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71.
新型螺环单体的合成和自由基聚合反应的研究王宏鲁剑涛冯品珍(中国科学技术大学研究生院化学部北京100039)关键词自由基聚合,新单体合成,螺环单体,自由基共聚虽然离子型开环聚合早已为人熟知,但是自由基开环聚合反应的研究和应用开发还刚刚起步.... 相似文献
72.
Yoshitaka Uenoyama Takahide Fukuyama Keisuke Morimoto Osamu Nobuta Hidefumi Nagai Ilhyong Ryu 《Helvetica chimica acta》2006,89(10):2483-2494
The carbonylation of alkanes 1 under radical‐reaction conditions was examined by using ethynyl triflone A as the unimolecular chain‐transfer (UMCT) reagent. Good to moderate yields of ethynyl ketones 2 were prepared by means of this three‐component coupling reaction. Higher CO pressures as well as lower concentrations of triflone A improved the efficiency of the reaction over the direct addition, the latter leading to alkylated ethynes 3 . In contrast to the reaction with A , the reaction of cyclohexane ( 1a ) with allyl triflone B (= ethyl 2‐methylene‐3‐[(trifluoromethyl)sulfonyl]propanoate) in the presence of CO gave a mixture of carbonylation products, including 8a formed from two molecules each of cyclohexane, CO, and allyl triflone B . 相似文献
73.
The stabilization modification of the halogen end groups of polystyrene prepared by atom transfer radical polymerization (ATRP) has been attempted. The reaction mechanism adopted is radical chain transfer reaction, and iso-propylbenzene is employed as not only the chain transfer agent but also the solvent. Moreover, Cu0 is used as the acceptor of the transformed halogen atom in some experiments. As evidenced by 1H NMR analysis of the modified products, the halogen end group can really be converted into the much more stable carbon-hydrogen structure. When Cu0 is not used, the conversion of the halogen end groups rises rapidly during the early stage and the increase rate slows down after about 8 h reaction. In view of the influence of reaction temperature on the modification, the conversion increases almost exponentially with temperature in the range of 80-100 °C, and the increase rate slows down at higher temperature. 1H NMR and SEC analyses prove that the modification reaction does not destroy the polymer backbone and the molecular weights remain almost the same as those of the unmodified samples. When Cu0 is introduced, the modification reaction proceeds much rapidly, the conversion of the halogen end groups rises almost linearly at the early stage and the nearly complete (>95%) dehalogenation of the polymeric chains is observed after only 12 h reaction. However, the molecular weights rise and the polydispersities become wider after the modification, which implies that the modification is accompanied with the couple termination of the polystyrene radicals besides chain transfer reaction. Furthermore, the couple termination can be restrained at some lower catalyst concentration. Indeed, the modified polymers show improved thermal stability, the initial weight loss temperatures is increased from 196 °C to 378 °C for the linear polystyrene and from 203 °C to 261 °C for the hyperbranched polystyrene. 相似文献
74.
Oxidative free radical reactions of enamino esters are described. Electrophilic carbon-centered radicals produced by the cerium(IV) ammonium nitrate (CAN) oxidation of β-dicarbonyl compounds undergo efficient addition to the C-C double bond of enamino esters. This CAN mediated free radical reaction between enamino esters and β-dicarbonyl compounds provides a novel method for the synthesis of highly substituted pyrroles. The direct CAN oxidation of β-enaminocinnamates gave the dimerization products effectively. 相似文献
75.
76.
Electrochemical Oxidation of Quercetin 总被引:1,自引:0,他引:1
《Electroanalysis》2003,15(22):1745-1750
The mechanism of electrochemical oxidation of quercetin on a glassy carbon electrode has been studied using cyclic, differential pulse and square‐wave voltammetry at different pH. It proceeds in a cascade mechanism, related with the two catechol hydroxyl groups and the other three hydroxyl groups which all present electroactivity, and the oxidation is pH dependent. Quercetin also adsorbs strongly on the electrode surface; and the final oxidation product is not electroactive and blocks the electrode surface. The oxidation of the catechol 3′,4′‐dihydroxyl electron‐donating groups, occurs first, at very low positive potentials, and is a two electron two proton reversible reaction. The hydroxyl group oxidized next was shown to undergo an irreversible oxidation reaction, and this hydroxyl group can form a intermolecular hydrogen bond with the neighboring oxygen. The other two hydroxyl groups also have an electron donating effect and their oxidation is reversible. 相似文献
77.
