Chromatography-Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.     

Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C−O Bond Formation

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.     

Surface grating formation and erasing on a-Se films

Surface relief formation at holographic recording on amorphous selenium films was demonstrated and investigated. The presence of this optical phase modulation component is essential for ensuring significant, stable and erasable optical recording in a-Se films at 290–320 K temperatures, where conventional photodarkening was known as insignificant and unstable. Photocrystallization can only be observed in super-exposed a-Se films at the given experimental conditions of hologram recording. Erasing behavior of surface relief gratings under heat treatment was also investigated in order to reveal further details of the mechanism. Photoinduced structural transformations within the amorphous phase, connected to local ordering under the condition of light-induced fluidity, are proposed as an explanation for the relief formation and erasing. The observed reversible optical recording process may be useful for the various optoelectronic applications of photoconductive a-Se layers. Received: 12 June 2000 / Accepted: 6 June 2001 / Published online: 30 August 2001     

Defining Integrality at Prime Sets of High Density over Function Fields

 Let F be a function field of characteristic over a finite field . Then for any finite set of F-primes S and any , there exists a set of F-primes W of density greater than such that and has a Diophantine definition over . (Here and is defined analogously.)     

Continuous modified Newton’s-type method for nonlinear operator equations

A nonlinear operator equation F(x)=0, F:H→H, in a Hilbert space is considered. Continuous Newton’s-type procedures based on a construction of a dynamical system with the trajectory starting at some initial point x ₀ and becoming asymptotically close to a solution of F(x)=0 as t→+∞ are discussed. Well-posed and ill-posed problems are investigated. Received: June 29, 2001; in final form: February 26, 2002?Published online: February 20, 2003 This paper was finished when AGR was visiting Institute for Theoretical Physics, University of Giessen. The author thanks DAAD for support     

Diophantine Undecidability of Function Fields of Characteristic Greater than 2, Finitely Generated over Fields Algebraic over a Finite Field

Let F be a function field of characteristic p > 2, finitely generated over a field C algebraic over a finite field C _p and such that it has an extension of degree p. Then Hilbert's Tenth Problem is not decidable over F.     

Hydrogen-bonded block mesogens derived from semiperfluorinated benzoic acids and the non-mesogenic 1,2-bis(4-pyridyl)ethylene

Thermal properties of benzoic acids carrying one or two semiperfluorinated alkoxy tails on the aromatic core have been investigated in binary mixtures with the non-liquid crystalline bidirectional trans-1,2-bis(4-pyridyl)ethylene. The hydrogen bonded complexes built from the complementary molecular species show a significantly enhanced mesophase stability compared with the fluorinated acids in their pure states. The mesophase morphologies of the complexes are governed mainly by the number of the partially fluorinated chains grafted to the acid component. Mixed systems comprising the one-chain acids exhibit a smectic C phase followed by a smectic A phase at more elevated temperatures. Incorporation of a second semiperfluorinated chain into the acid leads to the formation of columnar mesophases. These columnar phases of the H-bonded complexes should represent ribbon phases resulting from the collapse of the smectic layers.     

19F NMR study of the equilibria and dynamics of the Al3+/F- system

A careful reinvestigation by high-field 19F NMR (470 MHz) spectroscopy has been made of the Al3+/F- system in aqueous solution under carefully controlled conditions of pH, concentration, ionic strength (I), and temperature. The 19F NMR spectra show five distinct signals at 278 K and I = 0.6 M (TMACl) which have been attributed to the complexes AlFi(3-i)+(aq) with i < or = 5. There was no need to invoke AlFi(OH)j(3-i-j)+ mixed complexes in the model under our experimental conditions (pH < or = 6.5), nor was any evidence obtained for the formation of AlF6(3-)(aq) at very high ratios of F-/Al3+. The stepwise equilibrium constants obtained for the complexes by integration of the 19F signals are in good agreement with literature data given the differences in medium and temperature. In I = 0.6 M TMACl at 278 K and in I = 3 M KCl at 298 K the log Ki values are 6.42, 5.41, 3.99, 2.50, and 0.84 (for species i = 1-5) and 6.35, 5.25, and 4.11 (for species i = 1-3), respectively. Disappearance of the 19F NMR signals under certain conditions was shown to be due to precipitation. Certain 19F NMR signals exhibit temperature- and concentration-dependent exchange broadening. Detailed line shape analysis of the spectra and magnetization transfer measurements indicate that the kinetics are dominated by F- exchange rather than complex formation. The detected reactions and their rate constants are AlF2(2+) + *F- reversible AlF*F2+ + F- (k02 = (1.8 +/- 0.3) x 10(6) M-1 s-1), AlF3(0) + *F- reversible AlF2*F0 + F- (k03 = (3.9 +/- 0.9) x 10(6) M-1 s-1), and AlF3(0) + H*F reversible AlF2*F0 + HF (kH03 = (6.6 +/- 0.5) x 10(4) M-1 s-1). The rates of these exchange reactions increase markedly with increasing F- substitution. Thus, the reactions of AlF2+(aq) were too inert to be detected even on the T1 NMR time scale, while some of the reactions of AlF3(0)(aq) were fast, causing large line broadening. The ligand exchange appears to follow an associative interchange mechanism. The cis-trans isomerization of AlF2+(aq), consistent with octahedral geometry for that complex, is slowed sufficiently to be observed at temperatures around 270 K. Difference between the Al3+/F- system and the much studied Al3+/OH- system are briefly commented on.