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91.
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93.
The room temperature reaction of (Bu4N)3V5O14 with PhPO3H2 in methanol yields the pentanuclear V(V) cluster (Bu4N)[V5O7(OCH3)2(PhPO3)5]·CH3OH (1·CH3OH). In contrast, the hydrothermal reaction of (Ph4P) [VO2Cl2], PhPO3H2 and (NH4)H2PO4 at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph4P)2[V5O9(PhPO3)3(PhPO3H)2] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P21/n,a=12.167(2) Å,b=23.348(5) Å,c=22.508(5) Å,β=98.49(2)°,V=6323.9(19) Å3,Z=4,D calc=1.558 g cm?3; 3, triclinic, $P\bar 1$ ,a=13.478(3) Å,b=14.399(3) Å,c=23.638(5) Å,α=72.53(2)°,β=85.58(2)°,γ=69.88(4)°,V=4107.0(16) Å3,Z=2, Dcalc=1.479 g cm?3. 相似文献
94.
95.
André Deratani Thierry Maraldo Estelle Renard 《Journal of inclusion phenomena and macrocyclic chemistry》1995,23(2):137-146
Reduction of-cyclodextrin (-CD) aromatic ketone (acetophenone and acetonaphthones) inclusion compounds were carried out in the presence of a large number of chemically inert species as potential co-guests. In several cases, it was observed that stoichiometric molar ratios of these compounds to ketone significantly modify the chiral induction yielding the inverted alcohol enantiomer and increasing the face selectivity. The results were found to depend strongly on the respective structure and shape of both the ketone and the additive, and on the molar ratio of-CD:ketone:third compound. These observations suggest the formation of a three-component inclusion complex in which the geometry of binding of the substrate and its mobility are changed with respect to the binary system. 相似文献
96.
We have constructed molecular models of octameric micelles formed by a recently developed lipopeptide detergent consisting of a single amphipathic alpha-helix coupled to two acyl chains at either end of the helix. The models explain the experimentally observed aggregation behavior of peptides with different acyl chain lengths. The octameric micelles form a unique coiled-coil structure, with the acyl chains in a nearly frozen conformation inside the cylindrical assemblies. Two extreme models with helices either all parallel or in an alternating orientation suggest that the alternating orientation is energetically more favorable. The models suggest several new directions for further diversifying this new class of detergents for the structural studies of membrane proteins. 相似文献
97.
[reaction: see text] The photoinduced metalation of nonactivated C-Cl bonds of O-acetyl chlorohydrins is promoted by samarium diiodide. As a result of this, beta-elimination of O-acetyl chlorohydrins is achieved, affording the corresponding (Z)-alkenes with total or high stereoselectivity. 相似文献
98.
Beech CL Coope JF Fairley G Gilbert PS Main BG Plé K 《The Journal of organic chemistry》2001,66(7):2240-2245
A new "safety catch" linker for esters has been synthesized on polystyrene resin. This 2-tert-butoxyphenol resin 10 may be acylated to give a relatively stable ester that will allow nucleophilic chemistry without reaction at the linking ester group. Removal of the tert-butyl group with acid unmasks a highly reactive 2-hydroxyphenyl ester that reacts readily with nucleophiles to cause release of the product from the resin. This sequence has been exemplified by acylating the resin with various bromo acids, carrying out nucleophilic displacements with thiols, phenols, or amines, activating the ester with trifluoroacetic acid and cleaving from the resin with amines to give the (nucleophile) substituted carboxamides in high yield and purity. Kinetic studies with a model ester revealed half-lives for reaction with morpholine of 119 h for the tert-butoxyphenyl ester and 1 min for the corresponding phenol. 相似文献
99.
Abramovitch RA Beckert JM Gibson HH Belcher A Hundt G Sierra T Olivella S Pennington WT Solé A 《The Journal of organic chemistry》2001,66(4):1242-1251
The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed. 相似文献
100.