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1.
2.
Various phenylsulfonyl allene derivatives were prepared with double bonds tethered either to the alpha-position or the gamma-position of the allene. These substrates underwent a highly regio- and stereospecific thermal [2 + 2]-cycloaddition across the nonactivated cumulene double bond, forming distal cycloadducts (i.e., 57) in the case of alpha-tethered allenes and proximal adducts (i.e., 25) in the case of gamma-tethered allenes. The mechanistic rationale for the observed stereospecificity involves initial diradical formation, followed by a rapid ring closure to the more stable cis-fused ring system. The tether may be equipped with heteroatoms, allowing for the formation of fused heterocycles (e.g., 61), and the cycloaddition can be facilitated by the introduction of sterically bulky groups and/or by conformational rigidity to the tether. Other modes of cyclization were observed in the presence of sodium benzenesulfinate or Lewis acids, in which cases polar mechanisms prevail. The chemoselectivity is reversed for [4 + 2]-cycloadditions, which prefer instead to engage the vinyl sulfone moiety, independent of whether the tether is attached to the alpha- or gamma-position of the allene. 相似文献
3.
Schormann M Garratt S Hughes DL Green JC Bochmann M 《Journal of the American Chemical Society》2002,124(38):11266-11267
The reaction of the tin-substituted propene Me3Sn(R)CHCH=CHR (R = SiMe3) with MCl4 in dichloromethane in the presence of Me3SnCl gives the first examples of isolable sec-alkyl carbocation salts, [HC{CH(R)SnMe3}2]+M2Cl9- (M = Zr, Hf). The compounds are thermally stable and, unlike previously isolated trialkyl carbocations, do not require superacidic media or weakly coordinating anions for stability. The crystal structure and DFT calculations suggest polarization of the Sn substituents and hyperconjugation as the reason for the unexpected stability. The stabilizing effect of tin is significantly stronger than that of Si. The carbocations are effective initiators for the polymerization of isobutene, isoprene, and alpha-methylstyrene. 相似文献
4.
J. R. Brown J. H. O'Donnell 《Journal of polymer science. Part A, Polymer chemistry》1972,10(7):1997-2004
Mixtures of sulphur dioxide and butene-1 have been polymerized in the gas phase to the 1:1 alternating copolymer by electron irradiation. The rate of polymerization, measured by the decrease in gas pressure, decreased with increase in temperature over the range ?20 to +30°C. The initial G(-monomer) values decreased from 500 to 50 giving an Arrhenius activation energy of ?30 kJ mol?1. These results are consistent with a ceiling temperature-pressure relationship. The ceiling temperature is about 60°C lower than that observed previously in the liquid phase in accord with thermo-dynamic prediction. 相似文献
5.
6.
Espy MA Dehnhard D Edwards CM Palarczyk M Langenbrunner JL Davis B Burleson GR Blanchard S Gibbs WR Lail B Nelson B Park BK Zhao Q Cummings WJ Delheij PP Jennings BK Henderson R Häusser O Thiessen D Brash E Jones MK Larson B Brinkmöller B Maeda K Morris CL O'Donnell JM Penttilä S Swenson D Tupa D Bennhold C Kamalov SS 《Physical review letters》1996,76(20):3667-3670
7.
8.
Trevor N. Bowmer James H. O'Donnell Donald J. Winzor 《Journal of polymer science. Part A, Polymer chemistry》1981,19(5):1167-1174
Polystyrene of narrow molecular weight distribution, M w/M n ≈ 1.03, was subjected to γ irradiation at 100 and 150°C. The yields of scission and crosslinking, G(S) and G(X), where determined from the changes in molecular weight distribution using gel permeation chromatography, (GPC) with supporting evidence from osmometry and viscometry. The ratio G(S)/G(X) increased from 0.02 at 30°C, obtained previously, to 2.8 at 150°C. This was mainly due to a tenfold increase in G(S), whereas G(X) apparently decreased slightly. These results are compatible with increased disproportion of chain scission radicals relative to their combination, analogous to the temperature dependence of mutual termination in the free radical polymerization of styrene. There was no obvious discontinuity through the glass transition temperature, although there may be a change in sign of the temperature coefficient of G(X). This system provides an excellent example of the applicability of measurements of molecular weight distributions and averages to determinations of G(S) and G(X) under conditions when gel measurements are inappropriate, either because of the failure of the system to form gel, or, as in the present case, because of the very large radiation doses required for gel formation. 相似文献
9.
Ottenberg CM McDonald FC O'Donnell ET Skrabal SA White DP 《Inorganic chemistry》2002,41(26):7151-7158
Increased preorganization can be achieved by immobilizing ligands on solid supports. Photoluminescent porous silicon, which can undergo facile hydrosilylation, was used as a support for open chain neutral N- and O-donor ligands. The abilities of these ligands to bind the divalent metal ions Ni(2+), Cu(2+), Zn(2+), and Pb(2+) are examined. Immobilized ligands selectively complexed Cu(II) over the other metal ions studied. Ligands immobilized on photoluminescent porous silicon also removed a significant amount, up to 98%, of Cu(II) from copper(II)-spiked, organic-rich, seawater samples. 相似文献
10.
James O'Donnell Bruno Rusterholz Barbara Aebersold Denise Rüegg Wilhelm Simon Ernö Pretsch 《Mikrochimica acta》1994,113(1-2):45-52
In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992 相似文献