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31.
Leibold C Alvarez RM Cutin EH Della Vedova CO Oberhammer H 《Inorganic chemistry》2003,42(13):4071-4075
The IR (gas) and Raman (liquid) spectra of FC(O)NSCl(2) demonstrate the presence of a conformational mixture in both phases. According to a gas electron diffraction study, the main conformer (94(8)%) possesses a syn-syn structure (C(O)F group synperiplanar with respect to the SCl(2) bisector and the C=O bond synperiplanar to the N=S bond). Quantum chemical calculations (HF, B3LYP and MP2 with 6-31G basis set, and MP2/6-311(2df)) predict a syn-anti structure for the second conformer. Analysis of the IR (gas) spectrum results in a contribution of 5(1)% of the minor form, corresponding to a Gibbs free energy difference DeltaG degrees = G degrees (syn-anti) - G degrees (syn-syn) = 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electron correlation effects (DeltaG degrees = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (DeltaG degrees = 3.24 kcal/mol). 相似文献
32.
The new compound trifluoroacetylsulfenyl trifluoroacetate, CF(3)C(O)SOC(O)CF(3), which possesses two identical carbonyl substituents attached to the S-O bond, has been synthesized. The IR and UV spectra of the gas phase as well as the (13)C NMR spectrum of the solution in CDCl(3) were recorded and assigned. Quantum chemical calculations were performed with the ab initio methods HF and MP2 and the density functional approach B3LYP. The 6-31G basis set was chosen in all calculations. The molecule possesses a skew structure, and according to all computational methods, the syn-syn structure (C=O bonds of both C(O)CF(3) groups synperiplanar to S-O bond) represents the most stable conformer. In agreement with the quantum chemical calculations, the presence of small amounts (< or =5%) of a second conformer (anti-syn) cannot be excluded on the basis of the IR spectrum. The calculated values for the torsional angle around the S-O bond (delta(C-S-O-C)) of the syn-syn form are smaller than 80 degrees (72-78 degrees). Comparison with theoretical results for the corresponding disulfide CF(3)C(O)SSC(O)CF(3) and peroxide CF(3)C(O)OOC(O)CF(3) indicates that the structural properties of sulfenyl compounds are more similar to those of disulfides than to those of peroxides. 相似文献
33.
Romualdo Caputo Marina Della Greca Luigi Longobardo Gabriella Pinto 《Tetrahedron letters》2007,48(8):1425-1427
The general synthesis of a new class of non-natural diamino acids, 2-amino-3-[(2′-aminoalkyl)seleno]propanoic acids, or Se-(aminoalkyl)selenocysteines, is reported. Under the conditions devised, enantiopure N-Boc-protected β-l-iodoamines, which are readily generated from proteinogenic α-amino acids, were treated with the selenolate anion obtained from NaBH4 splitting of the Se-Se bond in commercial l-selenocystine. The Se-alkylation products were enantiomerically pure and the reaction is high yielding (92-98%), without any detectable traces of accompanying by-products. 相似文献
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The (17R,20S,22S,24S) C20-C29 segment of contignasterol has been stereoselectively prepared in 8 steps and 40% overall yield from (S)-carvone. Synthetic studies towards contignasterol's C/D ring functionalization/isomerization are also reported. 相似文献
36.
D. Drijard H. G. Fischer W. Geist P. G. Innocenti V. Korbel A. Minten A. Norton S. Stein O. Ullaland H. D. Wahl G. Fontaine C. Ghesquière G. Sajot P. Hanke W. Hofmann M. Panter K. Rauschnabel J. Spengler D. Wegener H. Frehse M. Heiden E. E. Kluge A. Putzer M. Della Negra D. Linglin R. Gokieli R. Sosnowski 《Zeitschrift fur Physik C Particles and Fields》1981,9(4):293-303
Inclusive production of ?0,f, andg 0 mesons and ofK s 0 ,K *0 (892), ? andK *0(1430)mesons has been measured at <y>~2.6 and <p T >~1.1 GeV/c in proton-proton interactions at \(\sqrt s = 52.5\) GeV. The negative particle from the two-body decays of these resonances were identified by a threshold Cerenkov counter and used for triggering. Starting from the measured differential cross section, total inclusive cross sections for the vector and tensor mesons were determined using various parametrizations for they andp T dependence of the differential cross section. The experimental results are discussed in the framework of production models based on the parton picture. The strangeness suppresion factor λ=(0.30±0.10) due toSU(3) symmetry breaking of the quark sea is derived. 相似文献
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39.
L. Hedjazi C.L. Martin S. Guessasma G. Della Valle R. Dendievel 《International Journal of Solids and Structures》2012,49(13):1893-1899
Crack propagation in a vitreous biopolymer material is simulated using the Discrete Element Method (DEM), which models the brittle material as an assembly of particles bonded together. The simulations are compared to experiments combining a high-speed camera monitoring of crack branching together with a micromechancial testing of samples where local mixture mode is generated by introducing a stress concentrator. Our experimental results show unstable crack propagation and branching occurring upon crack deviation by the action of the stress concentrator. The validity of the DEM simulations is checked by comparing its result to the Finite Element Method (FEM) and to an analytical expression under similar conditions. DEM results show a higher sensitivity to mixed mode compared to FEM and a better match with the analytical formulation. Finally, crack branching is correctly predicted using DEM without any specific criterion for the initiation of secondary cracks. 相似文献