Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

Stereochemistry and bonding in N-substituted-2-phenyl-3-cyanoaziridines

A series of ten N-alkyl(aralkyl)-2-phenyl-3-cyanoaziridines has been synthesized to continue investigations of the molecular stereochemistry and bonding of functionalized aziridines. Substantial spectroscopic evidence is presented which indicates the presence of stereoselective hyperconjugation between the phenyl and nitrile groups and the aziridine ring. The ¹H and ¹³C nmr chemical shifts are rationalized in terms of the interactions of the substituents on the aziridine ring, and how these interactions vary with the steric bulk of the nitrogen substituents. Various stereoselective coupling constants (¹H-¹H and ¹³C-¹H) are also reported.     

Specific and sensitive determination of medroxyprogesterone acetate in human serum by gas chromatography-mass spectrometry

The mass fragmentographic determination of medroxyprogesterone acetate (MPA) in serum, using as internal standard medroxyprogesterone propionate (MPP) synthesized from MPA, is described. After addition of MPP, the sera are extracted on Sep-Pak C18 cartridges and MPA and MPP are detected as their respective 3-enol trifluoroacyl esters. Serum samples from 84 patients with breast cancer, daily receiving MPA orally, were determined showing a large variation in MPA concentrations (4-349 ng/ml). Our proposed gas chromatographic-mass spectrometric (GC-MS) method, which can be considered as a reference, was compared with a radioimmunoassay (RIA) method showing a correlation coefficient of 0.73 (n = 69; p much less than 0.001). The assay was also used to determine sequential serum levels of patients receiving a single oral dose of MPA. With only minor adjustments, the GC-MS method allows the determination of serum concentrations of related steroids such as megestrol acetate and cyproterone acetate.