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PubMed2003

Formation of quaternary stereocenters by copper-catalyzed Michael reactions with L-valine amides as auxiliaries.

Extensive investigations of chiral auxiliaries and active metals for Michael addition of 1,3-dicarbonyl compounds with vinyl ketones are summarized. Our efforts result in a widely applicable auxiliary-mediated, copper(II) acetate-catalyzed procedure. For these purposes, L-valine diethylamide is an optimal chiral auxiliary giving quaternary stereocenters with up to 99 % ee at ambient temperature. No inert or anhydrous conditions are required, the solvent is simply acetone, and the auxiliary can be recovered almost quantitatively after workup.

Journal Article↗
PubMed2004

Vinyl sulfoxides as stereochemical controllers in intermolecular Pauson-Khand reactions: applications to the enantioselective synthesis of natural cyclopentanoids.

The use of sulfoxides as chiral auxiliaries in asymmetric intermolecular Pauson-Khand reactions is described. After screening a wide variety of substituents on the sulfur atom in alpha,beta-unsaturated sulfoxides, the readily available o-(N,N-dimethylamino)phenyl vinyl sulfoxide (1 i) has proved to be highly reactive with substituted terminal alkynes under N-oxide-promoted conditions (CH3CN, 0 degrees C). In addition, these Pauson-Khand reactions occurred with complete regioselectivity and very high diastereoselectivity (de=86->96 %, (S,R(S)) diastereomer). Experimental studies suggest that the high reactivity exhibited by the vinyl sulfoxide 1 i relies on the ability of the amine group to act as a soft ligand on the alkyne dicobalt complex prior to the generation of the cobaltacycle intermediate. On the other hand, both theoretical and experimental studies show that the high stereoselectivity of the process is due to the easy thermodynamic epimerization at the C5 center in the resulting 5-sulfinyl-2-cyclopentenone adducts. When it is taken into account that the known asymmetric intermolecular Pauson-Khand reactions are limited to the use of highly reactive bicyclic alkenes, mainly norbornene and norbornadiene, this novel procedure constitutes the first asymmetric version with unstrained acyclic alkenes. As a demonstration of the synthetic interest of this sulfoxide-based methodology in the enantioselective preparation of stereochemically complex cyclopentanoids, we have developed very short and efficient syntheses of the antibiotic (-)-pentenomycin I and the (-)-aminocyclopentitol moiety of a hopane triterpenoid.

Alkynes↗
PubMed2007

Dynamic kinetic resolution of secondary alcohols combining enzyme-catalyzed transesterification and zeolite-catalyzed racemization.

Hydrophobic zeolite beta containing low concentrations of Zr or Al was found to be a good catalyst for the racemization of 1-phenylethanol. The formation of styrene as a side product could be minimized by reducing the metal concentration in the zeolite beta. Combined with an immobilized lipase from Candida antarctica, the dynamic kinetic resolution of 1-phenylethanol to the (R)-phenylethylester can be achieved with high yield and selectivity. The reaction was best conducted in toluene as solvent at 60 degrees C, with higher temperatures leading to a loss in the enantioselectivity of the formed ester. By using high-molecular-weight acyl-transfer reagents, such as vinyl butyrate or vinyl octanoate, a high enantiomeric excess of the product esters of 92 and 98 %, respectively, could be achieved. This is attributed to a steric effect: the bulky ester is less able to enter the pore space of the zeolite catalyst where the active sites for racemization are localized. Close to 100 % conversion of the alcohol was achieved within 2 h. If the more common acyl donor, isopropenyl acetate, was used, the enantiomeric excess (ee) of the formed ester was only 67 %, and the reaction was considerably slower.

Alcohols↗
PubMed2007

Ruthenium-Lewis acid catalyzed asymmetric Diels-Alder reactions between dienes and alpha,beta-unsaturated ketones.

