Reaction of α-halogen substituted β-ethoxyvinyl trifluoromethyl ketones with 2-aminopyridine: new route to trifluoroacetyl-containing heterocycles

The reaction of α-halosubstituted β-ethoxyvinyl trifluoromethyl ketones with 2-aminopyridine gives 3-trifluoroacetyl imidazo[1,2-a]pyridine and 3-halo-1,1,1-trifluoro-4-(2-pyridinylamino)-3-buten-2-ones. The product ratio depends on the nature of the α-halogen atom and the solvent.     

Regioselective Sequential Additions of Nucleophiles and Electrophiles to Perfluoroalkylfullerenes: Which Cage C Atoms Are the Most Reactive and Why?

The sequential addition of CN^? or CH₃^? and electrophiles to three perfluoroalkylfullerenes (PFAFs), C_s‐C₇₀(CF₃)₈, C₁‐C₇₀(CF₃)₁₀, and C_s‐p‐C₆₀(CF₃)₂, was carried out to determine the most reactive individual fullerene C atoms (as opposed to the most reactive C?C bonds, which has previously been studied). Each PFAF reacted with CH₃^? or CN^? to generate metastable PFAF(CN)^? or PFAF(CH₃)₂^2? species with high regioselectivity (i.e., one or two predominant isomers). They were treated with electrophiles E⁺ to generate PFAF(CN)(E) or PFAF(CH₃)₂(E)₂ derivatives, also with high regioselectivity (E⁺=CN⁺, CH₃⁺, or H⁺). All of the predominant products, characterized by mass spectrometry and ¹⁹F NMR spectroscopy, are new compounds. Some could be purified by HPLC to give single isomers. Two of them, C₇₀(CF₃)₈(CN)₂ and C₇₀(CF₃)₁₀(CH₃)₂(CN)₂, were characterized by single‐crystal X‐ray diffraction. DFT calculations were used to propose whether a particular reaction is under kinetic or thermodynamic control.     

Study of the mechanism of base induced dehydrobromination of trans-β-bromostyrene

Observation that rates of dehydrobromination of trans-β-bromostyrene (1) and the Hofmann degradation of tetrabutyl ammonium cation depend on strength of base in different ways and that treatment of 1 with base results in fast abstraction of the β-proton imply the possibility that the dehydrobromination of 1 could proceed via α-elimination and Ph migration. In order to clarify this question, β-¹³C-labeled 1 was obtained and subjected to PTC dehydrobromination which proceeds without migration of Ph. The obtained results are consistent with an irreversible E1cB mechanism.     

Infrared spectroscopic studies of transition metal complexes and polarizability effect

The literature data on substituent influence on the CS, CN, NC, NN, and NO stretching frequencies (ν) in the IR spectra and in specific cases on their respective stretching force constants (k) have been analyzed for 28 series of the transition metal complexes. The ν and k values were first established to depend not only on the inductive and resonance effects but on the polarizability of substituents as well. The contribution of the polarizability effect varies from 0 to 57% with the type of series.     

Theory of reversible associative-dissociative diffusion-influenced chemical reaction. I. Geminate reaction

A many-particle, in the general case, inhomogeneous reacting system of independent pairs of reactants, where geminate reversible reaction A+B?C takes place, is considered in the framework of the kinetic theory approach. The kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the reaction course are established, as well as the relations between the kinetic dependencies under different initial conditions including the relations that extend the familiar literature results to the case of rather realistic model of the reacting system. Universal long-term kinetic laws of the reaction course are determined.     

Phosphorylation of pyridoxal azomethines. Synthesis of phosphorus containing azomethines and furopyridines

New O-phosphorylated pyridoxal derivatives have been synthesized through the reaction of azomethines with Р^V acid chlorides. 2-Chloro-2-thioxo-5,5-dimethyl-1,3,2-dioxaphosphinanes and diethylchlorothiophosphate have been employed as phosphorylating agents. Regardless of the nature of the phosphorylating agent, the reaction is regioselective at phenolic hydroxyl group. The structure of final products is determined by the nature of the substituent at the nitrogen atom. If R is alkyl or cycloalkyl group, the products of the reaction represent phosphorylated pyridoxal imines, whereas phosphorylated furopyridines are formed in the case R is aryl substituent.     

Catalyst-Free Arylation of Tertiary Phosphines with Diaryliodonium Salts Enabled by Visible Light

The visible-light-induced arylation of tertiary phosphines with aryl(mesityl)iodonium triflates to produce the quaternary phosphonium salts occurs under mild, metal, and catalyst-free conditions. Photo-excited EDA complexes between diaryliodonium salts and phosphines supposedly enable this transformation, which is difficult to achieve through the traditional ground-state reactions. Demonstrating high functional group tolerance, broad scope, and complete selectivity of the aryl group transfer, the method is particularly compatible with sterically congested phosphines, which are challenging under metal-based catalytic methods.     

Proton Relaxometry of Long-Lived Spin Order

A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D₂O and 240 s in deuterated methanol, which are much longer than the T₁-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years.