Halonium ion-mediated reaction of unsaturated hydroperoxy acetals. Competition between the formation of cyclic peroxides and the migration of the methoxy (or hydroxy) group

Monoozonolyses of dienes 2 in methanol gave in each case the corresponding unsaturated alpha-methoxy hydroperoxides 3. Capture of 2-alkyl-substituted cyclohexanone oxides by methanol was highly diastereoselective, thereby providing exclusively the hydroperoxides derived from attack by methanol from the less hindered face of the carbonyl oxide intermediates. Halonium ion-mediated reactions of the hydroperoxides 3 gave the novel methoxy- or hydroxy-migrated products, together with the expected halogen-substituted 1, 2-dioxanes and/or 1,2-dioxepanes, the composition of the product mixture being a function of the halogenating agent utilized and the structure of 3.     

Non-negative hereditary polynomials in a free *−algebra

We prove a non-negative-stellensatz and a null-stellensatz for a class of polynomials called hereditary polynomials in a free *-algebra.Partially supported by NSF, DARPA and Ford Motor Co.Partially supported by NSF grant DMS-0140112Partially supported by NSF grant DMS-0100367     

Fluorocarbon crowning: Langmuir-Blodgett deposition versus self-assembly at molecularly rough surfaces

Langmuir-Blodgett deposition of a single monolayer of 1,2,4,5-tetrakis[(N-(perfluoroundecanoamidoethyl)-N,N-dimethylammonium)methyl]benzene tetrabromide (1) onto a thin film made from alternating layers of poly(diallydimethylammonium chloride) (PDADMA) and poly(4-styrenesulfonate) (PSS) ions affords a uniform fluorinated surface of low energy. An analogous surface that has been constructed by self-assembly shows the same critical surface tension of 16.5 dyn/cm. A comparison of Zisman plots for these two modified films, in combination with analysis by X-ray photoelectron spectroscopy, indicates that Langmuir-Blodgett deposition produces a higher quality and more densely packed fluorocarbon surface that is very hydrophobic. In sharp contrast, the use of a single-chain analog (i.e., N-(perfluoroundecanoamidoethyl)-N,N,N-trimethylammonium bromide) (2)) affords relatively high energy surfaces by Langmuir-Blodgett deposition and by self-assembly.     

The synthesis of N-substituted tetrahydropyridines using the hetero-cope rearrangement

Several imines have been prepared from methacrolein dimer. Thermal rearrangement of these molecules resulted in the formation of N-substituted tetrahydropyridines.