Various amounts of n-alkylbenzenes (Cn: C6H5-CnH2n+1 (n = 3-16)) were doped into poly(methyl methacrylate) (PMMA) films, and the emission and thermal properties of each film were measured in detail together with their solid-state 13C NMR spectra. The aim of the present work was to estimate the size distribution of free volume in amorphous regions of polymer solids heavily doped with plasticizers by using Cn as models of a plasticizer. The excimer fluorescence yields of Cn in PMMA were found to depend on both the amount of Cn and the length of the alkyl chains of Cn, although the fluorescence spectra of all of the Cns in dilute fluid solution were almost the same. The quantitative analysis showed: (1) Cn with n ? 12 induces a phase separation in PMMA, in which almost all of the Cn molecules are in a separated phase, and thus they cannot penetrate regions in which PMMA chains are aggregated. This means that Cn with n ? 12 cannot enlarge the space between PMMA chains. (2) Smaller Cn (n < 11) can enter free volumes between PMMA chains that correspond to their molecular size, but they can enlarge them only to a limited extent. Thus, the amount by which plasticization can increase the free volume of PMMA is limited by the size of the dopant and the inherent free volume of the polymer matrix. (3) The efficiency of excimer formation was found to reveal the maximum amount of Cn that could fit in the free volume of PMMA. Thus our fluorescence measurements showed that PMMA solids that were plasticized to their limit had a free volume that was larger than the volume occupied by all the conformers of C5 and smaller than the volume occupied by almost all the conformers of C12. In conclusion, we were able to obtain information on plasticization and to demonstrate a method of monitoring microenvironments in polymer solids after they have been doped with plasticizers. 相似文献
78.
Evaluation of free hydroxyl radical scavenging activities of some Chinese herbs by capillary zone electrophoresis with amperometric detection 总被引:2,自引:0,他引:2
Due to the severe damage caused by free hydroxyl radicals (OH·) to cells and tissues, there is much interest in finding and studying effective and non-toxic OH· scavengers, including traditional Chinese herbs. In this paper, the simple and highly-sensitive technique of capillary zone electrophoresis with amperometric detection (CZE-AD) was used to study the OH· scavenging activities of aqueous extracts from some traditional Chinese herbs. Salicylic acid (SAL) was used as an OH· trap, and the content of OH· could be determined by assaying their products, 2,3-dihydroxybenzoic acid (2,3-DHBA) and 2,5-dihydroxybenzoic acid (2,5-DHBA). The optimum conditions for CZE-AD for the determination of 2,3-DHBA and 2,5-DHBA were explored. The linearity ranges of 2,3-DHBA and 2,5-DHBA were 1.0 ×10–7~1.0 ×10–4 mol L–1, and their detection limits were as low as 2×10–8 mol L–1, which were much better than the CE-UV method often used. The traditional Chinese herbs studied included Radix angelicae sinensis, Rhizoma coptidis, Ligustrum lucidum, Ligusticum wallichii, Radices glycyrrhizae and Semen plantaginis. The experiments showed that the aqueous extracts from all of the above traditional Chinese herds had free OH· scavenging activities, although to different degrees. 相似文献
79.
Carmen R. Alonso-Cruz Francisco J. Ortiz-López Ernesto Suárez 《Tetrahedron letters》2005,46(32):5265-5268
The reaction of derivatives of 3-acetyl-d-glucal, 3-acetyl-l-rhamnal, 3-acetyl-d-galactal, and 3-acetyl-d-lactal with sodium benzenesulfinate in acid medium catalyzed by HgSO4 afforded diastereoisomeric mixtures of the corresponding 2,3-dideoxy-3-(phenylsulfonyl)-hexopyranoses through a Ferrier rearrangement. The anomeric alkoxyl radical fragmentation of these γ-hydroxy sulfones using the system (diacetoxyiodo)benzene and iodine gave vinyl sulfones with structures of 1,2-dideoxy-4-O-formyl-2-(phenylsulfonyl)-pent-1-enitol and configurations d-erythro, l-erythro, and d-threo at the two stereogenic centers. 相似文献
80.
The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases. 相似文献