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121.
Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.2 Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.3 The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report 相似文献
122.
The title compound was obtained from 1,3-dichloro-adamantane and some silylating reagents with Na-HMPA. 相似文献
123.
124.
Masahito Segi Hiroaki Yamamoto Takeyoshi Hori Tadashi Nakajima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):599-602
Selenoaldehydes and selenoketones, generated by thermal retro-Diels-Alder reaction of their cycloadducts with cyclopentadiene, reacted with oxygen-functionalized conjugated dienes such as 1-acetoxy-1,3-butadiene, Danishefsky's diene, and 1,4-diacetoxy-1,3-butadiene to give the corresponding cycloadducts in good yields regioselectively. 相似文献
125.
Tadashi Kataoka Hironori Kinoshita 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):989-992
Abstract The Chalcogeno-Morita-Baylis-Hillman reaction was achieved by the reactions of 2-(methylchalcogeno)phenyl vinyl ketones with carbonyl compounds or acetals in the presence of BF3· Et2O. This reaction proceeds via the intramolecular Michael addition of the chalcogenide group to an enone moiety followed by the aldol reaction of the resulting chalcogenonio-enolate with an aldehyde. The reactions were worked up with triethylamine or saturated aqueous NaHCO3 to give the α -methylene aldols (the Morita-Baylis-Hillman adducts). 相似文献
126.
Caterina Fraschetti Antonello Filippi Maria Elisa Crestoni Tadashi Ema Maurizio Speranza 《Journal of the American Society for Mass Spectrometry》2013,24(4):573-578
The most common protocols for the quantitative determination of the enantiomeric excess (ee) of raw mixtures by ESI-MS reveal inadequate in cases where the distribution of diastereomeric derivatives diverges from the ee of original solutions. This phenomenon is attributable to a matrix effect, i.e., to the stereospecific formation of high order noncovalent adducts in the ESI droplets, which alters the actual availability of the diastereomeric species under MS analysis. In this frame, the assumption of classic protocols that the ionization correction factor q is independent on the composition of the mixture submitted to analysis is questionable. An alternative methodology is presented in this paper, which is aimed at circumventing the problem by excluding any chemical derivatization of the original raw mixture. It is based on the measurement of the actual distribution of ESI-formed proton-bound diastereomeric complexes from the enantiomeric mixture through a careful analysis of their reaction kinetics with a suitable reactant. 相似文献
127.
Abstract In this study, the formation of polyion complex micelles from a pair of poly(L-lysine) homopolymers (P(Lys)) and poly(ethylene glycol)-poly(aspartic acid) block copolymers (PEG-P(Asp)) with varying chain length was demonstrated in aqueous medium. There exists the lower critical chain length in the charged segments of both P(Lys) and PEG-P(Asp) to form stable polyion complex micelles in nanometric scale. The scaled average characteristic line width (ΓTK2) was independent on the detection angles for all combinations, suggesting that the formed polyion complex micelles may have a spherical shape. Furthermore, the transitional diffusion coefficient (DT) had no concentration dependence, indicating the micelle system was free from secondary aggregates (the cluster of micelles). It is of interest that the micellar size was almost constant (ca. 50 nm) regardless of the change in the chain length of the charged segments. Size distribution was extremely narrow, and the values of variance μ2/Γ 2) were always less than 0.1. Laser-Doppler electrophoresis measurements revealed that the polyion complex micelles were electrically neutral, suggesting that the PEG corona surrounding the polyion complex core may contribute to their stable dispersion in an aqueous medium through steric repulsion of the tethered hydrophilic chain, in this case, PEG. This system was considerably stable against the change in ionic strength, and it maintained a constant diameter in the region below 0.4 M NaCl. However, they dissociated under high ionic strength condition as 0.6 M NaCl. The system may have potential utility to include charged peptides and nucleotides in the core, delivering these biologically useful substances into a target site in the body. 相似文献
128.
Takayoshi Kimura Tasunori Suzuki Keisuke Takata Akina Soga Yutsa Nomoto Tadashi Kamiyama Yousuke Nakai Hideo Matsui Masao Fujisawa 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1467-1474
The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K 1 expressed in terms of mole fractions and standard thermodynamic properties of formation (Δf H, Δf G, Δf S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group. 相似文献
129.
Tatsunori Iwamura Takashi Ichikawa Hiroshi Shimizu Tadashi Kataoka 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):471-472
Abstract Reactions of thiazolo[3,2-b]-1,2,4-triazolium N-methylides with electron-deficient acetylenes gave the thiazole ring-opened products as a mixture of the E-and Z-isomers. In contrast, the N-phenacylides reacted with dimethyl acetylenedicarboxylate to give the thiobenzoates together with the thiazole ring-opened products. The mechanism for formation of these compounds is described. 相似文献
130.
Kenichiro Todoroki Hiroki Hashimoto Kazuyuki Machida Miki Itoyama Tadashi Hayama Hideyuki Yoshida Hitoshi Nohta Manabu Nakashima Masatoshi Yamaguchi 《Journal of separation science》2013,36(2):232-238
In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control. 相似文献