Methanol syntheses at low temperature in a liquid medium present an opportunity for full syngas conversion per pass. The aim of this work was to study the role of solvents polarity on low-temperature methanol synthesis reaction using eight different aprotic polar solvents. A “once through” catalytic system, which is composed of Cu nanoparticles and sodium methoxide, was used for methanol synthe...

Reaction rate constants and deuterium kinetic isotope effects for the reactions of BrOwith RCl (R ) methyl, ethyl, isopropyl, and tert-butyl) were measured using a tandem flowing afterglow-selected ion flow tube instrument. These results provide qualitative insight into the competition between two classical organic mechanisms, nucleophilic substitution (SN2) and base-induced elimination (E2). A...

Ion-molecule reactions of the type X(-) + CH3Y are commonly assumed to produce Y(-) through bimolecular nucleophilic substitution (SN2). Beyond this reaction, additional reaction products have been observed throughout the last decades and have been ascribed to different entrance channel geometries differing from the commonly assumed collinear approach. We have performed a crossed beam velocity ...

A high-level computational study using CCSD, CCSD(T), and G2(+) levels of theory has shown that unactivated vinyl substrates such as vinyl chloride would afford gas phase, single-step halide exchange by a pure in-plane sigma-approach of the nucleophile to the backside of the C--Cl sigma bond. Geometry optimization by CCSD/6-31+G* and CCSD(T)/6-31+G* confirms the earlier findings of Glukhovtsev,...

Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1R), and 1,3-di(R)-tetrazole-5-stannylenes (2R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability of 1R and 2R are calculated; with R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO2, CN and CF3. Asymmetric 2H appears more nucl...

Application of a dynamic microwave power system in the chemical synthesis of some phenothiazine and quinoline derivatives is described. Heterocyclic ring formation, aromatic nucleophilic substitution and heterocyclic aldehydes/ketones condensation reactions were performed on solid support, or under solvent free reaction conditions. The microwave-assisted Duff formylation of phenothiazine was ac...

When 9,10-dibromoanthracene was treated with bromine in CCl(4) without a catalyst, 1,2,3,4,9,10-hexabromo-1,2,3,4-tetrahydroanthracene (3) was obtained in 95% yield in the absence of other stereoisomers or rearomatization products. We investigated the base-induced elimination reaction of hexabromide 3 under various conditions. Pyridine-induced elimination of hexabromide 3 afforded 2,9,10-tribro...