Mécanisme de la réaction de cyclisation en milieu aqueux de carbanilates de propargyle en méthylène-4 oxazolidinones-2

The alkaline hydrolysis of propargyl 3-chlorocarbanilates was investigated kinetically using uv spectropotometry. The cyclization to 4-methoylene-2-oxazolisinones proceeds via the numcleophilic attack of the substrate anion concomitantly with that of the hydroxide ion on the triple bond. The nucleophilic attack leads directly to the heterocycle whereas the hydroxide ion attack gives rise to a ketocarbamate which is then cyclized to the oxazolidione.     

Automatic apparatus for the determination of carbon and hydrogen in organic compounds

A microanalytical determination of carbon and hydrogen in organic compounds is achieved by an original technique of coulometric titration in a nonaqueous medium. The apparatus, designed for the purpose, wholly automatic and monitored by a computer, makes possible the analysis of 23 samples without any intervention from the operator. Each analysis takes about 10 min and the precision of the method results in relative standard deviations of about 0.1 and 1% for carbon and hydrogen, respectively.     

The dichlorovinylation of enolates

The condensation of certain ketone and ester enolates with trichloroethylene proceeds with surprising ease to yield dichlorovinylation products. The $\text{trans}$ stereochemistry for one such product is established by X-ray, and subsequent transformations of these initial products to ethinyl or ω-chloroethinyl derivatives is described.     

Sterols with Cyclopropane-Containing Side Chains: Synthesis and Acid Isomerization

To test the eventual involvement of sterols with a cyclopropane containing side chain in bio-methylation processes, 24,25-methanocholest-5-en-3β-ol ( 5 ) and 24,25-methano-26-methylcholest-5-en-3β-ol ( 6 ) were synthesized. Together with the naturally occurring cyclopropane petrosterol ( 1 ), they were submitted to acid isomerization to provide chemical models for some of their potential metabolites.     

[1] Benzofuro[2,3-d] pyridazines. VI. Etude des reactions de scission des acyltetrahydrobenzofuropyridazones

The cleavage of the pyridazine ring of the acyltetrahydro [1] benzofuro [2,3-d] pyridazones was carried out by hydrolysis, alcoholysis or aminolysis reactions and they affect the lactam 3,4-bond. They lead chiefly to benzofuran derivatives with acid, ester, amide or hydrazide groups in the 2-position and eventually an acylated methylhydrazine group in the 3-position. The cyclization reactions of 3-hydrazinomethylbenzofuran-2-carboxylic acid and its derivatives or ethyl 3-bromome thylbenzofuran-2-carboxylate affords tetrahydrobenzofuropyridazones. The nmr spectra were studied.     

Differential diagnosis of prostate cancer and benign prostate hyperplasia using two-dimensional electrophoresis.

Prostate specific antigen (PSA) is a protease which is characteristic of the prostate. It is widely used as a serum marker for the early diagnosis of prostate cancer (PCa). Nevertheless, for concentrations between 4 and 10 ng/mL, PSA does not enable PCa to be distinguished from benign diseases, such as benign prostate hyperplasia (BPH). In sera, the use of a ratio between free PSA (PSA uncomplexed with protease inhibitor) and total PSA (free PSA and PSA bound to alpha-1 anti-chymotrypsin) enables the "gray zone" to be reduced, but an important proportion of patients are still wrongly classed. Using two-dimensional electrophoresis, we demonstrated using 52 PCa and 40 BPH well-documented clinical cases that BPH sera show a significantly greater percentage of low-molecular-weight free PSA elements (IwPSA) than PCa sera. In our study, the use of a ratio between IwPSA and standard free PSA enables the correct diagnosis of 100% of PCa and 82.5% of BPH cases as against when 73.1% and 42.5% respectively were correctly diagnozed using the total PSA and the free/total PSA ratio. This important finding may be related to differences in the mechanism secreting PSA from the prostate into the bloodstream. We have shown how a tissue marker may be turned into a powerful tumor marker by events probably unrelated to its expression.     

Cover Picture

The cover picture shows the metalloporphyrin heterodimer [(tpp)Mo$\rm{\mathop{-}^{4}}$Re(oep)](+) with the novel [Mo$\rm{\mathop{-}^{4}}$Re](5+) core. The core represents the first example of a quadruple bond between elements of different triads, thus proving that heterometallic quadruple bonds are not limited to the Group 6 metals. From the space-filling model it is clear that there is no interaction between the stabilizing porphyrin ligands. The ORTEP plot in a projection along the Re-Mo axis emphasizes the perfectly eclipsed geometry of the porphyrins, which is unambiguous proof of the existence of the quadruple bond in the solid state. The diamagnetism and large magnetic anisotropy of the cation, as determined by (1)H NMR spectroscopy, indicate that the quadruple bond is retained in solution. A logical and well-defined synthetic route was used to synthesize the dimer, and can be extended to other metalloporphyrins to generate further novel quadruple bonds (the picture was generated by Marina Boulan, St. Petersburg, Russia), full details are reported by J. P. Collman et al. on p. 1271 ff.     

Laser-induced temperature jump electrochemistry on gold nanoparticle-coated electrodes

Laser-induced temperature jumps (LITJs) at gold nanoparticle-coated indium tin oxide (ITO) electrodes in contact with electrolyte solutions have been measured using temperature-sensitive redox probes and an infrared charge-coupled device. Upon irradiation with 532 nm light, interfacial temperature changes of ca. 20 degrees C were recorded for particle coverages of ca. 1 x 1010 cm-2. In the presence of a redox molecule, LITJ yields open-circuit photovoltages and photocurrents that are proportional to the number of particles on the surface. When ssDNA was used to chemisorb nanoparticles to the ITO surface, solution concentrations as low as 100 fM of target ssDNA-modified nanoparticles could be detected at the electrode surface.     

Collision of a Solid with an Incompressible Fluid

We give a predictive theory of the collisions of a viscous incompressible fluid with solids. The theory is based on interior percussions which account for the very large stresses and contact forces resulting from the kinematic incompatibilities responsible for the collision. New equation of motion and constitutive laws result from the theory. Examples dealing with a fluid colliding with its container and with a diver impacting the water of a swimming pool are studied.