A useful ring transformation route to novel thiazepino[7,6-b]indoles from monochloro-β-lactam-fused 1,3-thiazino[6,5-b]indoles,analogues of cyclobrassinin

The Staudinger ketene-imine cycloaddition reactions of cyclobrassinin phytoalexin analogues 2-aryl-4,9-dihydro-1,3-thiazino[6,5-b]indoles with chloroacetyl chloride as a ketene source were investigated under different conditions. Both β-lactam ring formation and the N-chloroacetylation of the indole moiety took place. The indole N-chloroacetyl group can be easily removed by treatment in the presence of silica gel in methanol at reflux temperature. The selective β-lactam formation can be also achieved in certain cases under milder Staudinger conditions. The treatment of azeto[2,1-b]thiazino[6,5-b]indole-1-one derivatives with sodium ethoxide in ethanol provided the novel thiazepino[7,6-b]indole ring systems in a one-step ring transformation. The structures of the new ring systems were determined by means of IR and NMR spectroscopy.     

Ligand size distribution of phenanthroline-functionalized polyethylene glycol-iron(II) complexes determined by electrospray ionization mass spectrometry and computer simulation

The complex formation in solution, and the gas-phase dissociation of a phenanthrolineterminated poly(ethylene glycol) with Fe²⁺ ions were investigated. The size distribution of poly(ethylene glycol)-α-monomethyl-ω-5-[1,10]phenanthroline (mPEG_phen) was determined by electrospray ionization mass spectrometry (ESI-MS). Based on the measured ligand size distribution of mPEG_phen by ESI-MS, the 1:3 complex formation (Fe²⁺/mPEG_Phen) was computer-simulated as a pure random assembly process. The simulated distribution fits excellently to that of the complex Fe(mPEG_phen)₃²⁺ determined from the ESI-MS intensities. In addition, the collision-induced dissociation (CID) of the Fe(mPEG_phen)₃²⁺ complex was also studied by tandem mass spectrometry (ESI-MS/MS) and by computer simulation, as well. The ESI-MS/MS intensity distribution of the Fe(mPEG_phen)₂²⁺ formed from Fe(mPEG_phen)₃²⁺ by the loss of an mPEG_phen ligand under CID conditions fits quite well to the calculated one.     

Kolmogorov-Smirnov isometries and affine automorphisms of spaces of distribution functions

In this paper we describe the structure of surjective isometries of the spaces of all absolutely continuous, singular, or discrete probability distribution functions on R equipped with the Kolmogorov-Smirnov metric. We also study the structure of affine automorphisms of the space of all distribution functions.     

Synthesis of vinca alkaloids and related compounds part 94. Epimerization of compounds with aspidospermane and D‐secoaspidospermane skeleton

The individual epimerization steps of vincadifformine ( 1 ), deethylvincadifformine isomers ( 2,3 ), their synthetic intermediates ( 4–13 ) as well as that of simpler compounds with D‐secoaspidospermane skeleton ( 15–17 ) were studied a ) in protic medium (boiling deuteroacetic acidic) and b ) under reductive (with sodium borodeuteride in boiling acetic acid, or with sodium borohydride in boiling deuteroacetic acid) conditions.     

Reactions of 2-Deoxy-4, 5-O-Isopropylidene-D-Erythro- and D-Threo-Pent-1-Enose Derivatives

ABSTRACT

The reactivity of the title compounds has been studied toward different nucleophiles and electrophiles. Unlike other ketene dithioacetals, compounds 3-5 did not add nucleophiles to the double bond. Instead, in the presence of Lewis acids they underwent substitution reaction at position 3. If the nucleophile was not strong enough, formation of 6 and 7 were observed. With 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranose (18), a 3:1 mixture of 11 and 12 was formed from 4. These observations may be interpreted in terms of easy formation of the allylic carbocation I which gives diastereomers with nucleophiles. However, this allylic ether-like behaviour was ruled out by the fact that compounds 9 and 10 did not undergo [2,3] sigmatropic rearrangement with lithium diisopropylamide. With N-bromosuccinimide compound 3 gave the 2-bromo derivative 8. Compounds 3 and 8 resisted common mercury salt assisted demercaptalization procedures.     

Elementary Operators on Standard Operator Algebras

We present a new simple proof of the structural result for elementary operators on standard operator algebras. Using the idea of this short proof we can characterize surjective maps between standard operator algebras having a certain multiplicativity-like property appearing in the abstract definition of elementary operators of length one. In particular, we show that such maps are automatically additive.     

Optimization of Growth Conditions for Test Fungus Cultures used in Direct Bioautographic TLC Detection. 3. Test Fungus: Candida albicans

JPC – Journal of Planar Chromatography – Modern TLC - Optimum conditions have been established for culture of the fungus Candida albicans (ATCC 90028) for microbial detection of zones...     

Approximations for the maximum of a vector-valued stochastic process with drift

Giving a generalization of Berkes and Horváth (2003), we consider the Euclidean norm of vector-valued stochastic processes, which can be approximated with a vector-valued Wiener process having a linear drift. The suprema of the Euclidean norm of the processes are not far away from the norm of the processes at the right most point. We also obtain an approximation for the supremum of the weighted Euclidean norm with a Wiener process.     

Orthogonality Preserving Transformations on Indefinite Inner Product Spaces: Generalization of Uhlhorn's Version of Wigner's Theorem

We present an analogue of Uhlhorn's version of Wigner's theorem on symmetry transformations for the case of indefinite inner product spaces. This significantly generalizes a result of Van den Broek. The proof is based on our main theorem, which describes the form of all bijective transformations on the set of all rank-one idempotents of a Banach space which preserve zero products in both directions.