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941.
Microwave‐Assisted,Rhodium(III)‐Catalyzed N‐Annulation Reactions of Aryl and α,β‐Unsaturated Ketones with Alkynes
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Hyejeong Lee Yong‐Kyun Sim Dr. Jung‐Woo Park Prof. Dr. Chul‐Ho Jun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):323-333
New RhIII‐catalyzed, one‐pot N‐annulation reactions of aryl and α,β‐unsaturated ketones with alkynes in the presence of ammonium acetate have been developed. Under microwave irradiation conditions, the processes lead to rapid formation of the respective isoquinoline and pyridine derivatives with efficiencies that are strongly dependent on the steric nature of the aryl ring and enone substituents. By employing this protocol, a variety of isoquinoline and pyridine derivatives were prepared in high yields. In addition, a new one‐pot approach to the synthesis of pyridines, involving four‐component reactions of ketones, formaldehyde, NH4OAc, and alkynes, has been uncovered. This process takes place through a route involving initial aldol condensation of the ketone with formaldehyde to generate a branched α,β‐unsaturated ketone that then undergoes RhIII‐catalyzed N‐annulation with NH4OAc and the alkyne. 相似文献
942.
Goeun Sim Md Nur Alam Louis Godbout Theo van de Ven 《Cellulose (London, England)》2014,21(6):4595-4606
Structural changes in cellulose fibers were elucidated for carboxymethylated fibers and fibers that are oxidized by periodate and chlorite. Non-fibrillated and partially fibrillated softwood, kraft fibers (SKF, m-SKF) were carboxymethylated to investigate the contribution of the S1 layer to the swollen fiber structures. Carboxymethylated non-fibrillated fibers (CMF) form balloon-like structures as they swell heterogeneously. When partially fibrillated SKF is carboxymethylated (m-CMF), the fibers do not exhibit this ballooning phenomenon due to the degradation of the S1 layer. Carboxymethylation disrupts the native cellulose crystalline structure without breaking the fibers apart. Periodate–chlorite oxidized fibers, on the other hand, swell homogeneously without disrupting the native cellulose I crystalline form. Periodate–chlorite oxidation damages all three secondary layers to the extent that any microfibril confinement caused by the swelling is removed. Each chemistry and mechanical treatment affects the cellulose fibers differently to yield various swollen structures. 相似文献
943.
Catarina I. V. Ramos Patrícia M. R. Pereira M. Graça Santana‐Marques Rodrigo De Paula Mário M. Q. Simões M. Graça P. M. S. Neves José. A. S. Cavaleiro 《Journal of mass spectrometry : JMS》2014,49(5):371-379
Electrospray ionization mass spectrometry/mass spectrometry in the positive ion mode was used to investigate the gas‐phase chemistry of multicharged ions from solutions of porphyrins with 1,3‐dimethylimidazolium‐2‐yl (DMIM) and 1‐methylimidazol‐2‐yl (MIm) meso‐substituents. The studied compounds include two free bases and 12 complexes with transition metals (Cu(II), Zn(II), Mn(III), and Fe(III)). The observed multicharged ions are either preformed or formed during the electrospraying process by reduction or protonation and comprise closed‐shell and hypervalent mono‐radical and bi‐radical ions. The observed extensive and abundant fragmentation of the DMIM and MIm meso‐substituents is a characteristic feature of these porphyrins. Fragments with the same mass values can be lost from the meso‐substituents either as charged or neutral species and from closed‐shell and hypervalent radical ions. Reduction processes are observed for both the free bases and the metallated DMIM porphyrins and occur predominantly by formation of hypervalent radicals that fragment, at low energy collisions, by loss of methyl radicals with formation of the corresponding MIm functionalities. These findings confirm that, when using electrospray ionization, reduction is an important characteristic of cationic meso‐substituted tetrapyrrolic macrocycles, always occurring when delocalization of the formed hypervalent radicals is possible. For the Fe(III) and Mn(III) complexes, reduction of the metal centers is also observed as the predominant fragmentation of the corresponding reduced ions through losses of charged fragments testifies. The fragmentation of the closed‐shell ions formed by protonation of the MIm porphyrins mirrors the fragmentation of the closed‐shell ions of their DMIM counterparts. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
944.
