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81.
Raul F. Velasco César Guerrero Gloria Fra Alejandra Moure Juan Miguel-Siles Maria Teresa Quesada-Campos Jose Ramon Ruiz-Gomez Ian H. Gilbert Michael G. Thomas Timothy J. Miles 《Tetrahedron letters》2019,60(18):1243-1247
During the course of a research program aimed at identifying novel antileishmanial compounds, a multi-gram synthesis of N-(trans-4-((4-methoxy-3-((R)-3-methylmorpholino)-1H-pyrazolo[3,4-d]pyrimidin-6-yl)amino)cyclohexyl)-2-methylpropane-1-sulfonamide ((R)-1) was required. This letter describes optimisation of the reaction conditions and protecting group strategy for a key Buchwald-Hartwig coupling, delivering the required quantities of (R)-1, as well as further compounds in the series. 相似文献
82.
Irradiation of phenothiazine cation radical, Ph.+, with 1,1-diphenylethylene, DPE, causes its reduction to Ph and oxidation of DPE. Cyclodimeric products are formed from DPE.+. 相似文献
83.
In the majority of the literature describing green coloured materials used on ancient painting layers (15th or 16th century), two copper greens are mainly cited: malachite [CuCOr3 x Cu(OH)2] and verdigris [Cu(CH3COO)2 x [Cu(OH)2]3 x 2H2O]. It is shown, by micro-Raman spectroscopy, that the artists were actually employing more than these two copper greens, in particular various copper sulfates, among which the most common pigment found is posnjakite [CuSO4 x 3Cu(OH)2 x H2O]. In contrast to the PIXE (particle induced X-ray emission) technique, Raman spectroscopy is a technique of choice, able to distinguish not only a copper sulfate from a carbonate or acetate but also the different sulfates themselves; in this respect, we found that the high wavenumber region (2800-4000 cm(-1)), characteristic of H2O vibrations, is of particular interest. It is also shown that numerous green areas were created with mixtures of a copper sulfate mixed with other pigments, for instance to enhance the colour depth. Finally, in some cases, no green pigment is actually employed but the colour is obtained by intimately mixing yellow and blue pigments. All these results led to a new look at the pigments which were in use on the palettes of the ancient artists. 相似文献
84.
Lambert C Nöll G Zabel M Hampel F Schmälzlin E Bräuchle C Meerholz K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4232-4239
Two highly substituted azulene derivatives were synthesised by Pd-mediated dimerisation from the corresponding tolan species. One azulene derivative (2) has donor functionalities (dianisylaminophenyl and dianisylamino) in the 1-, 2-, 3- and 6-positions, while the other (1) has donors (dianisylaminophenyl) in the 2- and 6-positions and acceptors (nitrophenyl) in the 1- and 3-positions. Each azulene derivative shows strong bond length alternation in the solid state, determined by X-ray crystal analysis, and an intense CT band around 450-500 nm in its UV/Vis spectrum. The first-order hyperpolarisability of 1 and of 2 was measured by hyper-Rayleigh scattering and is about that of disperse red DR1. Both azulene derivatives show multiple oxidation processes. The intramolecular adiabatic ET behaviour of the mixed valence radical cations of 1 and of 2 was investigated by UV/Vis/NIR spectroelectrochemistry. The intervalence-CT band of 1(+) could be analysed by the Generalised Mulliken-Hush theory, which yields an electronic coupling V=1140 cm(-1) for the optically induced adiabatic hole transfer. 相似文献
85.
M. J. Whitcombe A. Gilbert A. Hirai G. R. Mitchell 《Journal of polymer science. Part A, Polymer chemistry》1991,29(2):251-259
The synthesis of methacrylate esters of 4-cyanophenyl-(4-(ω-hydroxyalkyloxy)) cinnamates, with spacer lengths of 2 and 6 methylene units and the synthesis of the corresponding acrylate ester with a spacer of 2 methylene units are described. The methacrylate monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with the analogous benzoate monomer of spacer length 6. The acrylate ester could not be polymerized successfully under the same reaction conditions. Polymers were characterized by NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermo-optic observations. Of the monomers prepared, only the cinnamate with a hexamethylene spacer shows a mesophase, seen on supercooling of the melt. All of the polymers prepared were liquid crystalline, with smectic behavior predominating in the polymethacrylates with the longer spacer group. A narrow nematic region is seen just below the clearing temperature with a range of 3–9°C, nematic character is increased in the copolymer series with the degree of incorporation of the cinnamate monomer with the spacer group of length 2. 相似文献
86.
A commercially available system is described for the fully automated clean-up and high-performance liquid chromatographic (HPLC) analysis of aflatoxins in foods and animal feeds. The system marketed primarily for handling solid-phase extraction columns has modified software to facilitate use with immunoaffinity columns. Sample extract clean-up followed by injection onto an HPLC column with post-column iodination and fluorescence detection is carried out completely unattended. A coefficient of variation of 5.1% for aflatoxin B1 analysis was obtained, and the accuracy of the system was demonstrated by the analysis of peanut butter certified reference material. 相似文献
87.
The present paper deals with the experimental and theoretical determination of energies of conjugation of organic molecules.A computation process has been applied, first to simple molecules comprising an hydrocarbon (styrene), an oxygen function (benzaldehyde) and a nitrogen function (aniline). The results are compared with those obtained from the literature.The application of this computation process to naphthoic acids permits the determination of energies of conjugation and isomerization of these molecules. 相似文献
88.
We report on the use of EPR spectroscopy and spin trapping technique to detect free radical intermediates formed in the presence of gold nanoparticles. Phosphine- and amine-protected gold nanoparticles were found to initiate air oxidation of organic substrates containing active hydrogen atoms, such as amines and phosphine oxides. Nanoparticles protected by stronger bound ligands (e.g., thiols) were inactive in these reactions. We also found that gold nanoparticles are able to abstract a halogen atom from the halogenated compounds, presumably due to the high affinity of gold metal for halogens. Reaction of Au nanoparticles with chloroform showed an unusual inverse isotope effect. The trichloromethyl spin adduct was observed when Au nanoparticles were mixed with CDCl(3) but not with CHCl(3). This unexpected behaviour suggests that C-H bond breaking is not the rate-determining step in Au-initiated hydrogen abstraction. 相似文献
89.
Imine 7 of 1,4-cyclohexanedione mono-ethylene ketal 6 was reacted with maleic anhydride, affording the cyclized adduct 8. Methyl esterification of 8, accompanied by transacetalization, led to the dihydrooxindole derivative 10. Aromatization of 10 was then accomplished with POCl(3), leading directly to the key-intermediate title compound 11 in 74% yield from ketone 6. Serotonin, melatonin, and bufotenin were then obtained by standard reactions. 相似文献
90.
Synthesis of grafting silane on a hydro soluble cellulose ether (HPMC) was described. In alkaline medium, this derivate is under gel form. With a decrease of the pH, a self-hardening occurs due to the silanol condensation. For potential biomedical use, we described the silated-HPMC synthesis, the gel behavior after steam sterilization and the parameters of the silanol condensation i.e. pH, silane percentage and temperature. Minimum kinetic of the condensation was observed for pH between 5.5 and 6.5. So temperature catalyzed the reaction and the self-hardening speed was increased by silane percentage. 相似文献