Synthesis of 5-alkylidene-2,5-dihydropyrrol-2-ones and their ring-transformation into 5,6-dihydrobenzo[h]chromones, 5,6,7,8-tetrahydrochromones and pyran-4-ones

Acid-mediated ring-transformations of 5-alkylidene-2,5-dihydropyrrol-2-ones, available by cyclization of 1,3-diketone dianions with bis(imidoyl) dichlorides of oxalic acid, resulted in formation of functionalized pyran-4-ones, such as 5,6-dihydrobenzo[h]chromones and 5,6,7,8-tetrahydrochromones.     

Development of a gas chromatography/ion trap mass spectrometry based method for the quantification of polybrominated diphenyl ethers and polychlorinated biphenyls in adipose tissue

A combined gas chromatographic mass spectrometric (GC/MS/MS) method for the determination of seven polybrominated diphenyl ethers (PBDEs) and seven marker polychlorinated biphenyls (PCBs) in adipose tissue has been developed. Adipose tissue was melted and filtered through anhydrous sodium sulphate to obtain pure fat. Clean-up was performed using a glass column containing acidified silica, deactivated alumina and anhydrous sodium sulphate. Polybrominated biphenyl (PBB) 155 and Mirex were added as internal standards for PBDEs and PCBs, respectively. Injection standards, PBB 103 and PCB 143, for PBDEs and PCBs, respectively, were added before analysis with GC/MS/MS. The developed GC/MS/MS method has the advantage of being more selective than single MS methods because matrix effects are largely eliminated. Validation of this method was conducted according to Commission Decision 2002/657/EC. Decision limits for PBDEs and PCBs ranged from 0.06-0.15 ng g(-1) and from 0.35-1.22 ng g(-1), respectively. Detection capabilities were all between 0.23-0.55 ng g(-1) for PBDEs and between 0.98-2.29 ng g(-1) for PCBs. Precision, recovery, bias and selectivity were tested, with satisfactory results.     

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

1,2,3-Thiadiazole derivatives with a nearly linear N-S…O grouping. X-ray crystal structure analysis of four methylated products of 4-phenyl-1,2,3-thiadiazole-5-carbaldoxime

The title oxime 6 was methylated under different conditions and yielded four monomethylated products 7-10 and two bismethylated products 11 and 12 which were easily distinguished by their ¹³C nmr spectra. In view of the potential thiapentalene character of 8, 9, 10 and 11 , their X-ray crystal structures were determined. The structural properties of the nitroso compound 9 are in accordance with a thiapentalene structure, whereas those of the other compounds deviate in the order 10 < 11 < < 8 .     

High-performance thin-layer chromatography assay for epoxide hydrolase activity and the determination of phenoxypropane-1,2-diols

A simple, rapid and sensitive high-performance thin-layer chromatographic assay for the determination of epoxide hydrolase activity in rat liver homogenates is described. It is extended to the determination of a series of phenoxypropane-1,2-diols. The hydrolase assay has the advantages of using a readily available substrate, 2,3-epoxypropyl 4-methoxyphenyl ether, of multiple sample application, and of the simultaneous determination of reaction product (diol) as well as unchanged substrate (epoxide). The use of an internal standard, 4-nitroanisole, results in high sensitivity and good reproducibility of the proposed method. The limit of diol detection is 20 pmol.     

Application of high-field NMR and cryogenic probe technologies in the structural elucidation of poecillastrin a,a new antitumor macrolide lactam from the sponge poecillastra species

Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe.