Metal-free activation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> by synergic effect of ionic liquid and microwave: chemoselective oxidation of benzylic alcohols to carbonyls and unexpected formation of anthraquinone in aqueous condition

H₂O₂ mediated oxidation of alcohols in ionic liquid is revisited, wherein, ionic liquids under the influence of microwave irradiation have been found to facilitate activation of H₂O₂ without any metal catalyst in aqueous condition. The method utilizes a neutral ionic liquid [hmim]Br both as catalyst and solvent for efficient and chemoselective oxidation of benzyl alcohol derivatives on aromatic (β, γ) alcohols, cyclic and aliphatic analogues, which can be a useful synthetic approach in total synthesis of complex organic compounds/natural products. Moreover, an unexpected oxidation of 9-anthracenyl propanol, a polyaromatic benzyl alcohol, resulting in the formation of 9,10-anthraquinone by the loss of propyl side chain was observed. Plausible mechanism and further exploration of this method on various other related substrates are discussed in detail.     

Investigations of pressure induced structural phase transformations in pentaerythritol

We have investigated the pressure induced structural changes in pentaerythritol {2,2-bis-(hydroxymethyl)-1,3-propanediol} with the help of X-ray diffraction studies. Our results show that this compound undergoes transformations to a lower symmetry phase between 5.2-5.9 GPa. It further undergoes phase transformations at ∼8.5 and ∼11 GPa; eventually evolving to a disordered phase beyond 14-15 GPa in agreement with our earlier Raman studies. On release of pressure from 18.5 GPa, the compound transforms back to the initial tetragonal phase.     

Two-dimensional weak pseudomanifolds on eight vertices

We explicitly determine all the two-dimensional weak pseudomanifolds on 8 vertices. We prove that there are (up to isomorphism) exactly 95 such weak pseudomanifolds, 44 of which are combinatorial 2-manifolds. These 95 weak pseudomanifolds triangulate 16 topological spaces. As a consequence, we prove that there are exactly three 8-vertex two-dimensional orientable pseudomanifolds which allow degree three maps to the 4-vertex 2-sphere.     

A reexamination of the degradation of polyvinylchloride by thermal analysis

Degradation of polyvinylchloride has been reexamined in the light of its DT-DSC-TG analytical behavior up to a temperature of 1000°C in an inert atmosphere. Four distinct stages of degradation have been identified. The first stage is almost eventless with no change in weight for untreated PVC samples. The second stage is almost exclusively dehydrochlorination. The third stage appears to be a structural reorganization involving such processes as cis-trans isomerization, aromatization, and crosslinking. The fourth stage appears to be a structural degradation and is associated with the evolution of hydrocarbons. The role of liberated hydrogen chloride has been better appreciated in catalyzing the above secondary reactions on the polyene residue obtained on partial or total dehydrochlorination. The effect of the particle dimension and chemical and physical pretreatments of the samples, such as low temperature dehydrochlorination by an alkali and vacuum heat treatment, respectively, on the degradation pattern has been studied. © 1994 John Wiley & Sons, Inc.     

The study of relatively low density stellar matter in presence of strong quantizing magnetic field

The effect of strong quantizing magnetic field on the equation of state of matter at the outer crust region of magnetars is studied. The density of such matter is low enough compared to the matter density at the inner crust or outer core region. Based on the relativistic version of semi-classical Thomas-Fermi-Dirac model in presence of strong quantizing magnetic field a formalism is developed to investigate this specific problem. The equation of state of such low density crustal matter is obtained by replacing the compressed atoms/ions by Wigner-Seitz cells with nonuniform electron density. The results are compared with other possible scenarios. The appearance of Thomas-Fermi induced electric charge within each Wigner-Seitz cell is also discussed.     

Sulfonylureas as Dual Acting Agents — Synthesis and Biological Activity

2‐Amino‐5‐aryl/alkyl‐1,3,4‐thiadiazoles 3a‐e were used as intermediates in the synthesis of some 1,3‐substituted urea derivatives 5a‐o to evaluate their antidiabetic activity as well as antibacterial activity. The obtained compounds exhibited marginal activity against the animal models and the selected microorganisms.     

