Search results for "Zen"
showing 10 items of 3479 documents
1980
Formation and behaviour of radiation induced free radicals in statistical copolymers from vinyl hydrosulfide and styrene (1:1, 1:4, and 1:10) were investigated by means of ESR spectroscopy. The corresponding homopolymers were also included in these studies. After γ-irradiation of the copolymers at 77 K and subsequent annealing to 293 K it was possible to detect thio radicals. Their relative yields were found to increase with increasing styrene content. Investigations regarding the thermal behaviour of the radiation induced radicals in the copolymers allowed the assumption of two mechanisms responsible for the formation of the thio radicals: First, the formation takes place via ion radicals …
Two strained hexahelicenophanes
2000
The crystal structures of the [6]helicenes 4,13-(1,10-decamethylenedioxy)hexahelicene, C36H34O2, (I), and 4,13-(1,8-octamethylenedioxy)hexahelicene, C34H30O2, (II), show strong steric interactions between the terminal benzene rings and the polymethylenedioxy chains. The shortest ring A and F distances amount to 2.941 (3) and 2.902 (3) A, respectively. The increased steric energy of the ground state is responsible for a significantly lower racemization barrier of (I) and (II) in comparison to the unsubstituted [6]helicene.
Unveiling the regioselectivity in electrophilic aromatic substitution reactions of deactivated benzenes through molecular electron density theory
2021
The origin of the meta regioselectivity in electrophilic aromatic substitution (EAS) reactions of deactivated benzene derivatives is herein analysed through Molecular Electron Density Theory (MEDT). To this end, the EAS reaction of benzenesulfonic acid with the nitronium NO2+ ion in H2SO4 solution has been studied at the ωB97X-D/6-311G(d,p) level. This reaction takes place through a two-step polar mechanism involving the formation of an unstable cation intermediate. The activation Gibbs free energies associated with the three competitive regioisomeric reaction paths are found in the narrow range of 15.5–18.3 kcal mol−1. By using the Eyring–Polanyi equation a relationship of 18.7 (ortho) : 8…
Valence Topological Charge-Transfer Indices for Reflecting Polarity: Correction for Heteromolecules
2005
Valence topological charge-transfer (CT) indices are applied to the calculation of dipole moments mu. The mu calculated by algebraic and vector semisums of the CT indices are defined. The model is generalized for molecules with heteroatoms and corrected for sp(3)-heteromolecules. The ability of the indices for the description of the molecular charge distribution is established by comparing them with mu of the valence-isoelectronic series of cyclopentadiene, benzene and styrene. Two CT indices, mu(vec) (vector semisum of vertex-pair mu) and mu(vec)V (valence mu(vec)) are proposed. The mu(vec) behaviour is intermediate between mu(vec) and mu(experiment). The correction is produced in the corr…
Azoxybenzene rearrangement catalyzed by solid acids
2008
Abstract For the first time, the potential of acidic cation-exchange resin (sulfonated polystyrene) to catalyze the Wallach rearrangement of azoxybenzene into 4-hydroxyazobenzene has been proved. This finding reveals an alternative reaction path possible in a heterogeneous process using solid acids and may help to clear some doubts concerning the rearrangement mechanism postulated so far. The resin-induced reaction was found to proceed exclusively in a non-polar medium. Reasonable yield was obtained particularly in isooctane due to favorable distribution of azoxybenzene throughout the resin's matrix. On the contrary, the HY type zeolite did not activate the rearrangement, most probably beca…
Compensation of steric demand by cation–π interactions, cobaltocenium cations as guests in tetraurea calix[4]arene dimers
2003
The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the vari…
Benzyl ions from 1,1-(2,2′-dimethoxyphenyl)-substituted 2-methylpropanes under electron ionization
2006
The electron ionization (EI)-induced fragmentations of a series of 1,1-(2,2'-dimethoxyphenyl)-substituted 2-methylpropanes (1-20) in both 70 eV and mass-analyzed ion kinetic energy (MIKE) spectra have been investigated. The EI-MS spectra of these compounds are characterized by the presence of abundant benzyl ions. These ions result from competitive hydrogen migration from the 2- and 2'-methoxy groups on the carbenium center of the diphenylmethyl cations formed by benzylic cleavage of the molecular ions. The relative abundances of the benzyl ions arising from such competitive processes are discussed and rationalized. The steric effect of the 3- or 3'-substituents is the main discriminating f…
Synthesis, crystal and molecular-electronic structure, and kinetic investigation of two new sterically hindered isomeric forms of the dimethyl[methyl…
2017
Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally characterized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group View the MathML source, a = 8.1542(2), b = 11.0728(3), c = 11.2680(3) Å, α = 116.557(3), β = 95.155(2), γ = 108.258(2)°, V = 831.97(4) Å3, Z = 2, R = 0.0251 for 2429 reflections; the crystals of 2 are monoclinic:…
Synthesis of a macrobicycle incorporating the tris(pyrazolyl)methane ligand.
2004
Steric crowding of the 3-position of tris(pyrazolyl)borate and -methane ligands has produced tetrahedral metal complexes with controlled reactivity. As an alternative, we propose to incorporate the tris(pyrazolyl)methane chelate in a macrobicyclic structure in order to create a cavity with well-defined dimensions and shape. Acid-catalyzed equilibration of excess of the new pyrazole 3-(1H-pyrazol-3-yl)benzenemethanethiol acetate with HC(3,5-Me(2)pz)(3) followed by hydrolysis affords a functionalized tris(pyrazolyl)methane, which reacts with 1,3,5-tris(bromomethyl)benzene in K(2)CO(3)/DMF to give the title compound. [structure: see text]