Study of SNAr Reactions of Halobenzenes with Imidazole under Ultrasonic and Microwave Irradiation

Summary. Nucleophilic aromatic substitution reactions with imidazole of haloarenes having strongly electron-withdrawing groups were studied under ultrasonic and microwave irradiations. The course of the S_NAr reactions was found to be strongly dependent on the electron-withdrawing properties of the substituents as well as on the leaving ability of the halogen atom. Microwave irradiation allowed to shorten the reaction time and to increase the yields compared with ultrasonic irradiation.     

Analysis of equilibrium in heme model systems, by a successive linear regression method

A method for determination of equilibrium constants in heme model systems is proposed, based on successive linear regression applied to spectrophotometric titrations. The method is illustrated for bis(dimethylglyoximate) iron(II) complexes with pyridine and 4-cyanopyridine ligands.     

A novel approach to the synthesis of 1,2-cis-glycopyranosides

Methyl 3,4,6-tri-O-benzyl-α-D-glucopyranoside and methyl 3,4,6-tri-O-benzyl-β-D-mannopyranoside were directly obtained by m-chloroperbenzoic acid treatment of (Z)-(2R,3R,4R)-6-methoxy-1,3,4-tribenzyloxy-5-hexen-2-ol.     

Cobalt oxide/tetraruthenated cobalt-porphyrin composite for hydrogen peroxide amperometric sensors

A new composite material constituted by mu-{5,10,15,20-tetra(4-pyridyl)porphyrinato cobalt(iii)}-tetrakis-{chloro-bis-(2,2'-bipyridine)ruthenium(ii)} complex (or CoTRP) and cobalt oxide, exhibiting high stability and sensitivity for the quantification of hydrogen peroxide, was obtained by the electrochemical polymerization of the tetraruthenated cobalt porphyrin in alkaline medium. The optimized experimental conditions for the preparation of the modified glassy carbon electrodes and for analysis of H2O2 were carefully determined. Fast sequential analysis (120 determinations h(-1)) in a wide linear dynamic range (5.0 x 10(-7) mol L(-1) to 2.0 x 10(-3) mol L(-1)), with high sensitivity and low detection limit (2.0 x 10(-7) mol L(-1)), was achieved by using these electrodes and the batch injection analysis (BIA) technique. Such characteristics allied to a good stability were explored for the specific determination of hydrogen peroxide in six commercial cosmetics and pharmaceutical product samples, giving results in excellent agreement with those obtained by the spectrophotometric method.     

Synthesis of 13c-labelled [s]-proline and its conformational analysis by nuclear magnetic resonance

In order to analyze completely the ring conformation of [S]-Proline (l-thiazolidine-4-carboxylic acid) this compound has been synthesized with its C_δ atom enriched at 90% in ¹³C. The ¹H-¹H, ¹³C-¹H, ¹³C-¹³C vicinal coupling constants measured at several pH values describe well the geometry of the thiazolidine ring. The results suggest that the ring has an average planar conformation only in a narrow range of pH close to the pK of the amine group. Above and below this pH the ring tends to adopt preferentially the S_γendo and S_γexo puckered conformations respectively. It is concluded that a good correlation exists between the value of the dihedral angle ø and the character S_γendo or S_γexo of the ring.     

Nuclearity controlled cyanide-bridged bimetallic CrIII-MnII compounds: synthesis, crystal structures, magnetic properties and theoretical calculations

The preparation, X-ray crystallography and magnetic investigation of the compounds PPh4[Cr(bipy)(CN)4].2 CH3CN.H2O (1) (mononuclear), [[Cr(bipy)(CN)4]2Mn-(H2O)4].4H2O (2) (trinuclear), [[Cr(bipy)(CN)4]2Mn(H2O)2] (3) (chain) and [[Cr(bipy)(CN)4]2Mn(H2O)].H2O.CH3CN (4) (double chain) [bipy=2,2'-bipyridine; PPh4 (+)=tetraphenylphosphonium] are described herein. The [Cr(bipy)(CN)4]- unit act either as a monodentate (2) or bis-monodentate (3) ligand toward the manganese atom through one (2) or two (3) of its four cyanide groups. The manganese atom is six-coordinate with two (2) or four (3) cyanide nitrogens and four (2) or two (3) water molecules building a distorted octahedral environment. In 4, two chains of 3 are pillared through interchain Mn-N-C-Cr links which replace one of the two trans-coordinated water molecules at the manganese atom to afford a double chain structure where bis- and tris-monodenate coordination modes of [Cr(bipy)(CN)4]- coexist. The magnetic properties of 1-4 were investigated in the temperature range 1.9-300 K. A Curie law behaviour for a magnetically isolated spin quartet is observed for 1. A significant antiferromagnetic interaction between CrIII and MnII through the single cyanide bridge [J=-6.2 cm(-1), the Hamiltonian being defined as H=-J(SCr1.SMn+SCr2.SMn] occurs in 2 leading to a low-lying spin doublet which is fully populated at T <5 K. A metamagnetic behaviour is observed for 3 and 4 [the values of the critical field Hc being ca. 3000 (3) and 1500 Oe (4)] which is associated to the occurrence of weak interchain antiferromagnetic interactions between ferrimagnetic Cr2III MnII chains. The analysis of the exchange pathways in 2-4 through DFT type calculations together with the magnetic bevaviour simulation using the quantum Monte Carlo methodology provided a good understanding of their magnetic properties.     

Enzymic Acylation of Methyl D- and L-Glucopyranosides and 6-Deoxy-glucopyranosides

Abstract

Methyl 6-O-butyryl-α-D- and L-glucopyranosides and methyl 6-deoxy-α-D- and L-glucopyranosides have been submitted to lipase catalyzed butyrylation, using porcine pancreatic, Candida cylindracea, and Pseudomonas cepacia lipases in organic solvents. The influence of the orientation of the secondary hydroxyl groups on the regioselectivity of the butyrylation is discussed.