The autoxidation of 2-(2-aminophenyl)-3- methylindole

Fischer indolisation of 2-aminophenyl ethyl ketone phenylhydrazone using glacial acetic acid saturated with hydrogen chloride as catalyst affords 3-methylindolo(l′:2′-3:4)2-methylquinazoline and 2-(2-aminophenyl)-3-methylindole. The latter compound is autoxidised to 2-(2-amino-phenyl)-3-hydroxy-3-methyl-3H-indole, a reaction which is shown to be dependent upon the presence of the primary amino group at the 2-position of the 2-phenyl substituent and which is much slower than the corresponding autoxidation of 2-(2-hydroxyphenyl)-3-methylindole to 3-hydroxy-2-(2-hydroxyphenyl)-3-methyl-3H-indole previously reported.Nitration of isopropyl phenyl ketone occurs preferentially at the ortho- rather than the meta- positions of the benzene nucleus.     

Weak radiative decays of hyperons within theSU(6) broken quark-diquark model

In view of persisting discrepancy between experimental and theoretical results, specially in the weak radiative decays of∑ ⁺ andΞ ⁰, we analyse these decays within the framework of the QCD inspired quark-diquark model. On introducing a slightSU(6) breaking we obtainα(∑ ⁺→p+γ)≈?0.9 which is in excellent agreement with experimental value. Other decays are also improved in this scheme.     

Molar extinction coefficients of some carbohydrates in aqueous solutions

Molar extinction coefficients of some carbohydrates viz. l-arabinose (C₅H₁₀O₅), d-glucose (C₆H₁₂O₆), d-mannose (C₆H₁₂O₆), d-galactose (C₆H₁₂O₆), d(-) fructose (C₆H₁₂O₆) and maltose (C₁₂H₂₄O₁₂) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by gamma ray transmission method in a narrow beam good geometry set-up. These coefficients have been found to depend upon the photon energy following a 4-parameter polynomial. These extinction coefficients for different sugars having the same molecular formula have same values varying within experimental uncertainty. Within concentration ranges studied, Beer-Lambert law is obeyed very well.     

Mössbauer effect studies on thermal decomposition of iron(III) hydroxy- and amino-benzoates

The thermal decomposition of iron(III) aminobenzoates (o-, m-, p-) and iron(III) hydroxybenzoates (p-, m-, p-) have been investigated from ambient temperature to 873 K in air using derivatography DTG-DTA-TG, Mössbauer, IR spectroscopy and XRD. The importance of Mössbauer spectra recorded at various stages of heating, without separating the product mixture, in studying the mode of decomposition is highlighted. The intermediates (e.g., Fe(II)-species) were confirmed. The nature of water of hydration and the order of stability (p->m->o-) have been investigated from decomposition temperatures. The kinetic model and parameters have been investigated for dehydration.P.U. and G.K.B. thank to Guru Nanak Dev. University, Amritsar for financial assistance.     

Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands

A series of 1-alkyl-4-aryl-1,2,3-triazoles (1-methyl-4-phenyl-1,2,3-triazole (1a); 1-propyl-4-phenyl-1,2,3-triazole (1b); 1-benzyl-4-phenyl-1,2,3-triazole (1c); 1-propyl-4-p-tolyl-1,2,3-triazole (1d)) have been prepared through a one-pot procedure involving in situ generation of the alkyl azide from a halide precursor followed by copper catalysed alkyne/azide cycloaddition (CuAAC) with the appropriate aryl alkyne. Cationic Re(I) complexes [Re(bpy)(CO)(3)(1a-d)]PF(6) (2a-d) were then prepared by stirring [Re(bpy)(CO)(3)Cl] with AgPF(6) in dichloromethane in the presence of ligands 1a-d. X-ray crystal structures were obtained for 2a and 2b. In the solid state, 2a adopts a highly distorted geometry, which is not seen for 2b, in which the plane of the triazole ligand tilts by 13° with respect to the Re-N bond as a result of a π-stacking interaction between the Ph substituent and one of the rings of the bpy ligand. This π-stacking interaction also results in severe twisting of the bpy ligand. Infrared spectra of 2a-d exhibit ν(CO) bands at ～2035 and ～1926 cm(-1) suggesting that these ligands are marginally better donors than pyridine (ν(CO) = 2037, 1932 cm(-1)). The complexes are luminescent in aerated dichloromethane at room temperature with emission maxima at 542 to 552 nm comparable to that of the pyridine analogue (549 nm) and blue shifted relative to the parent chloride complex. Long luminescent lifetimes are observed for the triazole complexes (475 to 513 ns) in aerated dichloromethane solutions at room temperature.     

Synthesis, characterisation and theoretical study of ruthenium 4,4'-bi-1,2,3-triazolyl complexes: fundamental switching of the nature of S1 and T1 states from MLCT to MC

The series of complexes [Ru(bpy)(3-n)(btz)(n)][PF(6)](2) (bpy = 2,2'-bipyridyl, btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy)(3)][Cl](2) (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1'-4' (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1'-3' through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4' increases by 0.98 eV compared to that of 3' due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S(1) states of 1'-3' are (1)MLCT in character whereas that of 4' is (1)MC. The optimisation of the T(1) state of 4' leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ(2)-btz)(κ(1)-btz)(2)](2+), confirming the (3)MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.