571-39-1Relevant academic research and scientific papers
Steroidal isomers with uniform mass spectra of their per-TMS derivatives: Synthesis of 17-hydroxyandrostan-3-ones, androst-1-, and -4-ene-3,17-diols
Parr, Maria K.,Zapp, Josef,Becker, Michael,Opfermann, Georg,Bartz, Ulrike,Schaenzer, Wilhelm
, p. 545 - 551 (2008/02/02)
In human sports doping control analysis most of the steroids are analyzed after enzymatic hydrolysis of the glucuronides as per-trimethylsilyl (TMS) derivatives applying gas chromatography-mass spectrometry (GC-MS). According to the recommendations of the World Anti-Doping Agency the identification of analytes should be based on retention time and on mass spectrometric characterization. This study shows that the bis-TMS derivatives of 16 specific C19 steroids, namely the stereoisomers of 5ξ-androst-1-ene-3ξ,17ξ-diol (8 isomers), androst-4-ene-3ξ,17ξ-diol (4 isomers), and 17ξ-hydroxy-5ξ-androstan-3-one (4 isomers), reveal very similar mass spectra. As a rule, when taking the retention times, which are provided as Kovac indices for all these isomers, into account, a restriction to two or three possible isomers is possible. Reliable identification should additionally include a comparison of the retention times of the analytes with the reference compounds measured concomitantly. In some cases standard addition may be appropriate. Due to the limited availability, the above mentioned isomers were synthesized by reduction of the corresponding α,β-unsaturated oxo steroids either with K-Selectride or by catalytic hydrogenation (Pd/C as catalyst). The products of the reactions were identified by means of nuclear magnetic resonance (NMR) characterization and by further reduction to the corresponding 5ξ-androstane-3ξ,17ξ-diols and GC-MS comparison with commercially available reference standards.
HIO3 and I2O5: Mild and selective alternative reagents to IBX for the dehydrogenation of aldehydes and ketones
Nicolaou,Montagnon, Tamsyn,Baran, Phil S.
, p. 1386 - 1389 (2007/10/03)
Economic and convenient: Iodic acid (1) and iodine pentoxide (2) form complexes 3 and 4, respectively, with DMSO when heated at 80°C for 1 h. The complexes are efficient agents for the dehydrogenation of ketones and aldehydes at 45-65°C. X-ray crystallographic analysis (see picture) shows that the iodine pentoxide. DMSO complex 4 self-assembles into a remarkable helix in the solid state.
Modulation of the reactivity profile of IBX by ligand complexation: Ambient temperature dehydrogenation of aldehydes and ketones to α,β-unsaturated carbonyl compounds
Nicolaou,Montagnon, Tamsyn,Baran, Phil S.
, p. 993 - 996 (2007/10/03)
The reactivity profile of IBX can be altered by complexation with various ligands (e. g. 1-4). A new complex, IBX·MPO, is a remarkably effective oxidant and allows the room-temperature dehydrogenation of carbonyl compounds, for example, the formation of cyclooctenones 6 and 7 from cyclooctanone 5. IBX = iodoxybenzoic acid; MPO = 4-methoxypyridine-N-oxide.
Unusual Enolizations in 19-Nor-3-ketosteroids
Abul-Hajj, Yusuf J.
, p. 1479 - 1481 (2007/10/02)
The direction of enolization of 19-nor-3-ketosteroids was found to proceed predominantly towards C-2 irrespective of the ring junction at C-5.