The complex [Ru(Cp)(R,R-BIPHOP-F)(acetone)][SbF(6)], (R,R)-1 a, was used as catalyst for asymmetric Diels-Alder reactions between dienes (cyclopentadiene, methylcyclopentadiene, isoprene, 2,3-dimethylbutadiene) and alpha,beta-unsaturated ketones (methyl vinyl ketone (MVK), ethyl vinyl ketone, divinyl ketone, alpha-bromovinyl methyl ketone and alpha-chlorovinyl methyl ketone). The cycloaddition products were obtained in yields of 50-90 % and with enantioselectivities up to 96 % ee. Ethyl vinyl ketone, divinyl ketone and the halogenated vinyl ketones worked best and their reactions with acyclic dienes consistently provided products with >90 % ee. alpha-Chlorovinyl methyl ketone performed better than alpha-bromovinyl methyl ketone. The reaction also provided a [4.3.1]bicyclic ring system in 95 % ee through an intramolecular cycloaddition reaction. Crystal structure determinations of [Ru(Cp)((S,S)-BIPHOP-F)(mvk)][SbF(6)], (S,S)-1 b, and [Ru(Cp)((R,R)-Me(4)BIPHOP-F)(acrolein)][SbF(6)], (R,R)-2 b, provided the basis for a rationalization of the asymmetric induction.

Alkadienes↗
PubMed1975

[Isothiocyanate and vinyl thio-oxazolidone contents of rape seeds and rape seed oil].

Comparative studies on the isothiocyanate content of rape-seeds and rape-seed oil show that, apart from nearly 300 mg/100 g of vinyl thio-oxazolidone, rape-seeds contain almost 200--300 mg/100 g of isothiocyanates of which 3-butenyl isothiocyanate and 4-pentenyl isothiocyanate (ratio of 4:1) are the main components as evidenced thin-layer and gaschromatographically. Only about 1 mg/100 g of isothiocyanates are found in pressed rape-seed oil; and but circa 10 mg/100 g, in extracted rape-seed oil. 3-Butenyl isothiocyanate and 4-pentenyl isothiocyanate (ratio of 4:1) are once more the main components. Thioglycerides are not detected in the oil. Vinyl thio-oxazolidone is found only in extracted rape-seed oil (about 2 mg/100 g).

Chromatography, Gas↗
PubMedDate not supplied

Early hepatic histologic alterations among chemical (vinyl monomer) workers.

Focal hepatocellular hyperplasia and focal mixed (hepatocytes and sinusoidal cells) hyperplasia are early histological alterations indicative of vinyl monomer exposure. To evaluate their uses in screening chemical workers, 93 liver biopsy specimens from 78 persons were examined in double-blind duplicative fashion. Forty-eight specimens were from exposed chemical workers, 35 of them having liver biopsy(ies) for hepatic test abnormalities and 13 for nonliver -related reasons. A comparison group consisted of 30 nonchemical workers who had undergone liver biopsy for nonliver related reasons. Twenty-three of the exposed workers (48%) had hepatic lesions consistent with exposure: 17 (35%) of these had focal hepatocytic hyperplasia, while 6 (13%) had focal mixed hyperplasia or more advanced lesions. Only five of the comparison group had like findings: four (13%) had focal hepatocytic hyperplasia; one had focal mixed hyperplasia and sinusoidal dilatation. This individual had persistent hepatic test abnormalities with the focal mixed hyperplasia and a sinusoidal dilatation, and on subsequent biopsy, angiosarcoma (and a history of using hair spray containing vinyl chloride propellant ). Ten individuals had 25 multiple biopsies also read double-blindly; 10 had two or more readings of the same biopsy. Duplicate 21 of 23 (91%) and multiple 27 of 28 (96%) biopsy interpretations in the same individual were identical. Only 6% of either duplicate and/or multiple readings disagreed. Both focal hepatocellular and mixed hyperplasia were always associated with abnormalities in hepatic test results of which indocyanine green clearance was the most sensitive and gamma-glutamyl transpeptidase the least specific.(ABSTRACT TRUNCATED AT 250 WORDS)

Biopsy↗
PubMed1975

Human, rat and mouse liver-mediated mutagenicity of vinyl chloride in S. typhimurium strains.

