Rhodium catalyzed hydroformylation of 2-phenylsulfonylbicyclo[2.2.1] alkenes: effect of the phenylsulfonyl group

The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and norbornadiene derivatives catalyzed by the unmodified Rh(CO)₂acac system are presented. The reaction, occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the regioselectivity of the process.     

Line Narrowing of a Tunable High Pressure CO2 Laser by Means of an Improved Non-Littrow Cavity

A model is reported to foresee ,for different mirror choices, the spectral properties of a high pressure, frequency tunable, CO₂ laser, operating with a non-Littrow grating mounting. The calculations show a larger frequency selectivity for not collimated plane cavities. The model is experimentally verified in a suitable high pressure laser. In particular narrowed linewidths less than 300MHz ( FWHM) are obtained.     

Comments on “power-law falloff in the Kosterlitz-Thouless phase of a two-dimensional lattice Coulomb gas”

A simple argument is presented by which one can show that the critical inverse temperature _c of a two-dimensional Coulomb gas (standard or hard-core) with activityz satisfies , where in the low-activity limit. Previous results yield .     

Quantum field theories of vortices and anyons

We develop the quantization of topological solitons (vortices) in three-dimensional quantum field theory, in terms of the Euclidean region functional integral. We analyze in some detail the vortices of the abelian Higgs model. If a Chern-Simons term is added to the action, the vortices turn out to be anyons, i.e. particles with arbitrary real spin and intermediate () statistics. Localization properties of the interpolating field, scattering theory and spin-statistics connection of anyons are discussed. Such analysis might be relevant in connection with the fractional quantum Hall effect and two-dimensional models of HighT _csuperconductors.     

Homolytic substitutions in indolinone nitroxide radicals—I: Reaction with aroyloxyl radicals

Indolinone nitroxides undergo a homolytic substitution with aroyl oxyl radicals, leading to two isomers, 7-aroyloxy- and 5-aroyloxy-derivative, respectively, whose structures were assigned on the basis of the ESR hfccs and of the ¹H NMR spectra of the corresponding amines. The presence of aroyl oxyl radicals in the reaction medium was demonstrated by thermal decomposition of benzoyl peroxide in the presence of aromatic acids.     

Synthesis of (s)-2-(2-methylbutyl)thiophene

Optically active (S)-2-(2-methylbutyl)thiophene was obtained by different procedures. Among them, the cross-coupling reaction between 2-methylbutylmagnesium chloride and 2-chlorothio-phene proved to be the most efficient one. Compound 1 was thus obtained in satisfactory yield and rather high optical purity (82%).     

Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane

Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.     

Modeling of overloaded gradient elution of nociceptin/orphanin FQ in reversed-phase liquid chromatography

The Reversed-phase (RP) gradient elution chromatography of nociceptin/orphanin FQ (N/OFQ), a neuropeptide with many biological effects, has been modeled under linear and non-linear conditions. In order to do this, the chromatographic behavior has been studied under both linear and nonliner conditions under isocratic mode at different mobile phase compositions--ranging from 16 to 19% (v/v) acetonitrile (ACN) in aqueous trifluoracetic acid (TFA) 0.1% (v/v)-on a C-8 column. Although the range of mobile phase compositions investigated was quite narrow, the retention factor of this relatively small polypeptide (N/OFQ is a heptadecapeptide) has been found to change by more than 400%. In these conditions, gradient operation resulted thus to be the optimum approach for non-linear elution. As the available amount of N/OFQ was extremely reduced (only a few milligrams), the adsorption isotherms of the peptide, at the different mobile phase compositions examined, have been measured through the so-called inverse method (IM) on a 5 cm long column. The adsorption data at different mobile phase compositions have been fitted to several models of adsorption. The dependence of the isotherm parameters on the mobile phase composition was modeled by using the linear solvent strength (LSS) model and a generalized Langmuir isotherm that includes the mobile phase composition dependence. The overloaded gradient separation of N/OFQ has been modeled by numerically solving the equilibrium-dispersive (ED) model of chromatography under a selected gradient elution mode, on the basis of the previously determined generalized Langmuir isotherm. The agreement between theoretical calculations and experimental overloaded band profiles appeared reasonably accurate.     

Syntheses, structures, and reactivity of new pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) 4-acyl-5-pyrazolonate complexes

New [CpM(Q)Cl] complexes (M = Rh or Ir, Cp = pentamethylcyclopentadienyl, HQ = 1-phenyl-3-methyl-4R(C=O)-pyrazol-5-one in general, in detail HQ(Me), R = CH(3); HQ(Et), R = CH(2)CH(3); HQ(Piv), R = CH(2)-C(CH(3))(3); HQ(Bn), R = CH(2)-(C(6)H(5)); HQ(S), R = CH-(C(6)H(5))(2)) have been synthesized from the reaction of [CpMCl(2)](2) with the sodium salt, NaQ, of the appropriate HQ proligand. Crystal structure determinations for a representative selection of these [CpM(Q)Cl] compounds show a pseudo-octahedral metal environment with the Q ligand bonded in the O,O'-chelating form. In each case, two enantiomers (S(M)) and (R(M)) arise, differing only in the metal chirality. The reaction of [CpRh(Q(Bn))Cl] with MgCH(3)Br produces only halide exchange with the formation of [CpRh(Q(Bn))Br]. The [CpRh(Q)Cl] complexes react with PPh(3) in dichloromethane yielding the adducts CpRh(Q)Cl/PPh(3) (1:1) which exist in solution in two different isomeric forms. The interaction of [CpRh(Q(Me))Cl] with AgNO(3) in MeCN allows generation of [CpRh(Q(Me))(MeCN)]NO(3).3H(2)O, whereas the reaction of [CpRh(Q(Me))Cl] with AgClO(4) in the same solvent yields both [CpRh(Q(Me))(H(2)O)]ClO(4) and [CpRh(Cl)(H(2)O)(2)]ClO(4); the H(2)O molecules derive from the not-rigorously anhydrous solvents or silver salts.