Access to 2-fluoroacrylates and their 3-chloro derivatives by chemical hydrogenolysis of 3,3-dichloro-2-fluoroacrylates

The formation of 3-chloro-2-fluoroacrylates 2 and 2-fluoroacrylates 3 by hydrogenolysis of 3,3-dichloro-2-fluoroacrylates 1 was studied by using Bu₃SnH, zinc, the sodium sulphite/sodium formate mixture or iron pentacarbonyl in the presence of a hydrogen donor (Et₃SiH or CH₃OH). The two last couples can be used to prepare the 3-chloro derivatives 2, whereas for the preparation of the 3,3-dihydro derivatives 3, zinc is the most appropriate reducing agent. Keywords: 2-Fluoroacrylate; 3-Chloro-2-fluoroacrylate; 3,3-Dichloro-2-fluoroacrylate; Tributyltin hydride; Zinc; Sodium sulphite; Sodium formate; Iron pentacarbonyl; NMR spectroscopy; IR spectroscopy     

Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol

Several complexes of the formula trans-[Pt(Meug)(Am)Cl₂], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η²-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, ¹H NMR, ¹³C NMR and 2D NMR spectra of the complexes were recorded and analyzed.     

Cationic polymerization of dienes VII. New electron donors in the polymerization of 1,3-pentadiene initiated by aluminum trichloride in non-polar solvent

The aim of this research was to investigate new bulky electron donors (EDs) generating hindered active species in the cationic polymerization of 1,3-pentadiene initiated by AlCl₃ in pentane, in order to avoid or strongly reduce the reaction between the active species and the double bonds of the polymer which are responsible for side reactions. At room temperature, the polymerization in the presence of new ED, such as OPh₂, N(PhBr)₃, NPh₃ and SPh₂, allowed to obtain higher conversions and lower insoluble fractions than without electron donor. The formation of a complex ED/AlCl₃ was shown for each electron donor. However, in the case of NPh₃ and SPh₂, variations of the polymer microstructure demonstrated an interaction between active species and these EDs. Similar results were obtained at lower temperature (−10 °C). The beneficial effect of the presence of electron donors such as NPh₃ and SPh₂ demonstrated the validity of the concept of sterically hindered active species, but the polymerization was still uncontrolled.     

A sensitive and specific method for the determination of total ribavirin in human red blood cells by liquid chromatography-tandem mass spectrometry

A sensitive and specific method using high-performance liquid chromatography (LC)-tandem mass spectrometry (MS) for the analysis of total ribavirin in human red blood cells (RBC) is developed and validated. The method involves the addition of an internal standard and perchloric acid, the conversion of ribavirin phosphorylated metabolites to ribavirin, purification with a solid-phase exchange cartridge, and LC-MS-MS analysis. The MS-MS is selected to monitor m/z 245-113 for ribavirin and m/z 250-113 for [13C]ribavirin using positive electrospray ionization. The calibration curve is linear over a concentration of 100-10,000 ng/mL with a limit of quantitation of 100 ng/mL. Mean interassay accuracy for quality control (QC) at 100, 1000, and 10,000 ng/mL are 101.8%, 99.4%, and 98.8%, respectively. Mean interassay precision (%CV) for QC at 100, 1000, and 10,000 ng/mL are 5.0%, 5.0%, and 2.5%, respectively. Extractibility of total ribavirin from RBC is confirmed with RBC obtained from a [(14)C]ribavirin-dosed monkey. The method is used to determine the free and total ribavirin concentration in human RBC obtained from hepatitis C patients treated with ribavirin.     

Measurement and Identification of (R)- and (S)-6-O-Desmethylnaproxen Enantiomers as Diastereomeric O-Ethoxycarbonyl/(R)-(+)-1-Phenylethylamides in Urine by GC and GC-MS

Enantioseparations of (R)- and (S)-6-O-desmethylnaproxens as O-ethoxycarbonyl/(R)-(+)-1-phenylethylamides and (R)- and (S)-naproxens as (R)-(+)-1-phenylethylamides were achieved by achiral gas chromatography in a single run within 11 min. The characteristic mass spectral patterns facilitated easier peak identification. The method for determinations of (R)-naproxen (1.0 to 50 ng) and (S)-naproxen (100 to 2000 ng) was linear with acceptable repeatability and accuracy. The enantiomeric composition ratios between (R)- and (S)-6-O-desmethylnaproxens and between (R)- and (S)-naproxens in urine sample collected six hours after oral administration of (S)-naproxen tablets were measured to be 2.2 (± 0.2):97.8 (± 0.2) and 2.1 (± 0.1):97.9 (± 0.1), respectively.     

High pressure studies on new chiral compounds exhibiting TGBA phase

Effects of high pressures on phase sequences of the two homologousn=16 andn=18 of the (3-fluoro-4 ((R) or (S)-methylheptyloxy) 4, (4-fluoro benzoyloxy) tolans) series have been studied. Both compounds exhibit the new twisted Smectic A phase called Twist Grain Boundary TGB_A phase. The high pressure experiments were performed by thermobarometric analysis. The order of the transitions (first or second) have been determined in respect to pressure and temperature. The pressure-temperature phase diagrams show that the TGB_A phase is stabilized by increasing pressure; an inducedN ^* phase appears under high pressure for n=18 leading to the observation of TGB_A-N ^*-I triple point.     

Rare earth impurities in high purity lanthanum oxide determined by neutron activation analysis

Individual rare earth impurities in high purity La₂O₃ (99.9%) have been determined by NAA after pre-separation of the matrix (La). The separation is carried out on an anion exchanger (Dowex 1×8) using different mixtures of methanol/nitric acid as eluants. The rare earth elements from Dy to Lu are eluted quantitatively using a 10% 1M HNO₃-90% methanol mixture, while the light rare earths from Ce to Gd are eluted quantitatively using a 10% 0.05M HNO₃-90% methanol mixture. La, which is retained on the column, is eluted using 0.1M HNO₃. The recoveries of the various rare earth elements have been checked using radiotracers and also by spiking the sample with known amount of elements, and the recoveries are found to be quantitative. Results obtained on a typical high purity lanthanum oxide are reported here.     

Photocrosslinking of functionalized rubber. II. Photoinitiated cationic polymerization of epoxidized liquid natural rubber

Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 John Wiley & Sons, Inc.