Exposure of S. typhimurium strains TA 1530, TA 1535 and G-46 to vinyl chloride increased the number of His+ revertants/plate 16, 12 or 5 times over the spontaneous mutation rate. After 6 h of exposure to vinyl chloride, the mutagenic response for TA 1530 strain was enhanced 7-, 4- or 5-fold when fortified postmitochondrial liver fractions from humans, rats or mice were added. The enzyme-mediated vinyl chloride mutagenicity was dependent on an NADPH generating system and the enzyme activity was localized in a liver microsomal fraction; 9,000 times g liver supernatant was three times more active than microsomes, while liver cytosol or alcohol dehydrogenase did not affect the mutagenicity. Phenobarbitone pretreatment of rats and mice increased the mutagenic response by up to 15-40 percent as compared to untreated controls. The relative mutagenic activities of VCM, taking the value from mouse liver as 100, for TA 1530 strain mediated by 9,000 times g tissue fractions were: rat liver, 80; mouse and rat kidney, 20 and 16; mouse and rat lung, less than 7; human liver (from four biopsy specimens) 170, 64, 70 and 46. Chloroacetaldehyde and chloroacetic acid, a urinary metabolite of VCM, showed toxic effects, while chloroethanol was weakly mutagenic for TA 1530 strain.

Acetaldehyde↗
PubMed1975

Mutation induction in Chinese hamster V79 cells by two vinyl chloride metabolites, chloroethylene oxide and 2-chloroacetaldehyde.

Chloroethylene oxide and 2-chloroacetaldehyde, two possibly carcinogenic metabolities of vinyl chloride in mammals, caused a dose-dependent induction of 8-azaguanine- and ouabain-resistant mutants in Chinese hamster V79 cells in vitro. Up to one-hundred-fold higher concentrations of 2-chloroethanol or monochloroacetic acid, a urinary vinyl chloride metabolite in rats and man, were inactive.

Acetaldehyde↗
PubMedDate not supplied

Decontamination of vinyl urinary drainage bags with bleach.

The purpose of the study described here was to investigate whether vinyl urinary leg and bed bags used for a 4-week period in the acute rehabilitation setting could be safely reused after having been decontaminated daily with a diluted bleach rinse. Rehabilitation patients who had bladder dysfunction and used vinyl urinary drainage bags (N = 88) were randomly assigned to control (C) and experimental (E) groups; 54 patients completed the study. Group C's bags were replaced weekly; group E's were replaced after 4 weeks. The bags of patients in both groups were decontaminated in identical fashion each day. On the patient's admission to the study, a baseline assessment was completed, a urine culture was obtained, and sterile drainage equipment was provided. Each week for 4 weeks, urine and bag characteristics and signs and symptoms of urinary tract infection were noted. No statistically significant differences (p < .5) were found between the groups. There were no clinical signs of infection requiring treatment, no changes in bag appearance or integrity, and no infection outbreaks associated with a single urinary tract pathogen that would indicate cross-contamination.

Colony Count, Microbial↗
PubMed1981

Determination of vinyl acetate in air by gas chromatography.

A gas chromatographic analysis for vinyl acetate is presented. Vinyl acetate was sampled by adsorbing on activated carbon. It was desorbed with carbon disulfide with a mean efficiency of 83.0%. The analytical column was packed with 10% free fatty acid phase on acid-washed Chromosorb-P. Gas chromatographic identification was also conducted on another column packed with 0.4% Carbowax-1500 on Carbopack A. Analysis was performed on a chromatograph equipped with a flame ionization detector. The precision (coefficient of variation) for the analytical procedure using a free fatty acid phase column was 4.0%. Based on a 10 litre air sample, the calculated limit of detection by this procedure was 0.1 parts per million.

Adsorption↗
PubMed1975

Cell adhesion to polymeric materials: implications with respect to biocompatibility.

The adhesion of radio-labeled chick embryo muscle cells to the surfaces of radiation grafted hydrogels and other polymeric materials was measured in vitro. The degree of adhesion was determined by measuring the percentage of cells which remained adherent to the surfaces after 180 min of contact time (plating efficiency). Plating efficiency was found to vary between 2 and 94% depending on the nature of the surface. Preadsorption of albumin, gamma-globulin or fibrinogen markedly affected subsequent adhesion of cells. Radiation grafted poly(2-hydroxyethyl methacrylate) and poly(N-vinyl-2-pyrrolidone) hydrogels on silicone rubber demonstrated exceptionally low adhesiveness in this assay. The potential for using this cell adhesion assay as a general screening test for biomaterials is discussed.

Adsorption↗
PubMed1977

Temperature control of a bone cement by addition of a crystalline monomer.

