Structures of two N-{2-([(5-amino-1,3,4-thiadiazol-2-yl)difluoromethyl]-4-halophenyl}acetamides

Abstract  

The compounds, N-{2-[(5-amino-1,3,4-thiadiazol-2-yl)difluoromethyl]-4-chlorophenyl}acetamide (1: X = Cl) and N-{2([(5-amino-1,3,4-thiadiazol-2-yl)difluoromethyl]-4-bromo-phenyl}acetamide (1: X = Br), are isostructural. The molecules are near ‘‘V’’ shaped with the angles between the two aromatic planes ca. 84° in each case. The various intermolecular interactions, namely N–H···O, N–H···N, N–H···F, and C–H···N hydrogen bonds and C–H···π, C–Cl···π and C–O···π interactions, generate 3-D arrays. Compound (1: X = Cl) crystallizes in the monoclinic space group P21/c with a = 16.9032(7) ?, 10.2193(4) ?, c = 7.5227(4) ?, β = 100.179(3)° and Z = 4. Compound (1: X = Br) crystallizes in the monoclinic space group P21/c with a = 17.2119(4) ?, 10.2167(2) ?, c = 7.5677(2) ?, β = 100.326(2)° and Z = 4.     

Rearrangement, nucleophilic substitution, and halogen switch reactions of alkyl halides over NaY Zeolite: formation of the bicyclobutonium cation inside the zeolite cavity

Rearrangement and nucleophilic substitution of cyclopropylcarbinyl bromide over NaY and NaY impregnated with NaCl was observed at room temperature. The first-order kinetics are consistent with ionization to the bicyclobutonium cation, followed by internal return of the bromide anion or nucleophilic attack by impregnated NaCl to form cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl chlorides. The product distribution analysis revealed that neither a purely kinetic distribution, similar to what is found in solution, nor the thermodynamic ratio, which favors the allylcarbinyl halide, was observed. Calculations showed that bicyclobutonium and cyclopropylcarbinyl carbocations are minimal over the zeolite structure, and stabilized by hydrogen bonding with the framework structure. A new process of nucleophilic substitution is reported, namely halogen switch, involving alkyl chlorides and bromides of different structures. The reaction occurs inside the zeolite pores, due to the confinement effects and is an additional proof of carbocation formation on zeolites. The results support the idea that zeolites act as solid solvents, permitting ionization and solvation of ionic species.     

Quasi-Norm interpolation error estimates for the piecewise linear finite element approximation of p-Laplacian problems

Summary. In this work, new interpolation error estimates have been derived for some well-known interpolators in the quasi-norms. The estimates are found to be essential to obtain the optimal a priori error bounds under the weakened regularity conditions for the piecewise linear finite element approximation of a class of degenerate equations. In particular, by using these estimates, we can close the existing gap between the regularity required for deriving the optimal error bounds and the regularity achievable for the smooth data for the 2-d and 3-d p-Laplacian.Mathematics Subject Classification (1991): 65N30     

Electron emission spectra in low energy positron-atom collisions

Energy spectra of electrons ejected from an Ar target, in the forward direction, by a low energy positron beam have been measured and compared with theory. Structures are present in these spectra at energies compatible with electron capture to continuum states of the scattered positron (ECC) and with binary collisions.     

Synthesis of new 3‐(trifluoromethyl)‐1H‐indoles by reduction of trifluoromethyloxoindoles

This work describes the synthesis of new 3‐trifluoromethylindoles. Different isatins were trifluoromethylated using (trifluoromethyl) trimethylsilane (Me₃SiCF₃) as a nucleophilic agent giving new 3‐hydroxy‐3‐(trifluoromethyl)indolin‐2‐one. Different “one‐step” procedures to transform the latter compounds into the reduced indoles were attempted, but failed. For the synthesis of the new trifluoromethylindoles the corresponding 2‐oxo‐3‐(trifluoromethyl)indoles were reduced using borane/THF complex to furnish 3‐(trifluoromethyl)indolin‐3‐ol that additionally were dehydrated using thionyl chloride in pyridine to give excellent yields of the desired products.     

Synthesis of the Four Epimeric Tosylates of (5R)-2, 3-Epoxy-5-isopropenyl-cyclohexanol

Described is the synthesis of the four optically pure epoxy-tosylates 5, 6, 9 and 12, each with four chiral centers determined, from a single starting material, (R)(-) carvone.     

Regiospecific Baeyer-Villiger Oxidation of α,α-Dichlorocyclobutanones: A Norbisabolide γ-lactone Analogue1

Details and methodological comparisons are presented on the preparation of a norbisabolide γ-lactone analogue (4) via dichloroketene cycloaddition to limonene followed by regioselective Baeyer-Villiger oxidation (CH₃CO₃H) of the α,α-dichlorocyclobutanones 3 and C-Cl reduction (Zn/HOAc). The sequence of reduction followed by oxidation (HOCI) applied to 3 produced 4 in much better yield.