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Bridged species thermodynamic stability

The thermodynamic stabilities of phenonium ions have been determined based on bromide-transfer equilibria in the gas phase and, depending on the substituents, the bridged species (1) has been proposed as an intermediate or transition state on the potential-energy surface for the 1,2-aryl rearrangement of triarylvinyl cations (see Scheme 1). Phenonium ion (3) has been presented as an intermediate to account for the fact that lactonization of methyl 4-aryl-5-tosyloxy hexanoate (2) produces y-lactone (4) selectively under thermodynamic conditions, but affords 5-lactone (5) preferentially under kinetic conditions. It has been shown that anodic oxidation of frany-stilbene in alcohols in the presence of KF or BU4NBF4 is accompanied by its electro-oxidative rearrangement into diphenylacetaldehyde acetals. The mechanism outlined in Scheme 2 has been proposed" for the transformation. [Pg.487]

The cavitands are essentially synthesized from their resorc[4]arene precursors which are readily obtained by resorcinol condensation with aldehydes. The main feature comes from the different configurations that are expected for this tetrameric species and the relative thermodynamical stability of each isomer, which has been widely investigated by several authors. In addition, the conformational mobility of the resorc[4]arene molecules will depend on substitution at the upper and lower rims [28, 36, 40, 41]. The first attempt to synthesize a phosphorus bridged cavitand was to treat resorc[4]arene la (1, R=CH3) with phenylphosphonic dichloride or phenylphosphonothioic dichloride. Only inseparable isomer mixtures were obtained and isolation of the desired cavitands was not possible [42]. The first isolated phosphorylated resorcinol-based cavitand was described in 1992 by Markovsky et al., who prepared compound D from la and four equivalents of o-phenylenechlorophos-phate in the presence of triethylamine [43, 44]. For this compound, a tautomeric temperature and solvent dependent equilibrium exists between the spirophosphorane structure and the cyclic phosphate form (Scheme 4). [Pg.60]


See other pages where Bridged species thermodynamic stability is mentioned: [Pg.205]    [Pg.666]    [Pg.128]    [Pg.604]    [Pg.502]    [Pg.210]    [Pg.25]    [Pg.666]    [Pg.210]    [Pg.199]    [Pg.396]    [Pg.80]    [Pg.369]    [Pg.3946]    [Pg.604]    [Pg.469]    [Pg.394]    [Pg.292]    [Pg.791]    [Pg.511]    [Pg.11]    [Pg.46]    [Pg.59]    [Pg.14]    [Pg.43]    [Pg.290]    [Pg.693]    [Pg.216]    [Pg.914]    [Pg.138]    [Pg.1048]    [Pg.362]    [Pg.324]    [Pg.353]    [Pg.1510]    [Pg.914]    [Pg.440]    [Pg.27]    [Pg.324]    [Pg.7059]    [Pg.27]    [Pg.324]    [Pg.283]    [Pg.148]    [Pg.107]   
See also in sourсe #XX -- [ Pg.38 , Pg.40 ]




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Bridged species

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Stability, stabilization thermodynamics

Thermodynamic stabilization

Thermodynamical stability

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