Electrical conductivity of thermally degraded poly(vinyl chloride)–polyacrylonitrile blends

Finely powdered blends of poly(vinyl chloride) (PVC) and polyacrylonitrile (PAN) have been thermally degraded at 275°C for 24 h in an inert atmosphere to effect complete de-hydrochlorination of PVC to a conjugated polyene structure and simultaneous internal polymerization of nitrile groups in PAN to a conjugated polyimine sequence. The room temperature d.c. conductivity of the degraded blends showed clear synergistic behavior. A maximum conductivity has been observed with a blend of 60 PAN/40 PVC which is about 4 orders of magnitude over the linearly weighted average conductivity of the individual degraded homopolymers. The results have been interpreted in terms of a possible donor-acceptor interaction between the degraded homopolymers leading to mutual doping and, hence, an enhanced electrical conductivity. © 1995 John Wiley & Sons, Inc.     

Oxidative behaviour and relative reactivities of α,β-unsaturated compounds towards bis(dihydrogentellurato)cuprate(III) and -argentate(III) in alkaline medium

The kinetics of oxidation of three alpha beta-unsaturated compounds, CH2CHX (X=CN, CONH2 and CO2-) by bis(dihydrogentellurato)metallate(III) ions ([MIII-(H2TeO6)2]5-, M=Cu or Ag) have been studied in an alkaline medium. The reactions take place according to the rate expression: The k3 values are 2.42*10-2, 1.67*10-2 and 1.10*10-2mol6dm-2s-1 for oxidations of the respective substrate by the copper(III) complex and 1.49*10-2, 1.07*10-2 and 0.80*10-2mol6dm-2s-1, respectively, in the oxidations by silver(III), all at 303K. [CuIII(H2TeO6)2]5- reacts faster than the corresponding reactions with [AgIII(H2TeO6)2]5-. The oxidation rates follow the order: CN CONH2CO2-. The oxidations of the substrates by [CuIII(H2TeO6)2]5- take place by an outer-sphere mechanism, unlike [AgIII-(H2TeO6)2]5-, which reacts by an inner-sphere mechanism. The substrates are oxidized to diols under kinetic control and a tentative reaction mechanism leading to the formation of oxidation products is suggested. The activation parameters of the reactions have been evaluated. This revised version was published online in June 2006 with corrections to the Cover Date.     

Motion of aromatic hydrocarbons in the microporous aluminum methylphosphonates AlMePO-alpha and AlMePO-beta

(2)H wide-line NMR has been used, in conjunction with molecular dynamics simulations where appropriate, to follow the reorientation of the monoaromatic compounds benzene, toluene, and p-xylene within the one-dimensional channels of the alpha- and beta-polymorphs of aluminum methylphosphonate, Al(2)(CH(3)PO(3))(3). Variable-temperature, static, (2)H NMR spectra of adsorbed d(6)-benzene, d(3)-, d(5)-, and d(8)-toluenes, and d(3),d(3)-p-xylene were matched by line shape simulation. The motion of p-xylene in both polymorphs is approximated by the long axis of the molecule describing a cone within the channels, the half-angle of which is greater for the slightly wider channels in AlMePO-beta (27-30 degrees cf. 18-19 degrees). The (2)H NMR of d(3)-toluene is simulated using a similar model, whereas the signal from aromatic deuterons in d(5)- and d(8)-toluenes is simulated by a ring undergoing 2pi/3 flips around the para axis. The reorientation of benzene shows the largest differences between the two pore structures. In AlMePO-beta it tumbles with little restriction, although at low temperatures the spectral details are better matched by allowing the molecule to spend a greater proportion of its time closer to the wall. In AlMePO-alpha the much broader line shape arises from constrained motion within the strongly triangular channels. Molecular dynamics simulations of benzene in the two structures confirm the differences. They support a model for benzene in AlMePO-alpha where its motion is restricted to rotations about its 6-fold axis and 2pi/3 jumps between symmetry-related sites in the pores, so that the plane of the aromatic ring remains approximately parallel to the c-axis.