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81.
Stuart Lang Neil Muir Franziska Schönebeck Andrew H. Payne 《Tetrahedron letters》2005,46(23):4027-4030
The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields. 相似文献
82.
C. I. J. M. Stuart 《Foundations of Physics Letters》1991,4(5):479-492
Aprediction puzzle leads to a form ofnecessary realism which forces the rejection of a central tenet of the Copenhagen interpretation. This leads to reconsidering conceptual difficulties related to Bell's locality premise. It is shown that aparadox of elementary probability theory puts new light on Bell's assumption that causality and statistical independence are mutually incompatible.
Nemo dat quod non habet : No one can offer more than he has ability to give; in that spirit, this paper is dedicated to the memory of J.S. Bell. 相似文献
83.
David M. A. Stuart 《Communications in Mathematical Physics》1992,149(3):433-462
In this paper we prove the validity of formal asymptotic results on perturbation theory for kind solutions of the sine-Gordon equation, originally obtained by McLaughlin and Scott. We prove that for appropriate perturbations, of size in an appropriate norm, slowly varying in time in the rest frame of the kink, the shape of the kink is unaltered in theL
norm toO() for a time ofO(1/). The kink parameters, which represent its velocity and centre, evolve slowly in time in the way predicted by the asymptotics. The method of proof uses an orthogonal decomposition of the solution into an oscillatory part and a one-dimensional zero-mode term. The slow evolution of the kink parameters is chosen so as to suppress secular evolution of the zero-mode.Partially supported as a graduate student at Princeton University of NSF grant 215 6211 相似文献
84.
Microwave transitions up to J = 53 in the ground vibrational state of deuterothioformaldehyde, CD2S, were studied between 8 and 40 GHz. A detailed centrifugal distortion analysis yields accurate constants for comparison with force field values. The isotopic species 13CH2S, CH234S, CH233S, 13CD2S, CD234S, and CD233S were studied in natural abundance. Accurate average zero-point structures were determined for both CD2S and CH2S: Changes in the zero-point geometry for deuterium substitution were established. Quadrupole fine structure arising from the 33S nucleus has been measured in CH233S and CD233S. Analysis gives the following coupling constants (for both molecules) as χaa = ?11.7 and χbb - χcc = 88.1 MHz. The dipole moment of CD2S was measured to be 1.6588(8)D and an accurate comparison with CH2S was made; the ratio of dipole moments was found to be 1.0062(4). The spectroscopic and bonding properties of CH2S will be compared with formaldehyde and other molecules. 相似文献
85.
Ignatov SK Rees NH Tyrrell BR Dubberley SR Razuvaev AG Mountford P Nikonov GI 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):4991-4999
The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction. 相似文献
86.
Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties 总被引:1,自引:0,他引:1
Christopher M. Timperley Robert E. Arbon Michael Bird Stuart A. Brewer Malcolm W. Parry David J. Sellers Colin R. Willis 《Journal of fluorine chemistry》2003,121(1):23-31
Ten fluoromonomers of structure (RFO)2P(O)OCH2CH2OC(O)CRCH2 were made in 30-64% yield by treating the chloridates (RFO)2P(O)Cl with HOCH2CH2OC(O)CRCH2 in chloroform in the presence of triethylamine [RF=CF3CH2, C2F5CH2, C3F7CH2, C4F9CH2, C4F9CH2CH2 or C6F13CH2CH2; R H or Me]. The chloromonomer (CCl3CH2O)2P(O)OCH2CH2OC(O)CHCH2 was obtained analogously in 29% yield. Polymerisation of the acrylate monomers, but not the methacrylate monomers, could be effected using α-azoisobutyronitrile as a radical initiator. Acrylic polymers having CF3CH2O, CCl3CH2O and C6F13CH2CH2O side-chains were obtained as translucent rubbers. Specimens of cotton fabric were treated with solutions of the polymers, and average water and oil repellency ratings measured. Fabric coated with the polymer with the C6F13CH2CH2O side-chain afforded protection from penetration of the test liquids. Treated fabrics were subjected to the limiting oxygen index (LOI) test according to BS EN ISO 4589-2 (1999): this test determines the point at which a material just burns in a volumetric flow of oxygen and nitrogen. The treated fabrics were more fire-resistant (LOI 22-29%) than the untreated fabric (LOI 18%). Fabric coated with the CCl3CH2O-based polymer can be considered fire-retardant (LOI 29%). The fluoromonomers were tested for anti-acetylcholinesterase activity and were found to be poor enzyme inhibitors; they are predicted to possess low acute toxicity. 相似文献
87.
