2) unit with two nonequivalent Ag-Cl bonds. The residual acidity of the silver cation is satisfied by one secondary Ag-Pt interaction [Ag-Pt(1) = 2.82 A] in which the platinum atom acts as a donor. Kinetic studies have demonstrated that the silver assistance operates both through a simple associative step and through a pathway in which the above trinuclear complex is an active intermediate. In a noncoordinating solvent the latter species evolves with AgCl loss and formation of a dinuclear Pt,Pt complex showing a rare single chloride bridge. 相似文献
147.
We have designed and synthesized a new family of readily available highly modular phosphite-oxazoline ligands for the Pd-catalyzed asymmetric allylic substitution reactions. The introduction of a pi-acceptor flexible bulky biphenyl phosphite moiety in the ligand design is highly adventitious in the product outcome. Thus, this ligand series affords excellent reaction rates (TOF's up to >2400 mol.(mol.h)-1) and enantioselectivities (ee's up to >99%) and, at the same time, shows a broad scope for different substrate types. 相似文献
148.
JiaChengNING ShuMAO YeDiGUAN 《中国化学快报》2005,16(1):17-19
Eleven (S)-(-)-bishydrocarbyl-(l-alkanoylpyrrolidin-2_yl)_methanol derivatives of three types were synthesized from L-proline.asymmtncally selective alkylation products were obtained oy LDA treatment and alkylation using methyl 2-bromoethyl ether, and three types of chiral α-Substituted-γ-butyrolactones were obtained by hydrolyzing the alkylation products, with %e.e. beijing up to 89 percent. 相似文献
149.
2,4,6-三硝基苯酚改性锆铝复合氧化物固定相分离富勒烯的色谱性能研究 总被引:1,自引:0,他引:1
制备了用于分离C60和C70的2,4,6-三硝基苯酚改性锆铝复合氧化物高效液相色谱固定相,考察了流动相中甲苯的含量、柱温及流速对C60和C70分离的影响,同时比较了酸腐蚀前后锆铝复合氧化物基质对分离的影响,结果表明,2,4,6-三硝基苯酚改性酸腐蚀后锆铝复合氧化物填料对富勒烯表现出较强的分离能力,具有作为富勒烯制备分离的潜力。 相似文献
150.
A. Vecchio Carlo Finoli Damiano Di Simine Vincenza Andreoni 《Fresenius' Journal of Analytical Chemistry》1998,361(4):338-342
Microbial biomass provides available ligand groups on which metal ions bind by different mechanisms. Biosorption of these
elements from aqueous solutions represents a remediation technology suitable for the treatment of metal-contaminated effluents.
The purpose of the present investigation was the assessment of the capability of Brevibacterium sp. cells to remove bivalent ions, when present alone or in pairs, from aqueous solutions, using immobilized polyacrylamide
cells of the microorganism in a flow-through system. The biosorption capacity of Brevibacterium cells was studied for lead, cadmium and copper. The metal cell binding capacity followed the order Cu > Pb > Cd, based on
estimated qmax. These values, expressed as mmol metal/g dry weight cells, were 0.54 for Cu, 0.36 for Pb and 0.14 for Cd. Polyacrylamide-gel
immobilized cells were effective in Pb, Cu and Cd removal. Lead removal was not affected by the presence of Cd and Cu; lead
instead inhibited Cd and Cu removal. The desorption of the metal, by fluxing a chelating solution, restored the metal binding
capacity of the cells, thus affording the multiple use of the same biomass in the remediation treatment.
Received: 31 July 1997 / Revised: 22 December 1997 / Accepted: 30 December 1997 相似文献