Unique charge-separated pyridinium-barbituric acid zwitterions

A synthetic procedure for the preparation of the unusual charge-separated pyridinium barbiturate zwitterion 2 from 1,3-dimethylbarbituric acid and 2-pyridinecarbaldehyde in methanol was developed. The structure of the compound was confirmed with X-ray analysis to demonstrate the strong charge separation throughout the molecule. One would expect that this charge separation would increase its reactivity; however, contrary to this expectation, the compound is very stable in acidic media, and in the presence of a base, decarbonylation occurs on one barbituric acid while the zwitterionic moiety of the molecule stays intact.     

A study of oligoprenyl coupling reactions with allylic stannanes

All-E or E,Z,E-oligoprenols may be synthesized from allylic stannanes by reaction with prenyl aldehydes. [reaction: see text]     

Intersecting all edges of centrally symmetric polyhedra by planes

A1 least three planes are needed in order to cut all edges of a 3-dimensional centrally symmetric convex polytope by planes which miss all vertices of the polytope. In contrast, there exist centrally symmetric convex tessellations of the 2-sphere for which two planes are sufficient.     

über die Darstellung von kondensierten Azolo-[1,2,4]-triazinen aus heterocyclischen Diazoverbindungen

Diazotized 3-amino-1,2,4-triazole reacted with 1,3-cyclohexanedione or its 5,5-dimethyl derivative to give the tricyclic 1,2,4-triazine derivatives1 a and1 b. With 1,3-indanedione the tetracyclic compound8 was obtained. Compound1 a or the diacetyl derivative4 a are transformed in an acid catalyzed reaction into the fully aromatic system6 a with simultaneous rearrangement. Chemical reductions of systems1, 10 and12 have been investigated and the compounds9, 11 and13 were isolated and identified. Diazotized 2-aminothiazole readily formed the coupling products with reactive methylene compounds, but only14 could be prepared pure by cyclodehydration.     

Complexation of metals with piperazine-containing azamacrocyclic fluorophores

Azamacrocyclic fluorophores containing piperazine units were synthesized using sequential rhodium-catalyzed regioselective hydroformylation-reductive amination. A piperazine unit is introduced into the macrocycles to act simultaneously as electron donor and binding site. The macrocycles chelate divalent cations, either Zn2+ or Co2+, which considerably enhanced fluorescence. Complexation with Zn2+ was additionally confirmed by NMR.     

Synthesis of (S)‐3‐heteroaryl‐2‐hydroxy‐l‐propyl benzoates by ‘ring switching’ methodology

(S)‐5‐Benzoyloxymethyl‐3‐[(E)‐(dimethylamino)methylidene]tetrahydrofuran‐2‐one (6), prepared in 5 steps from L‐glutamic acid (1), was used as precursor in a one step ‘ring switching’ synthesis of (S)‐2‐hydroxy‐3‐heteroaryl‐l‐propyl benzoates 13‐18, 23, 24. In the reaction of 6 with 2‐aminopyridine (21) and 2‐amino‐4,6‐dimethylpyrimidine (22) the corresponding dimethylamine substitution products (25, 26) were obtained.     

Rate limiting steps of the porous La0.6Sr0.4Co0.8Fe0.2O3−δ electrode material

The electrode reaction of porous La_0.6Sr_0.4Co_0.8Fe_0.2O_3?δ films deposited onto Ce_0.9Gd_0.1O_1.95 (CGO) was investigated by impedance spectroscopy within the temperature and oxygen partial pressure (pO₂) ranges of 500 ≤ T ≤ 700 °C and 10^? 4 < pO₂ < 1 atm, respectively, using Ar and He as gas carriers. The electrochemical impedance spectroscopy (EIS) measurements reveal a high frequency (HF) and a low frequency (LF) regions in the Nyquist plane. The high frequency (HF) region was fitted with a Warburg-type impedance element, and the low frequency (LF) region was reproduced with a resistance in parallel to a constant phase element. Both, the slight dependence of the polarization resistance (R_W) and the small variation of the apex frequency (f_v) of the HF Warburg-type element, on pO₂, suggest that this contribution corresponds to the oxygen diffusion in the bulk of the La_0.6Sr_0.4Co_0.8Fe_0.2O_3?δ electrode material. The variation of the polarization resistance of the LF region (R_rcpe) with pO₂ indicates that as T increases, the limiting step evolves from dissociative oxygen adsorption to oxygen gas diffusion in the pores of the mixed ionic/electronic conductor (MIEC) electrode.