The application of smartphones to medical devices has been gaining attention in addressing accessibility and cost issues in healthcare, and the detection of medically relevant compounds has been demonstrated using customized smartphone hardware and/or software. Metabolomics, a newly rising omics field, has also spawned many medical applications but requires highly sophisticated and expensive equipment. Here, we describe a portable smartphone platform, built with readily available and affordable materials, that can perform all of the critical aspects of metabolomics. Excluding the smartphone itself, the total materials for the platform were obtained at less than US $20. For spectral data acquisition, the system utilized visible light (400–700 nm) and a built-in camera. All of the data processing, statistical analysis, and final-visualization components necessary for decision making were implemented in the smartphone platform. The platform is generally applicable as long as the analytes absorb visible light. We provide a proof-of-concept example wherein the metabolomics platform was applied to the assessment of cisplatin-induced kidney toxicity in a rat model, correctly predicting 7 out of 8 test samples. 相似文献
945.
We report a seedless synthetic method of gold octahedral nanoparticles in an aqueous phase. Eight facets with {111} crystalline structures of octahedral nanoparticles could be formed in an aqueous medium when the gold salt was reduced by ascorbic acid at room temperature in the presence of cetyltrimethylammonium bromide as a shape-inducing agent, and hydrogen peroxide as a reaction promoter. The growth kinetics and surface crystalline structures were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy. 相似文献
946.
The apparent second-order rate constant (k OH) for hydroxide-ion-catalyzed conversion of 1 to N-(2'-methoxyphenyl)phthalamate (4) is approximately 10(3)-fold larger than k OH for alkaline hydrolysis of N-morpholinobenzamide (2). These results are explained in terms of the reaction scheme 1 --> k(1obs) 3 --> k(2obs) 4 where 3 represents N-(2'-methoxyphenyl)phthalimide and the values of k(2obs)/k(1obs) vary from 6.0 x 10(2) to 17 x 10(2) within [NaOH] range of 5.0 x 10(-3) to 2.0 M. Pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of 1 decrease from 21.7 x 10(-3) to 15.6 x 10(-3) s(-1) with an increase in ionic strength (by NaCl) from 0.5 to 2.5 M at 0.5 M NaOH and 35 degrees C. The values of k obs, obtained for alkaline hydrolysis of 2 within [NaOH] range 1.0 x 10(-2) to 2.0 M at 35 degrees C, follow the relationship k(obs) = kOH[HO(-)] + kOH'[HO (-)] (2) with least-squares calculated values of kOH and kOH' as (6.38 +/- 0.15) x 10(-5) and (4.59 +/- 0.09) x 10(-5) M (-2) s(-1), respectively. A few kinetic runs for aqueous cleavage of 1, N'-morpholino-N-(2'-methoxyphenyl)-5-nitrophthalamide (5) and N'-morpholino-N-(2'-methoxyphenyl)-4-nitrophthalamide (6) at 35 degrees C and 0.05 M NaOH as well as 0.05 M NaOD reveal the solvent deuterium kinetic isotope effect (= k(obs) (H 2) (O)/ k(obs) (D 2 ) (O)) as 1.6 for 1, 1.9 for 5, and 1.8 for 6. Product characterization study on the cleavage of 5, 6, and N-(2'-methoxyphenyl)-4-nitrophthalimide (7) at 0.5 M NaOD in D2O solvent shows the imide-intermediate mechanism as the exclusive mechanism. 相似文献
947.
