Fluoride effect on the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates

Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd.     

Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

Thermodynamic properties of organic compounds in aqueous solution. II. Apparent molal heat capacities of piperidines,morpholines, and piperazines

Apparent molal heat capacities of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of ΔC _p for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined.     

Reaction of singlet oxygen with some benzylic sulfides

Product distribution, total quenching rate (k_T), and rate of chemical reaction (k_r) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines.     

A discussion on the energies involved in specific adsorption of ions

The change in specific adsorption of I^? ions on the series of metals Au, Hg, Bi, Pb, Cd, and Ga is analyzed using data of specifically adsorbed charge and shift in potential of zero charge. Factors determining the change in adsorbability are discussed in the light of previous formulations. It is shown that the work connected with water desorption as an ion becomes adsorbed, usually neglected or underestimated in previous discussions, is very likely to be the main factor determining the change in adsorbability along the series of metals. A rough estimation of energies involved in water desorption suggests that metal—water surface bonds are probably weak on sp-metals so that they are unable to affect the reactivity of metal surfaces with respect to the gas phase as strong covalent surface bonds are involved, for instance in the hydrogen evolution reaction. Conversely, the strong effect of water desorption on the specific adsorption of ions may be an indication of ion—metal interactions to be substantially independent of the nature of the metal. This suggests that covalent contributions to the surface bond are apparently minor for metals more electropositive than Au.     

Low oxidation state ruthenium chemistry : IV. The reactions of M(CO)2(PPh3)3 complexes (M = Fe,Ru) and the hydrogenation and isomerization of alkenes catalyzed by RuL(CO)2(PPh3)2 (L = H2, PPh3)

The complexes M(CO)₂(PPh₃)₃ (I, M = Fe; II, M = Ru) readily react with H₂ at room temperature and atmospheric pressure to give cis-M(H)₂(CO)₂(PPh₃)₂ (III, M = Fe;IV,M = Ru). I reacts with O₂ to give an unstable compound in solution, in a type of reaction known to occur with II which leads to cis-Ru(O₂)(CO)₂(PPh₃)₂(V). Even compound IV reacts with O₂ to give V with displacement of H₂; this reaction has been shown to be reversible and this is the first case where the displacement of H₂ by O₂ and that of O₂ by H₂ at a metal center has been observed. III and IV are reduced to M(CO)₃(PPh₃)₂ by CO with displacement of H₂; Ru(CO)₃- (PPh₃)₂ is also formed by treatment of IV with CO₂, but under higher pressure. Compounds II and IV react with CH₂CHCN to give Ru(CH₂CHCN)(CO)₂- (PPh₃)₂(VI) which reacts with H₂ to reform the hydride IV.cis-Ru(H)₂(CO)₂(PPh₃)₂(IV) has been studied as catalyst in the hydrogenation and isomerization of a series of monoenes and dienes. The catalysts are poisoned by the presence of free triphenylphosphine. On the other hand the ready exchange of H₂ and O₂ on the “Ru(CO)₂(PPh₃)₂” moiety makes IV a catalyst not irreversibly poisoned by the presence of air. It has been found that even Ru(CO)₂(PPh₃)₃(II) acts as a catalyst for the isomerization of hex-1-ene at room temperature under an inert atmosphere.     

On the Effect of the Aglycon Structure of Three Aryl β-D-Galactosides on the Yield and the Regioselectivity of the Transglycolytic Synthesis of N-Acetyllactosamine

ABSTRACT

We examined the effect as donors of three aryl β-D-galactosides (i.e. p-nitrophenyl β-D-galactopyranoside, o-nitrophenyl β-D-galactopyranoside and phenyl β-D-galacto-pyranoside) on the regioselectivity and the yield of the synthesis of N-acetyllactosamine obtained from the transglycosylation reaction catalyzed by a crude preparation of β-D-galactosidase from Bacillus circulans at 25 °C, 37 °C and 55 °C, respectively. Using p-nitrophenyl β-D-galactopyranoside the reaction results were fully regiospecific at all the temperatures considered: the maximum molar yield (74%) was obtained at an incubation temperature of 55 °C. Using o-nitrophenyl β-D-galactopyranoside as the donor the reaction was still highly regioselective and the maximum molar yield (50%) was achieved at an incubation temperature also of 55 °C. Using phenyl β-D-galactopyranoside transglycolytic products appear only at an incubation temperature of 55 °C but at very low molar yield (about 14%) and lower regioselectivity.     

Ambivalent role of metal chlorides in ring opening reactions of 2H-azirines: synthesis of imidazoles,pyrroles and pyrrolinones

2H-Azirines were found to react with imines, enaminones and enaminoesters in the presence of metal salts. Imidazoles, pyrroles and new pyrrolinones derivatives are isolated in good overall yields. The role of metal salts was investigated as they can act as Lewis acids or electron donors. Mechanisms are proposed suggesting that imidazoles arise from addition of azirine to imines via radical or ionic mechanism; pyrroles and pyrrolinones are obtained from azirines with enamino derivatives when the salt acts as a Lewis acid. In the latter case the properties of the metallic compound influence the reaction regioselectivity.     

Extensions of automorphisms and gauge symmetries

We characterize the automorphisms of aC ^*-algebra which extend to automorphisms of the crossed product by a compact group dual. The case where the inclusion is equipped with a group of automorphisms commuting with the dual action is also treated. These results are applied to the analysis of broken gauge symmetries in Quantum Field Theory to draw conclusions on the structure of the degenerate vacua on the field algebra.Dedicated to Huzihiro ArakiResearch supported by MURST and CNR, GNAFA     

On classification ofN=2 supersymmetric theories

We find a relation between the spectrum of solitons of massiveN=2 quantum field theories ind=2 and the scaling dimensions of chiral fields at the conformal point. The condition that the scaling dimensions be real imposes restrictions on the soliton numbers and leads to a classification program for symmetricN=2 conformal theories and their massive deformations in terms of a suitable generalization of Dynkin diagrams (which coincides with the A-D-E Dynkin diagrams for minimal models). The Landau-Ginzburg theories are a proper subset of this classification. In the particular case of LG theories we relate the soliton numbers with intersection of vanishing cycles of the corresponding singularity; the relation between soliton numbers and the scaling dimensions in this particular case is a well known application of Picard-Lefschetz theory.