SYNTHESIS AND SPECTRAL STUDIES OF SOME NEW [(ALKOXYCARBONYLVINYL)ARYL- AND BENZYLSULFONYLMETHYL] SULFONES

Abstract

Some new 1,1,2-trisubstituted ethylenic sulfones have been prepared by the condensation of aryl- and benzylsulfonylmethylsulfonylacetic acid esters with araldehydes.     

Where is SUSY?

The searches for supersymmetry at the Large Hadron Collider (LHC) have so far yielded only null results and have considerably tightened the bounds on the sparticle masses. This has generated some skepticism in the literature regarding the ‘naturalness of SUSY’ which qualitatively requires some sparticles to be relatively light. Re-examining some of the bounds from LHC searches, it is argued with specific examples that the above skepticism is a red herring because (i) a quantitative and universally accepted definition of ‘naturalness’ is not available and (ii) even if some conventional definitions of naturalness is accepted at their face values, the alleged tension with the apparently stringent LHC bounds wither away once the strong assumptions, by no means compelling, underlying such bounds are relaxed.     

Figures of merit of magnetostrictive single crystal iron-gallium alloys for actuator and sensor applications

Energy density, magnetomechanical coupling factor and a dimensionless sensing gage factor of 〈1 0 0〉 oriented single crystal iron-gallium alloys with 16, 17.5, 19, 24.7 and 29 at% gallium were studied as functions of stress and magnetic field. To estimate these quantities, the samples were characterized under different quasi-static stress and magnetic field conditions. The experimental behavior was modeled using an energy-based non-linear approach. Both the experimental data and the model simulations were used to calculate material parameters such as magnetic permeability, piezo-magnetic strain coefficient (d₃₃), inverse piezo-magnetic coefficient (stress sensitivity, d*₃₃) and Young's modulus in the material. These quantities were used to obtain energy density, magnetomechanical coupling factor and sensing gage factor as functions of magnetomechanical conditions. Maximum energy density of around 3 kJ/m³, magnetomechanical coupling factor higher than 0.75 and sensing gage factor on the order of 10³ were calculated.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

2-Arylethenyl-2″-Arylethynyl Sulfones: A Potential Source for New Heterocycles

Abstract

Different heteroatoms viz., N, S & Se have been incorporated into 2-arylethenyl-2′-arylethynyl sulfones by nucleophilic reaction with benzylmine, hydrogen sulfide and sodium hydrogen selenide.     

Acid-Catalyzed Hydrolysis of Some N,N-Dibenzylalkanesulfinamides in 50% Acetonitrile–Water

Abstract

The hydrolysis of some N,N-dibenzylalkanesulfinamides (RSONH(CH₂Ph)₂; 1, R = Me; 2, R = ⁱPr; 3, R = ^tBu; 4, R = 1-adamantyl) has been studied in 50% (v:v) acetonitrile–water solutions of hydrobromic and hydrochloric acids, mainly at 44.8 °C, using ultraviolet (UV) spectrophotometry to determine pseudo first-order rate constants. The compounds were found to hydrolyze by concurrent bimolecular neutral, acid-catalyzed, and acid-dependent nucleophilic (halide ion) catalysis pathways. The last-named is predominant in reactions in HBr solutions, but in HCl solutions, the acid-catalyzed pathway is predominant. The results indicate that both steric and electronic effects are important in these reactions. There appears to be no mechanistic switchover in the series 1→4.     

Synthesis and anion binding of 2-arylazo-meso-octamethylcalix[4]pyrroles

2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and ¹H NMR in DMSO and CDCl₃, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl₃ revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion.

     

Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

The association reaction between silyl radical (SiH₃) and H₂O₂ has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH₃–H₂O₂ association in the temperature range 250–600 K, k(T) = 6.89 × 10^?13 T ^?0.163exp(?0.22/RT) cm³ molecule^?1 s^?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH₂(OH)₂ + H, is the major decomposition channel followed by secondary dissociation leading to SiO.     

Octahedral CuII and NiII complexes manifesting with N′-[1-(pyridin-2-yl)ethylidene] acetohydrazide: Structural outlooks and spectral characteristics

A tridentate hydrazone precursor, N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide (L) (1:1 refluxed product of acetichydrazide and 2-acetylpyridine), produced two octahedral Cu^II and Ni^II derivatives, [CuL₂]·NO₃ (1) and [NiL₂]·ClO₄·H₂O (2). Both are subjected to X-ray diffraction system, and structural investigation shows that the central metal atom (Cu^II or Ni^II) adopts a distorted octahedral geometry with N₄O₂ donor sets by coordination of a pair of independent hydrazone precursors. Besides X-ray study, IR and UV-vis spectra, thermal analysis and room temperature magnetic moments are utilized for establishing significant characteristics of both complexes. It is apparent that the M-N_pyridine bonds are slightly longer than the M-N_imino bonds, Cu1-N1 and Cu1-N4 [2.300(2) and 2.038(2) ?] for 1 and Ni1-N1 and Ni1-N4 [2.075(2) and 2.084(1) ?] for 2, Cu1-N2 and Cu1-N5 [2.062(1) and 1.932(1) ?] for 1 and Ni1-N2 and Ni1-N5 [2.008(2) and 1.975(2) ?] for 2, respectively. As per our observation, the effective magnetic moment value (μ_eff) is found to be 1.77 B.M. for 1 and 3.06 BM for 2, respectively.     

Synthesis of (R)‐Japonilure and (4R,9Z)‐9‐Octadecen‐4‐olide,Pheromones of the Japanese Beetle and Currant Stem Girdler

Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)‐japonilure (1) and (4R,9Z)‐9‐octadecen‐4‐olide (2), has been achieved.