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61.
Neil Burford Jack Passmore Xiaoping Sun 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):487-488
62.
Neil B. Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2001,39(19):3311-3319
We used real‐time Fourier transform infrared to monitor the conversion of both thiol and ene (vinyl) functional groups independently during photoinduced thiol–ene photopolymerizations. From these results, the stoichiometry of various thiol–ene and thiol–acrylate polymerizations was determined. For thiol–ene polymerizations, the conversion of ene functional groups was up to 15% greater than the conversion of thiol functional groups. For stoichiometric thiol–acrylate polymerizations, the conversion of the acrylate functional groups was roughly twice that of the thiol functional groups. With kinetic expressions for thiol–acrylate polymerizations, the acrylate propagation kinetic constant was found to be 1.5 times greater than the rate constant for hydrogen abstraction from the thiol. Conversions of thiol–acrylate systems of various initial stoichiometries were successfully predicted with this ratio of propagation and chain‐transfer kinetic constants. Thiol–acrylate systems with different initial stoichiometries exhibited diverse network properties. Thiol–ene systems were initiated with benzophenone and 2,2‐dimethoxy‐2‐phenylacetophenone as initiators and were also polymerized without a photoinitiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3311–3319, 2001 相似文献
63.
64.
A simple, rapid determination is reported for danthron (1,8-dihydroxyanthraquinone) in pharmaceutical tablets. In a flow-injection system, danthron is reduced by sodium dithionite in methanol/borate buffer to give a fluorescent complex. Linearity ranges from 30 μg ml?1 to below 0.1 μg ml?1. In urine samples, danthron is separated from other fluorescing species by reversed-phase high-performance liquid chromatography before its reduction by dithionite in a post-column reactor. Urine preparation requires no extraction. Spiked urine samples were studied in the working range of 0.02–2.0 μg ml?1 danthron. 相似文献
65.
Summary Benzothiazole-2-selenone, BTSeH, was prepared by treating 2-chlorobenzothiazole with Na2Se, and the 6-ethoxy analogue (EtOBTSeH) was obtained similarly. From BTSeH, the species [R4N][BTSe] (R=Me, Et Bu-n), Zn-(BTSe)2(pyr)2, (BTSe–)2, Zn(BTSe-)2I2 and Me2C=CH-CH(SSeTB)Me were obtained. Addition of [n-Bu4N] [BTSe] to [Zn(BTSe)2]
n
afforded [n-Bu4N] [Zn(BTSe)3(H2O)]. The Se n.m.r. spectra of these species are briefly reported. 相似文献
66.
Huters AD Quasdorf KW Styduhar ED Garg NK 《Journal of the American Chemical Society》2011,133(40):15797-15799
We report the first total synthesis of (-)-N-methylwelwitindolinone C isothiocyanate. Our route features a number of key transformations, including an indolyne cyclization to assemble the [4.3.1]-bicyclic scaffold, as well as a late-stage intramolecular nitrene insertion to functionalize the C11 bridgehead carbon en route to the natural product. 相似文献
67.
Grainger RS Patel B Kariuki BM Male L Spencer N 《Journal of the American Chemical Society》2011,133(15):5843-5852
Three peri-substituted trisulfide-2-oxides are prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine. The 1,2,3-trithiane-2-oxide ring adopts a sofa conformation in the solid state, with a pseudoaxial oxygen and evidence of ring strain (peri-interaction). Heating the trisulfide-2-oxides in the presence of a diene results in formal sulfur monoxide (SO) transfer to form unsaturated cyclic sulfoxides, along with a recyclable 1,8-naphthalene disulfide. The presence of o-methoxy or o-tert-butyl substituents on the naphthalene ring lowers the temperature and increases the rate at which SO transfer occurs. Trapping experiments and kinetic studies are consistent with the generation of triplet SO, followed by in situ trapping by diene. Transfer of SO also occurs upon irradiation at room temperature, but yields of sulfoxide are lower. Dehydration of the sulfoxides under Pummerer conditions gives thiophenes, including the naturally occurring thioperillene. Two dienes form thiophenes directly under the SO transfer conditions. The methodology is applied in a formal synthesis of the antiplatelet medication Plavix. 相似文献
68.
A nonribosomal peptide synthetase-like enzyme (NRPS325) from Aspergillus terreus was reconstituted in vitro and was shown to synthesize thiopyrazines using an unprecedented mechanism. Substrate promiscuity of NRPS325 toward different amino acids and free thiols was explored to produce >60 different thiopyrazine compounds. 相似文献
69.
Quasdorf KW Huters AD Lodewyk MW Tantillo DJ Garg NK 《Journal of the American Chemical Society》2012,134(3):1396-1399
We report the total synthesis of (-)-N-methylwelwitindolinone C isonitrile, in addition to the total syntheses of the 3-hydroxylated welwitindolinones. Our routes to these elusive natural products feature the strategic use of a deuterium kinetic isotope effect to improve the efficiency of a late-stage nitrene insertion reaction. We also provide a computational prediction for the stereochemical configuration at C3 of the hydroxylated welwitindolinones, which was confirmed by experimental studies. 相似文献
70.
Gandon LA Russell AG Güveli T Brodwolf AE Kariuki BM Spencer N Snaith JS 《The Journal of organic chemistry》2006,71(14):5198-5207
A novel approach to 2,4-disubstituted piperidines is reported, involving the radical cyclization of 7-substituted-6-aza-8-bromooct-2-enoates. Cyclization with tributyltin hydride affords the trans piperidines with trans/cis diastereomeric ratios ranging typically from 3:1 to 6:1. Cyclization with tris(trimethylsilyl)silane affords the same products with diastereomeric ratios of up to 99:1 in certain cases. The enhancement in diastereoselectivity results from the selective rearrangement of the minor stereoisomer through a cascade process involving radical cyclization to the piperidine radical, 1,5-radical translocation, and attack of the translocated radical onto the sulfonamide with extrusion of SO2 in a Smiles-type rearrangement. Slower trapping of the piperidine radical by tris(trimethylsilyl)silane compared to tributyltin hydride accounts for the occurrence of the rearrangement cascade in the former case. 相似文献