A large deviation principle for (r,p)-capacities on the Wiener space

Summary We formulate and prove a large deviation principle for the (r, p)-capacity on an abstract Wiener space. As an application, we obtain a sharpening of Strassen's law of the iterated logarithm in terms of the capacity.     

Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti(O-i-Pr)(4)/2 i-PrMgCl Reagent. Efficient Synthesis of Optically Active beta,gamma-Unsaturated Esters with an alpha-Substituent

Treatment of 3,4-alkadienyl carbonates 2a-i with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), readily generated by the reaction of Ti(O-i-Pr)(4) with 2 i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford vinyltitanium compounds 3 which, in turn, reacted with H(3)O(+), D(2)O, or iodine to give alpha-substituted beta,gamma-unsaturated esters 4 in good to excellent yields. The olefin moiety of the hydrolysis product 4 has (Z)-geometry mainly except for 4h. Starting from chiral 2f or 2g, the reaction proceeded stereospecifically to give optically active alpha-substituted beta,gamma-unsaturated ester 4f or 4g having (Z)-olefin geometry exclusively.     

Effect of polymer on electron-donating character of polymer donor. II. Formation of charge-transfer complex between polymers containing N-dimethylaniline group and trinitrotoluene

Formation of charge-transfer complexes with trinitrotoluene (TNT) as a common acceptor was studied in detail by using dimethyltoluidine (DMT), poly-N-dimethyl-p-aminostyrene (poly-ASt), and also copolymers of aminostyrene (ASt) and styrene (St) as donors. A smooth bathochromic shift in λ_max was observed with increasing ASt unit content in copolymers. Values of the constant for charge transfer complex formation K_CT were found to increase smoothly with ASt unit content. However, the K_CT value with DMT did not coincide with the value extrapolated from the plot of K_CT value versus ASt unit content to zero ASt unit content, but was found to be much higher than the limiting value, in contradiction to the results obtained with maleic anhydride (MAnh). The entropy of complex formation with DMT was found to be exceptionally small; this small value may be responsible for the high K_CT value with DMT.     

Unusual impurity effect on room-temperature ferromagnet Sr3YCo4O10.56

We have prepared polycrystalline samples of Sr₃YCo₄O_10.56, Sr_2.4Ca_0.6YCo₄O_10.54, and Sr₃YCo_3.76Mn_0.24O_10.59, and found that these materials show unusual impurity effects on their transport and magnetic properties. A tiny amount of impurities such as Mn or Ca suppresses room-temperature ferromagnetism of Sr₃YCo₄O_10.56. With the suppression, their resistivities and thermopowers are also dramatically changed. We propose that the unusual impurity effects are caused by the suppression of orbital ordering.     

Attempts at Solvolytic Generation of Phenyl Cations

New substrates and reaction conditions which may be expected to yield phenyl cation intermediates have been investigated. The approaches used were: (a) solvolysis of PhX in fluorinated alcohols, where X = ? N (O) = NOTs (tosyloxyazoxy), ? N (O) = NONf (Nf = C₄F₉SO) and ? OSO₂\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm + } $\end{document} (CH₃)₃ōTf (Tf=CF₃SO); (b) solvolysis of ArBr, PhOTf and PhOSO₂\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm + } $\end{document}(CH₃)₃ōTf (phenyl ‘betylate triflate’) in super-acid solvents (FSO₃H · SbF₅, SbF₅, AgSbF₆). Analysis of the product mixtures provided no evidence for the intermediacy of phenyl cations as a major pathway in any of the reactions. This result is remarkable, since the ‘betylate’, for example, is a better leaving group by a factor of at least 10⁵ than the ‘super’ leaving group triflate in the solvolysis of alkyl sulfonates. These results are a further indication of the extremely low stability of phenyl cations, as well as of the very special properties of the nitrogen leaving group in arenediazonium ions.     

15β-Hydroxylation of Lithocholic Acid by cunninghamella sp.

The microbiological transformation of lithocholic acid (3α-hydroxy-5β-cholanic acid) into 3α, 15β-dihydroxy-5β-cholanic acid by Cunninghamella sp. is Investigated. The structure has been determined on the basis of two-dimensional ¹H-NMR.