The peak temperature reached during the polymerization of a bone cement was reduced by addition of solid N-vinylcarboazole to the powder component. It was also necessary to saturate the liquid component with N-vinylcarbazole to prevent dissolution from the modified powder component on mixing. It is believed that this technique is generally applicable and opens up the possibility of achieving temperature control of bone cements with choice from a range of crystalline monomers.

Bone Cements↗
PubMed1978

Effect of comonomer ratio on hydrocortisone diffusion from sustained-release composite capsules.

The daily in vitro release of hydrocortisone from composite polymer capsules is reported here for over 120 days. Increase in vinyl acetate comonomer content of the ethylene-vinyl acetate copolymer matrix brought about an increase in the diffusion rate. Variation in the initial drug content of the capsules from 40 mg to 20 mg affects the daily drug release less significantly than the variation in copolymer ratio. The correlation between vinyl acetate comonomer content and the percent crystallinity of the copolymer matrix is suggested as one of the possible major factors in controlling diffusion rate from this drug-polymer system. The diffusion constant (D) calculated was 0.212 X 10(10) cm2/sec when the copolymer carrier has 30% vinyl acetate content and 0.430 X 10(11) cm2/sec when the copolymer carrier has 20% vinyl acetate content for capsules with 20 mg initial drug content, and 0.118 X 10(-11) cm2/sec and 0.226 X 10(-11) cm2/sec, respectively, for capsules with 40 mg initial drug content.

Capsules↗
PubMedDate not supplied

Assessment of tissue reactions to biomaterials: a model system using the foreign body response in the mouse lung to intravenously injected divinyl copolymer beads.

We have developed a reproducible model of granuloma formation in the mouse lung using a narrow size range (45-53 micron) of divinyl benzene copolymer beads as a standard test material. Approximately 10,000 beads are given by intravenous injection into the tail veins of mice whence they embolize to the lung and incite granuloma formation. This delivery system eliminates the superimposed inflammatory reaction due to trauma that occurs when materials are directly implanted at the test site by surgical incision. Granuloma size was quantitated at intervals from 3 h to 6 weeks by tracing mid-bead granuloma areas on the ground glass screen of a light microscope at a known magnification and measuring the areas with a digitizer interfaced with a microcomputer programmed to prepare histograms and to merge data from replicate experiments. At 3 h only a few polymorphonuclear leukocytes could be observed adhering to the beads. At 48 h, the time of maximum granuloma size (mean area = 7501 micron2), the granulomas consisted of both polymorphonuclear and mononuclear leukocytes. After 6 weeks, the granulomas were smaller, composed predominantly of mononuclear leukocytes and had a mean area of 2893 micron2. This model system allows the analysis of a large number of measurements, is reproducible, and provides a useful method for comparing the hosts' inflammatory response to a variety of potential biomaterials, as well as for determining the effectiveness of antiinflammatory drugs.

Animals↗
PubMedDate not supplied

A calorimetric study of the interaction of synthetic phospholipid liposomes with vinyl monomers, acrylates and methacrylates.

Mono-, di-, and trimethacrylates (monomers) are widely used in dentistry as restorative materials, adhesives, prosthetic devices, etc. It is known that the residual monomers released from the cured resin have been implicated in toxicological effects. In order to monitor the biological actions at the membrane level induced by monomers, we studied the changes in the phase transition temperature (T) and enthalpy (delta H) of dipalmitoyl-phosphatidylcholine liposomes induced by 37 different monomers using differential scanning calorimetry (DSC). The monomers that caused large changes in the T and delta H were vinyl monomers; acrylates; monomethacrylates that contain hydroxy, carbonyl, amino and phenyl groups; dimethacrylates with short-chain substituents; and aliphatic trimethacrylates. It is suggested that the changes in the T and delta H values may be due not only to hydrophobic interactions, but also to interactions induced by the double bonds or the functional groups in the monomers. On the other hand, methacrylates with simple alkyl ester linkage and dimethacrylates with bisphenol A groups exhibited the smallest changes. The changes in the T and delta H induced by highly hydrophobic methacrylates were small due to their slower interaction. These changes in transition properties of liposomes seem to be related to biological activities.

Acrylates↗