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51.
Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline,
and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh3 and NEt4Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate.
In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important
variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the
presence of PdCl2−PPh3−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that
is indispensable for an efficient overall reaction. 相似文献
52.
Since its inception five decades ago, imprinted sol-gel materials went practically unnoticed, until in the 1970s the conceptual introduction of molecular imprinting in synthetic polymers triggered a new interest in this field. The recent growth in interest in organic–inorganic hybrid materials prepared by sol-gel chemistry and the development of a variety of new strategies for imprinting polymeric matrices have led to a growing activity in what became known as molecularly imprinted sol-gel materials. This paper intends to give an overview of recent progress in molecular imprinting in sol-gel matrices, the potential analytical applications of these tailor-made materials and their limitations, with the aim of drawing attention to useful information and to enhancing interest in this practically unexplored but promising field. 相似文献
53.
Monica Bartolomei Maurizio Cignitti Marina Cotta Ramusino Gianfranco La Manna 《Journal of Molecular Structure》1995,330(1-3):431-435
7,8-dihydroquinoline-4,5 (1H,6H)-dione (1) and 7,8-dihydroquinoline-2,5-(1H,6H)-dione (2) in their tautomeric oxo and hydroxy forms have been studied by ab initio Hartree-Fock calculations; tautomerization energies predict a more stable hydroxy structure having an intramolecular hydrogen bond for compound 1, whereas the oxo form is slightly-preferred for compound 2. Fourier Transform-Infra Red (FT-IR) spectra in CHCl3 solution indicate that the predicted most stable tautomers in the vapour phase remain as such. 相似文献
54.
Kyu Ho Chae Kyung Hee Sung 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):975-984
A polymeric photobase generator containing oxime–urethane groups was prepared by copolymerization of methyl methacrylate and methacryloxyethyl benzophenoneoxime urethane, and its photo and thermal crosslinking reaction after irradiation was examined from the measurement of UV and IR absorption spectral changes, insoluble fraction, and molecular weight changes. The photo‐crosslinking reaction of the copolymer film was more efficient when irradiations were carried out with 310 nm UV light in the presence of benzophenone than with 254 nm UV light without the addition of benzophenone. The crosslinking reaction increased after postexposure baking (PEB), and this thermal crosslinking reaction mechanism was studied from the identification of the photolysis products of a model compound, benzophenoneoxime phenylurethane, by a high‐performance liquid chromatography. The results indicate that the thermal crosslinking reaction of the copolymer after PEB is due to the formation of urea‐type chemical bonds. Resist properties of the copolymer were examined from the measurement of normalized thickness and micropattern development. A negative tone image with a resolution of 2 μm was obtained with this copolymer, having a sensitivity (D) of 1200 mJ/cm2 and contrast (γn) of 1.31, when irradiation was carried out with 310 nm UV light in the presence of benzophenone following chloroform development. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 975–984, 2004 相似文献
55.
The linking of pyrimidines to polystyrene supports via either a 2- or 4-thioether provides access to pteridines through solid-phase synthesis. Oxidative cleavage (dimethyldioxirane) followed by nucleophilic substitution by amines, azide, or water completes a traceless synthesis of pteridines. 相似文献
56.
Hyoung Sik Kim Min Kang Min Woo Song Jin Won Park Byoung Ryul Min 《Reaction Kinetics and Catalysis Letters》2004,81(2):251-257
Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability
for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
57.
A new approach to indolizines has been developed using a 5-endo-trig iodocyclization of allylic esters followed by isomerization and dehydroiodination facilitated by triethylamine at rt. This mild procedure enabled us to synthesize a number of highly substituted indolizines in good yields. 相似文献
58.
Tae?Shin?Chung Young?Mee?Na Shin?Won?Kang Ok-Sang?JungEmail author Young-A?Lee 《Transition Metal Chemistry》2005,30(5):541-545
Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [PtII (X)2 (N–N)] (X = Cl, OH, X2 = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [PtIV (OH)(Y)(X)2(N–N)] (Y = OH, OCH3). The crystal structures of [PtIV(OH)(OCH3)(Cl)2(dmpda)]·2H2O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) Å3, Z = 2R = 0.0503) and [PtIV(OH)2(ipm)(ippda)]·3H2O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) Å3, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH3; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions. 相似文献
59.
Lee JS Zhang MH Yun EK Geum D Kim K Kim TH Lim YS Seo JS 《Experimental & molecular medicine》2005,37(5):427-435
Vimentin is an intermediate filament that regulates cell attachment and subcellular organization. In this study, vimentin filaments were morphologically altered, and its soluble subunits were rapidly reduced via cadmium chloride treatment. Cadmium chloride stimulated three major mitogen-activated protein kinases (MAPKs): extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK), and p38, and led apoptotic pathway via caspase-9 and caspase-3 activations. In order to determine whether MAPKs were involved in this cadmium-induced soluble vimentin disappearance, we applied MAPK-specific inhibitors (PD98059, SP600125, SB203580). These inhibitors did not abolish the cadmium-induced soluble vimentin disappearance. Caspase and proteosome degradation pathway were also not involved in soluble vimentin disappearance. When we observed vimentin levels in soluble and insoluble fractions, soluble vimentin subunits shifted to an insoluble fraction. As we discovered that heat-shock protein 27 (HSP27) was colocalized and physically associated with vimentin in unstressed cells, the roles of HSP27 with regard to vimentin were assessed. HSP27-overexpressing cells prevented morphological alterations of the vimentin filaments, as well as reductions of soluble vimentin, in the cadmium-treated cells. Moreover, HSP27 antisense oligonucleotide augmented these cadmium-induced changes in vimentin. These findings indicate that HSP27 prevents disruption of the vimentin intermediate filament networks and soluble vimentin disappearance, by virtue of its physical interaction with vimentin in cadmium-treated SK-N-SH cells. 相似文献
60.
Lead is extracted from urine with ammonium pyrrolidien dithiocrbamate into methyl isobutyl ketone, and 20 μl of the extract is injected into a water carrier stream in a flow-injection/atomic absorption system. The procedure is simple, quick, accurate and reproducible. Recoveries are 96–105%. The mean urine lead contents of 20 unexposed and 20 printing-press lead exposed workers was found to be 39.0 ± 8.3 and 71.7 ± 26.3 μg Pb l?1, respectively. 相似文献