Experimental and theoretical approaches to the study of the reactivity and mechanism of the substitution of phenyl 1-(2,4-dinitronaphthyl) ether with anilines derivatives

Reactions of aniline derivatives in dimethyl sulfoxide with phenyl 1-(2,4-dinitronaphthyl) ether yield aryl 1-(2,4-dinitronaphthyl) amine, which results in substitution of the phenoxy groups at the naphthyl ipso carbon atom. Rate constants were measured spectrophotometrically, and reaction proton transfer was rate limiting. The values of the rate coefficients indicate a rate-limiting proton transfer mechanism with significant substituent effects. The calculated activation parameters were of regular variation with substituents in 4- and 3-position in the aniline nucleophile, and the reaction proceeded through a common mechanism. Hammett's reaction constant showed that the reaction rate constants depend on the electron density of the nitrogen atom of aniline derivative, whereas the coefficient value obtained from the Brönsted relation indicated that the reaction was significantly associative and quite zwitterion like. Computational studies of the substitution were carried out based on density functional theory, and theoretical to the experimental agreement was achieved.     

Photocatalytic Oxidation of HMF under Solar Irradiation: Coupling of Microemulsion and Lyophilization to Obtain Innovative TiO2-Based Materials

The photocatalytic oxidation of biomass-derived building blocks such as 5-hydroxymethylfurfural (HMF) is a promising reaction for obtaining valuable chemicals and the efficient long-term storage of solar radiation. In this work, we developed innovative TiO₂-based materials capable of base-free HMF photo-oxidation in water using simulated solar irradiation. The materials were prepared by combining microemulsion and spray-freeze drying (SFD), resulting in highly porous systems with a large surface area. The effect of titania/silica composition and the presence of gold-copper alloy nanoparticles on the properties of materials as well as photocatalytic performance were evaluated. Among the lab-synthesized photocatalysts, Ti₁₅Si₈₅ SFD and Au₃Cu₁/Ti₁₅Si₈₅ SFD achieved the higher conversions, while the best selectivity was observed for Au₃Cu₁/Ti₁₅Si₈₅ SFD. The tests with radical scavengers for both TiO₂-m and Au₃Cu₁/Ti₁₅Si₈₅ SFD suggested that primary species responsible for the selective photo-oxidation of HMF are photo-generated electrons and/or superoxide radicals.     

Kinetics of the Reaction of 2-Chloro-quinoxaline with Hydroxide Ion in ACN–H2O and DMSO–H2O Binary Solvent Mixtures

The kinetics of alkaline hydrolysis of 2-chloroquinoxaline (QCl) with hydroxide ion was investigated spectrophotometrically at different percentages of aqueous–organic solvent mixtures with acetonitrile (10–60% v/v) and with dimethylesulphoxide (10–80%) over the temperature range from 25 to 45 °C. The reaction was performed under pseudo first order conditions with respect to 2-chloroquinoxaline (QCl). An increase in the percentage of organic solvent (v/v) has different effects on the reaction rate constants, presumably due to hydrogen bond donor and acceptor differences of the media and other solvatochromic parameters. The data were discussed in terms of the Kamelt-Taft parameter and E _T(30). A nonlinear relation between the logarithm of the rate constant and reciprocal of the dielectric constant suggests the presence of selective solvation by the polar water molecules. Activation parameters ΔH ^#, ΔS ^# and ΔG ^# were determined and discussed.     

Taming Gold(I)–Counterion Interplay in the De‐aromatization of Indoles with Allenamides

A careful interplay between the π electrophilicity of a cationic Au^I center and the basicity of the corresponding counterion allowed for the chemo‐ and regioselective inter‐ as well as intramolecular de‐aromatization of 2,3‐disubstituted indoles with allenamides. The silver‐free bifunctional Lewis acid/Brønsted base complex [{2,4‐(tBu)₂C₆H₃O}₃PAuTFA] assisted the formation of a range of densely functionalized indolenines under mild conditions.     

Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics

A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe₂, CF₃, CO₂Me, CN, NO₂, ?C?C‐(p‐C₆H₄?NHex₂), ?C?C?(p‐C₆H₄?CO₂Oct)) at [RhX(PMe₃)₄] ( 1 ) (X=?C?C?SiMe₃ ( a ), ?C?C‐(p‐C₆H₄?NMe₂) ( b ), ?C?C?C?C?(p‐C₆H₄?NPh₂) ( c ) or ?C?C?{p‐C₆H₄‐C?C?(p‐C₆H₄‐N(C₆H₁₃)₂)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S₁ state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (Φ_ISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T₁ state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated.