TBAI/TBHP‐Promoted Generation of Malonyl Radicals: Oxidative Coupling with Styrenes Leads to γ‐Keto Diesters

A metal‐free protocol for oxidative coupling of malonic esters with styrenes to form γ‐keto diesters has been developed. Key to the success of this process is the generation of malonyl radicals from unfunctionalized malonic esters under organo‐catalysis conditions with TBAI and TBHP. This process tolerates both terminal and internal olefins with diverse malonic esters. It provides a new green metal‐free alternative to traditional metal mediated process for generation of malonyl radicals and there by γ‐keto diesters.     

Diffraction of SH-waves by a half-plane

An alternative method has been developed in solving the diffraction problem of pulses by a half-plane. Taking the normal incidence of a harmonic pulse on a perfectly rigid half-plane, the total reflected and diffracted fields of SH-waves in closed forms has been evaluated. This agrees with the results obtained by earlier workers.The author would like to thank Dr. S. C. Das Gupta for suggesting the problem and for guidance in preparing this paper.     

In(OTf)3-catalyzed synthesis of 4-thiocyanotetrahydropyrans via a three-component reaction

A three-component coupling of aldehydes, homoallylic alcohols and ammonium thiocyanate is achieved in the presence of 10 mol % of In(OTf)₃ in refluxing dichloromethane to produce 4-thiocyanotetrahydropyrans in excellent yields with all cis-selectivity. This method is simple, selective and convenient for introducing an SCN group onto a tetrahydropyran ring.     

Size-dependent properties of Zn(m)S(n) clusters: a density-functional tight-binding study

We present the results of our theoretical calculations on structural and electronic properties of ligand-free Zn(n)S(n) [with n ranging from 4 to 104 (0.8-2.0-nm diameter)] clusters as a function of size of the clusters. We have optimized the structure whereby our initial structures are spherical parts of either zinc-blende or wurtzite structure. We have also considered some hollow bubblelike structures. The calculations are performed by using a parametrized linear combination of atomic orbitals-density-functional theory-local-density approximation-tight-binding method. We have focused on the variation of radial distribution function, Mulliken populations, electronic energy levels, band gap, and stability as a function of size for both zinc-blende and wurtzite-derived ZnS clusters. We have also reported the results of some nonstoichiometric Zn(m)S(n) (with m+n=47, 99, 177) clusters of zinc-blende modification.     

The first total synthesis of sequosempervirin A through an orthoester Claisen rearrangement—ring closing metathesis sequence

The first total synthesis of sequosempervirin A, a norlignan with a unique spirocyclic structure has been accomplished using an orthoester Claisen rearrangement—ring closing metathesis sequence.     

Structure,bonding, and spectra of cyclic dithia radical cations: a theoretical study

Ab initio molecular orbital and hybrid density functional theory methods are employed to characterize the structure, bonding and properties of several cyclic dithia radical cation systems, particularly in the context of intra molecular two-center three-electron (2c-3e) bonding between two sulfur atoms. The calculated results are able to interpret the time-resolved transient optical spectra obtained from pulse radiolysis technique for these positively charged dithia systems in aqueous solution. Visualization of the appropriate molecular orbital (MO) in the systems is able to depict the presence of a 2c-3e bond between two sulfur atoms and its sigma character. Geometry optimizations of these doublet systems are carried out at restricted open shell Becke's half-and-half (BHH) nonlocal exchange and Lee-Yang-Parr (LYP) nonlocal correlation functionals (BHHLYP) with 6-311+G(d,p) basis set including solvent effects adopting Onsager's reaction field model. Hessian calculations are done at the same level to check the nature of the equilibrium geometry. Energy data are further improved by performing MP2/6-311+G(d,p) calculations on these radical cation systems. Excited-state calculations are done following configuration interaction with single-electron excitation (CIS) method and the optical transition wavelength from the highest doubly occupied molecular orbital (HDOMO) to the lowest singly occupied molecular orbital (LSOMO) is seen to correspond and match to the position of the absorption maxima (lambda(max)) obtained from the experimental spectra for all these radical cation systems in aqueous solution. These calculations are able to resolve a long-standing ambiguity in the assignment of intra molecular 2c-3e bonding in the case of the 3-methyl-2,4-dithiapentane radical cation system and to provide new insights into bonding features of this odd electron system as well as of other cyclic dithia systems studied.     

Multiphoton dissociation/ionization of CHCl3 and CFCl3 at 355 nm: an experimental and theoretical study

Nonresonant laser-induced multiphoton dissociation/ionization studies have been conducted for trichloromethane (CHCl3) and trichlorofluoromethane (CFCl3) at 355 nm, using time-of-flight mass spectrometry (TOFMS). The molecular ion signal was found to be missing for both these compounds, and very similar fragmentation patterns were observed. Ab initio molecular electronic structure calculations were performed to help understand the fragmentation pattern of these molecules in the laser field. The energetics of different dissociation channels in the ground states of [CHCl3]+*, [CHCl2]+, [CFCl3]+* and [CFCl2]+, as well as neutral CHCl3, CHCl2*, CFCl3 and CFCl2* systems, were calculated. On comparing theoretical results with experimentally observed ion signals and their relative abundances in TOFMS, it is inferred that these molecules undergo sequential Cl atom elimination followed by photoionization of the fragments. The absence of [CFCl]+ has been interpreted on the basis of resonant A state-mediated two-photon absorption by CFCl, and the subsequent prompt photodissociation processes occurring for this state.     

Niobium(III) as an analytical reagent. : Part I. The titrimetric determination of iron,copper, thallium,molybdenum, uranium and vanadium

Niobium(III) solutions can be used in direct titrations of copper(II), iron(III), thallium(III), moIybdenum(VI), vanadium(V) and uranium(VI) in milligram amounts. Phenosafranine is generally satisfactory as the indicator, but potentiometric end-points can also be used. Copper and iron can be determined successively when a mixed indicator containing phenosafranine and méthylene blue is used. Thallium(I) and thallium (III) can be determined in mixtures. The niobium (III) solutions are stable for several days under a carbon dioxide atmosphere.     

N,N'-diphenyldithiomalonamide as a gravimetric reagent for nickel and cobalt

N,N'-Diphenyldithiomalonamide, (C₆H₆. NH. CS)₂CH₂, is found to be a very suitable gravimetric reagent for nickel(II) and cobalt(II). The complexes, of composition Ni(C₁₅H₁₃N₂S₂)₂ and Co(C₁₅H₁₃N₂S₂)₃, are stable and can be weighed after drying at 110°. Separation from base metals has been studied, and the structural interpretation is supported by DTA, TG, infrared and NMR data.