van der Gucht J Besseling NA Cohen Stuart MA 《Journal of the American Chemical Society》2002,124(21):6202-6205
The effects of supramolecular equilibrium polymers on surface forces are studied by both a phenomenological Landau type analysis and a molecular model based on a Bethe-Guggenheim approximation. We point out that surface forces brought about by equilibrium polymers may be completely different from what can be found with "ordinary" polymers. The new feature is the role of inversion (a)symmetry or "directionality" of the associating unit molecules ("monomers"). Symmetric B-B monomers (where B denotes a self-complementary binding group) give rise to nondirectional chains and lead to attractive forces between similar surfaces. Asymmetric A-D monomers (where A and D denote complementary acceptor and donor groups, respectively) produce directional chains and can cause strong repulsion. The range of the attractive force has a maximum at intermediate concentration, while the range of the repulsive force increases over the whole concentration range. 相似文献
88.
Spring DR Krishnan S Blackwell HE Schreiber SL 《Journal of the American Chemical Society》2002,124(7):1354-1363
Diversity-oriented synthesis of structurally complex and diverse small molecules can be used as the first step in a process to explore cellular and organismal pathways. The success of this process is likely going to be dependent on advances in the synthesis of small molecules having natural product-like structures in an efficient and stereoselective manner. The development, scope, and mechanism of the oxidation of organocuprates was investigated and exploited in the atropdiastereoselective synthesis of biaryl-containing medium rings (9-, 10-, and 11-membered rings). The methodology was performed on high-capacity, large polystyrene beads by metalating aryl bromides with i-PrBu(2)MgLi, followed by transmetalating with CuCN x 2LiBr and then oxidizing with 1,3-dinitrobenzene, and was used in a diversity-oriented synthesis of biaryl-containing medium rings (library total theoretical maximum 1412 members). The high capacity beads were arrayed into 384-well plates and, using a process optimized during the development of a one bead/one stock solution technology platform, converted into arrays of stock solutions, with each stock solution containing largely one compound. These stock solutions were used in numerous phenotypic and protein-binding assays. The process described outlines a pathway that we feel will contribute to a comprehensive and systematic chemical approach to exploring biology (chemical genetics). 相似文献
89.
The syntheses of the proposed structures of hachijodine B 1, ikimine B 2 and niphatesine D 3 from S-citronellol are described. Our results suggest that the gross structures of hachijodine B and niphatesine D are correct, but that ikimine B was incorrectly assigned. We have also established that the previous absolute stereochemical assignment for niphatesine D is unreliable. 相似文献
90.
Frank Javor Gerald F. Thomas Stuart M. Rothstein 《International journal of quantum chemistry》1977,11(1):59-71
The goodness of the local fit of an approximate wave-function, \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document}, to the exact function, ψ0, is \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. From this quantity the global accuracy of \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document} is defined and a “working supposition” is presented, which quantitatively relates the global accuracy to the accuracy of expectation values. Two criteria based on the accuracy of the reduced local energy and the density respectively, are presented as alternatives to \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. The relative global accuracies of eight wave-functions for H2 are determined using the two criteria. The ‘working supposition’ is applied and predictions are made concerning the relative accuracies of the expectation values of the following operators: z2, r2, x2 + y2, 3z2 ?; r2, ξ, r, r, and EL (the reduced local energy). The success rate is high (>90%) except for those operators which are sensitive to interelectron coordinates or derivatives of the wave-function. 相似文献