Kinetics of oxidation of heterocyclic secondary alcohols by N-chloro-r-2,c-6-diphenyl-t-3 methyl piperidin-4-one (NCP) in perchloric acid medium

An investigation of the kinetics of oxidation of epimeric piperidin-4-ols, oxan-4-ols, and cyclohexanol by N-chloro-r -2, c -6-diphenyl-t -3-methylpiperidin-4-one (NCP) in aqueous acetic acid in the presence of perchloric acid shows that the reaction is first-order each in substrate and oxidant. Both H₃O⁺ and Cl^? which catalyze the reaction, exhibit a fractional order kinetics. While increase in ionic strength increases the rate slightly, an inverse dependence is observed between rate and solvent polarity. Addition of r -2-c -6-diphenyl-t -3-methylpiperidin-4-one, one of the reaction products, did not influence the rate. Also, no kinetic isotope effect has been observed. A plausible mechanism consistent with these observations is proposed and the relative reactivities of the substrates are explained on conformational grounds. © 1994 John Wiley & Sons, Inc.     

Bargellini condensation of coumarins. Expeditious route to o-carboxyvinylphenoxyisobutyric acids and application to the synthesis of sesquiterpenes helianane, heliannuol A and heliannuol C

The direct Bargellini condensation of coumarins involving reaction with chloroform and acetone in the presence of aqueous sodium hydroxide furnished o-carboxyvinylphenoxyisobutyric acids in good yields. The utility of this new useful protocol was demonstrated by the transformation of the three diesters 9b, 9f and 9g to the sesquiterpenes helianane 4, heliannuol A 2 and heliannuol C 3, respectively.     

A new class of multiset Wilf equivalent pairs

We say the pair of patterns (σ,τ) is multiset Wilf equivalent if, for any multiset M, the number of permutations of M that avoid σ is equal to the number of permutations of M that avoid τ. In this paper, we find a large new class of multiset Wilf equivalent pairs, namely, the pair (σ_n-2(n-1)n, σ_n-2n(n-1)), for n?3 and σ_n-2 a permutation of {1^x₁,2^x₂,…,(n-2)^x_n-2}. It is the most general multiset Wilf equivalence result to date.     

Synthesis of O-methyl epi-heliannuol E

A synthesis of the methyl ether of an epimer of the alleochemical heliannuol E is described. The route involves indium mediated allylation of a benzopyranone carboxylate and subsequent one carbon degradation to a vinyl group.     

Temperature dependence of positron annihilation characteristics on the surfaces of graphite powders

Positron lifetime measurements have been made on graphite powders, grafoils, and pyrolytic graphite crystals with different surface areas in the temperature range between 25° and 600 °C. Three positron lifetimes were found in these systems: a short-lived component (0.2 ns) due to positrons in the bulk; a component (0.45 ns) due to surface-trapped positrons; and a long-lived component (2 ns) ofo-Ps in the voids or the interfacial spaces of powders. Both bulk and surface positron lifetimes increase as a function of temperature. Correlations between the intensity of surface-trapped positrons and the surface area and between Ps formation and the surface area of graphite are found. The Ps formation probability increases as a function of temperature. A thermal desorption model interprets the emission process of Ps atoms from the surface of graphite to the vacuum and gives an activation energy of 0.23±0.02 eV.Preliminary results of this paper were presented at the March Meeting of American Physical Society, Los Angeles. Bull. Am. Phys. Soc.28, 347 (1983)