Studies in spiroheterocycles. Part V. Synthesis of new fluorinated spiro[3H-indole-3,2′-oxiran]-2(1H)-ones

Reinvestigation of the reaction of 3-aroylmethyleneindol-2-ones with hydrogen peroxide has revealed that a 1:1 isomeric mixture of spiro[3H-indole-3,2′-oxiran]-2(1H)-ones is formed. The structures of the two isomers have been confirmed by their ir, pmr and mass spectral studies. Mass fragmentation patterns of these compounds are discussed.     

Highly efficient synthesis of isoquinolines via nickel-catalyzed annulation of 2-iodobenzaldimines with alkynes: evidence for dual pathways of alkyne insertion

[reaction: see text] A wide range of substituted isoquinolines were synthesized via a highly efficient nickel-catalyzed annulation of the tert-butyl imines of 2-iodobenzaldehydes and various alkynes; examination of the regiochemistry of isoquinolines synthesized indicates that there are two different alkyne insertion pathways for the catalytic reactions.     

2,4,6-Trichloro-1,3,5-triazine Catalyzed Chemoselective Transthioacetalization of Aldehyde Acetals and Oxathioacetals

Summary. A mild and efficient transthioacetalization of aldehyde acetals and oxathioacetals was carried out using 2,4,6-trichloro-1,3,5-triazine as a mild and inexpensive catalyst. Chemoselective transacetalization is impressive as aldehyde O,O- and O,S-acetals are converted into the corresponding S,S-acetals in the presence of ketones or their acetals and oxathiocetals in nearly quantitative yields.     

X-ray structure of physiological copper(II)-bis(L-histidinato) complex

The isolation and the X-ray crystal structure of physiological copper(II)-L-histidine complex are reported. The neutral five-coordinate complex shows distorted square pyramidal geometry with bidentate and tridentate L-histidine ligands. The basic character of the pendent imidazole group and H-bonding interactions of bidentate L-histidine ligand are important for copper transport. The unique structural features help explain the origin of its thermodynamic stability and kinetic reactivity in human blood along with the ternary copper(II)-amino acid complexes. The role of L-histidine in interaction with copper(II)-albumin, in cellular uptake of copper, and in treatment of Menkes disease can be studied using these results.     

EXAFS studies of cobalt oxides and oxide glasses

The exafs of Co²⁺ has been studied in rare earth cobaltites and in sulphate and borate glasses. It has been found that the environment of Co²⁺ ions is very similar in these cases. It appears feasible to study local structures in glasses using probe ion exafs. Communication No. 151 from the Solid State and Structural Chemistry Unit.     

Potentiometric estimation of sulfide ion using the Fe(III)-EDTA complex

The Fe(III)-EDTA complex reacts with sulfide ion in a fast electron transfer reaction, oxidising the latter to elemental sulfur and getting itself reduced to Fe(II). The reaction has been developed for the quantitative estimation of sulfide ion by titration against the Fe(III)-EDTA complex, measuring the redox potential of the system. Repeated use of a given quantity of the complex solution by the process of regeneration has been demonstrated. The possibility of its practical application in liquid phase oxidation processes of recovering sulfur from H₂S is emphasized.     

Oxidative verdoheme formation and stabilization by axial isocyanide ligation

The effect of isocyanides as axial ligands on the formation and stability of verdoheme by oxidation has been examined. The reaction of [Fe(III)(OEPO)]2 with t-butyl isocyanide under dioxygen-free conditions results in the formation of (t-BuNC)2Fe(II)(OEPO*) with an electron paramagnetic resonance at g=2.009 with a peak-to-peak separation of 23.5 G at 4 K. (OEPO is the trianion of octaethyloxophlorin and OEPO* is the radical dianion obtained from OEPO by one-electron oxidation.) Exposure of chloroform solutions of either (2,6-xylylNC)2Fe(II)(OEPO*) or (t-BuNC)2Fe(II)(OEPO*) to dioxygen followed by the addition of ammonium hexafluorophosphate results in their transformation into the diamagnetic verdohemes, [(2,6-xylylNC)2Fe(II)(OEOP)](PF6) and [(t-BuNC)2Fe(II)(OEOP)](PF6), yields 68 and 70%, respectively. (OEOP is the anion of octaethyl-5-oxaporphyrin.) The oxidation reactions of (2,6-xylylNC)2Fe(II)(OEPO*) and (t-BuNC)2Fe(II)(OEPO*) have also been monitored by 1H NMR spectroscopy. No resonances due to paramagnetic products could be detected, the reactions appear to result only in the formation of the diamagnetic verdohemes, and the products are not susceptible to further oxidation.     

Theoretical study of the excited singlet and triplet states of alloxan

The possibility of excited‐state protomeric shifts in the biologically important molecule, alloxan, is investigated. We have focused on the S₁ and T₁ excited states of alloxan and its hydroxy tautomers. Modifications brought in by excitation on the relative stabilities, activation barriers, and optimized geometries, computed at the MNDO, AM1, and PM3 levels of approximation, have been discussed for both excited electronic states. The absorption and fluorescence spectra for the three tautomers are also discussed. Results show significant changes in the geometries on excitation, although the changes are similar for the singlet and triplet excited states. Though the relative stability orders do not change, the 2‐hydroxy tautomer is stabilized, while the 4‐hydroxy tautomer gets destabilized on excitation. The excited states are (n,π*) states, involving the promotion of a nonbonding oxygen lone pair from the CO? CO? CO moiety, which explains why the oxygens of this group become less basic and the 4‐hydroxy tautomer gets destabilized on excitation. However, the activation barriers do not reduce significantly on excitation, and this precludes the possibility of ground‐ or excited‐state proton transfer in the gas phase. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Nonlinear dynamics of confined polymer melts with attractive walls

A scaling model is presented to analyze the reversible strain-hardening phenomenon in end-tethered polymer clay nanocomposites (Krishnamoorti, R.; Giannelis, E. P. Langmuir 2001, 17, 1448). It is assumed that for attractive clay-polymer interactions a fraction of the polymer chains that span the space between opposite clay plates get adsorbed on them, thereby bridging the plates. Under large amplitude oscillatory shear, such bridges are stretched, and this results in the strain-hardening behavior. The onset of strain hardening is predicted to be dependent only on the average distance separating the two plates and is independent of the frequency of the oscillations and the polymer molecular weight.     

Synthesis and characterization of crosslinked polydiacetylene and its two-component interpenetrating polymer networks

The synthesis of crosslinked polydiacetylenes and its two-component interpenetrating polymer networks (IPNs) was carried out utilizing its polar and flexible substituent groups. Polydiacetylenes were crosslinked by the formation of allophanate linkages utilizing urethane groups in the substituent groups of the polydiacetylenes. Elemental analysis, DSC, TMA, solvent resistance, and IR spectra are presented as evidence for the formation of crosslinked polydiacetylenes. IPNs of polydiacetylenes and an epoxy resin (diglycidyl ether of bisphenol A) were synthesized by using simultaneous and sequential methods of synthesis. A study of phase morphology of the simultaneous and sequential IPNs was carried out using electron microscopy, TMA, and DSC.