Agapito F Nunes PM Costa Cabral BJ Borges dos Santos RM Martinho Simões JA 《The Journal of organic chemistry》2008,73(16):6213-6223
The C-H bond dissociation enthalpies (BDEs) for the five- and six-membered ring alkanes, alkenes, and dienes were investigated and discussed in terms of conventional strain energies (SEs). New determinations are reported for cyclopentane and cyclohexane by time-resolved photoacoustic calorimetry and quantum chemistry methods. The C-H BDEs for the alkenes yielding the alkyl radicals cyclopenten-4-yl and cyclohexen-4-yl and the alpha-C-H BDE in cyclopentene were also calculated. The s-homodesmotic model was used to determine SEs for both the parent molecules and the radicals. When the appropriate s-homodesmotic model is chosen, the obtained SEs are in good agreement with the ones derived from group additivity schemes. The different BDEs in the title molecules are explained by the calculated SEs in the parent molecules and their radicals: (1) BDEs leading to alkyl radicals are ca. 10 kJ mol (-1) lower in cyclopentane and cyclopentene than in cyclohexane and cyclohexene, due to a smaller eclipsing strain in the five-membered radicals relative to the parent molecules (six-membered hydrocarbons and their radicals are essentially strain free). (2) C-H BDEs in cyclopentene and cyclohexene leading to the allyl radicals are similar because cyclopenten-3-yl has almost as much strain as its parent molecule, due to a synperiplanar configuration. (3) The C-H BDE in 1,3-cyclopentadiene is 27 kJ mol (-1) higher than in 1,4-cyclohexadiene due to the stabilizing effect of the conjugated double bond in 1,3-cyclopentadiene and not to a destabilization of the cyclopentadienyl radical. The chemical insight afforded by group additivity methods in choosing the correct model for SE estimation is highlighted. 相似文献
948.
Fustero S Román R Sanz-Cervera JF Simón-Fuentes A Cuñat AC Villanova S Murguía M 《The Journal of organic chemistry》2008,73(9):3523-3529
The preparation of N-methylpyrazoles is usually accomplished through reaction of a suitable 1,3-diketone with methylhydrazine in ethanol as the solvent. This strategy, however, leads to the formation of regioisomeric mixtures of N-methylpyrazoles, which sometimes are difficult to separate. We have determined that the use of fluorinated alcohols such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as solvents dramatically increases the regioselectivity in the pyrazole formation, and we have used this modification in a straightforward synthesis of fluorinated analogs of Tebufenpyrad with acaricide activity. 相似文献
949.
K. P. Lopes L. S. Cavalcante A. Z. Simões R. F. Gonçalves M. T. Escote J. A. Varela E. Longo E. R. Leite 《Journal of Sol-Gel Science and Technology》2008,45(2):151-155
NiTiO3 (NTO) nanoparticles encapsulated with SiO2 were prepared by the sol–gel method resulting on core-shell structure. Changes on isoelectric point as a function of silica
were evaluated by means of zeta potential. The NTO nanoparticles heat treated at 600°C were characterized by X-ray diffraction,
transmission electron microscopy (TEM) and energy dispersive X-ray analysis. TEM observations showed that the mean size of
NTO is in the range of 2.5–42.5 nm while the thickness of SiO2 shell attained 1.5–3.5 nm approximately. 相似文献
950.
Beneito-Cambra M Herrero-Martínez JM Simó-Alfonso EF Ramis-Ramos G 《Rapid communications in mass spectrometry : RCM》2008,22(22):3667-3672
A method for the rapid classification of proteases, lipases, amylases and cellulases used as enhancers in cleaning products, based on precipitation with acetone, hydrolysis with HCl, dilution of the hydrolysates with ethanol, and direct infusion into the electrospray ion source of an ion-trap mass spectrometer, has been developed. The abundances of the ([M+H]+ ions of the amino acids, from the hydrolysates of both the enzyme industrial concentrates and the detergent bases spiked with them, were used to construct linear discriminant analysis models, capable of distinguishing between the enzyme classes. For this purpose, the variables were normalized as follows: (A) the ion abundance of each amino acid was divided by the sum of the ion abundances of all the amino acids in the corresponding mass spectrum; (B) the ratios of pairs of ion abundances were obtained by dividing the ion abundance of each amino acid by each one of the ion abundances of the other 17 amino acids in the corresponding mass spectrum. Using normalization procedure B, excellent class-resolution between proteases, lipases, amylases and cellulases was achieved. In all cases, enzymes in industrial concentrates and manufactured cleaning products were correctly classified with >98% assignment probability. 相似文献