The allylic nucleophilic substitution of Morita-Baylis-Hillman acetates with isocyanides: a facile synthesis of trisubstituted olefins

Morita-Baylis-Hillman acetates undergo smooth allylic nucleophilic substitution (S_N2′) with tosylmethyl isocyanide (TosMIC) in the presence of a catalytic amount of BF₃·OEt₂ under mild conditions to furnish trisubstituted olefins in high yields with (E)-stereoselectivity.     

Strategic utilization of catalytic metathesis and photo-thermal metathesis in caged polycyclic frames

Highly functionalized cage compounds have been prepared via cross-metathesis (CM) using Grubbs modified N-tolyl catalyst 7. A strategic utilization of photo-thermal metathesis and catalytic metathesis sequence for the synthesis of functionalized caged molecules has been demonstrated.     

Towards the catalytic formation of α,β-vinylesters and alkoxy substituted γ-lactones

A facile, one pot, high yield synthesis of α,β-vinylester (1-14) and alkoxy substituted γ-lactones (15-28) has been achieved by the photochemical reaction of terminal acetylene (ferrocenyl phenyl trimethylsillyl, hexyl and cyclohexyl) with alcohol (methanol, ethanol and isopropanol) and carbon monoxide in presence of iron pentacarbonyl as a catalyst. The selectivity of the compounds depends on the time of photolysis of the reaction as well as the solvent used. A stable reaction intermediate ferrole was isolated, and further photolysis with alcohols, resulted in the formation of α,β-vinylester. All the compounds were fully characterised by spectroscopic methods and the molecular structures of compounds 1, 16, 17 and 20 were established crystallographically.     

A one-flask synthesis and characterization of novel symmetrical pyridyl monoselenides and X-ray crystal structure of bis(5-bromo-2-pyridyl) selenide and bis(2-bromo-5-pyridyl) selenide

The present work reports an efficient one-pot synthesis of symmetrical pyridyl monoselenides by the reaction of bromo-/iodopyridines with the isopropylmagnesium chloride, ⁱPrMgCl followed by quenching with selenyl chloride, SeCl₂. The current methodology constitutes a convenient synthesis of bis(5-bromo-2-pyridyl) selenide (I), bis(2-bromo-5-pyridyl) selenide (II) and bis(2,5-dibromo-3-pyridyl) selenide (III) under cryogenic conditions requiring shorter time duration to give satisfactory yields. The hitherto unknown compounds have been characterized by elemental analysis and various spectroscopic techniques i.e., ¹H NMR, ¹³C NMR, FT-IR, mass spectrometry and X-ray crystallography.     

Response Surface Optimization of Medium Components for Naringinase Production from <Emphasis Type="Italic">Staphylococcus xylosus MAK2</Emphasis>

Response surface methodology was used to optimize the fermentation medium for enhancing naringinase production by Staphylococcus xylosus. The first step of this process involved the individual adjustment and optimization of various medium components at shake flask level. Sources of carbon (sucrose) and nitrogen (sodium nitrate), as well as an inducer (naringin) and pH levels were all found to be the important factors significantly affecting naringinase production. In the second step, a 22 full factorial central composite design was applied to determine the optimal levels of each of the significant variables. A second-order polynomial was derived by multiple regression analysis on the experimental data. Using this methodology, the optimum values for the critical components were obtained as follows: sucrose, 10.0%; sodium nitrate, 10.0%; pH 5.6; biomass concentration, 1.58%; and naringin, 0.50% (w/v), respectively. Under optimal conditions, the experimental naringinase production was 8.45 U/mL. The determination coefficients (R ²) were 0.9908 and 0.9950 for naringinase activity and biomass production, respectively, indicating an adequate degree of reliability in the model.     

Studies on the curing and thermal behaviour of diglycidyl ether of bisphenol-A (DGEBA) in the presence of aromatic diimide–diacids

This paper describes the synthesis and characterization of aromatic diimide–diacids (DIDAS) obtained by reacting pyromellitic dianhydride (PMDA), 4,4′-oxo diphthalic anhydride (ODA), 1,4,5,8-naphthalene tetra carboxylic dianhydride (NTDA) with excess of 4-aminobutyric acid (B) or 6-aminohexanoic acid (H) using N,N-dimethyl formamide (DMF) as solvent. The synthesized compounds were used as curing agents to investigate the effect of structure on the curing and thermal behaviour of diglycidyl ether of bisphenol-A (DGEBA). Structural characterization of DIDAS was done by using FTIR, ¹H-NMR, ¹³C-NMR spectroscopy and elemental analysis. Curing behaviour of DGEBA in the presence of aromatic DIDAS was investigated by differential scanning calorimetry (DSC). The peak exotherm temperature (T _P) was low in the case of DIDAS synthesized from ODA and high in the case of DIDAS synthesized from NTDA. Thermal stability of the isothermally cured DGEBA with DIDAS was investigated using dynamic thermogravimetry in nitrogen atmosphere. The char yield was highest for resin cured with DIDAS containing NTDA.     

Noncovalent assembly of ferrocene on modified gold surfaces mediated by uracil–adenine base pairs

Redox-active ferrocene was assembled on gold surfaces through the hydrogen bonding interactions between adenine-substituted ferrocene and a uracil-terminated organothiol monolayer. The surface coverage of ferrocene Γ could be varied from ca. 4 × 10^? 11 to 2.0 × 10^? 10 mol cm^? 2 by diluting the thiol-modified uracil derivative with inert 1-octanethiol. A decrease in the apparent electron transfer rate constant for ferrocene, k_app, from ca. 50 to 10 s^? 1 was observed upon increasing Γ.     

Theoretical studies of decomposition kinetics of CF3CCl2O radical

The unimolecular decomposition reaction of CF₃CCl₂O radical has been investigated using theoretical methods. Two most important channels of decomposition occurring via C–C bond scission and Cl elimination have been considered during the present investigation. Ab initio quantum mechanical calculations are performed to get optimized structure and vibrational frequencies at DFT and MP2 levels of theory. Energetics are further refined by the application of a modified Gaussian-2 method, G2M(CC,MP2). The thermal rate constants for the decomposition reactions involved are evaluated using Canonical Transition State Theory (CTST) utilizing the ab initio data. Rate constants for C–C bond scission and Cl elimination are found to be 6.7 × 10⁶ and 1.1 × 10⁸ s^?1, respectively, at 298 K and 1 atm pressure with an energy barrier of 8.6 and 6.5 kcal/mol, respectively. These values suggest that Cl elimination is the dominant process during the decomposition of the CF₃CCl₂O radical. Transition states are searched on the potential energy surface of the decomposition reactions involved and are characterized by the existence of only one imaginary frequency (NIMAG = 1) during frequency calculation. The existence of transition states on the corresponding potential energy surface is further ascertained by performing intrinsic reaction coordinate (IRC) calculation.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.