One-pot five-component high diastereoselective synthesis of polysubstituted 2-piperidinones from aromatic aldehydes,nitriles, dialkyl malonates and ammonium acetate

Molecular Diversity - A novel five-component diastereoselective synthesis of polysubstituted 2-piperidinones is reported. The Knoevenagel condensation–Michael addition–Mannich cascade...     

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.     

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.     

Middle-ear response in the chinchilla and its relationship to mechanics at the base of the cochlea

The responses of the malleus and the stapes to sinusoidal acoustic stimulation have been measured in the middle ears of anesthetized chinchillas using the M?ssbauer technique. With "intact" bullas (i.e., closed except for venting via capillary tubing), the vibrations of the tip of the malleus reach a maximal peak velocity of about 2 mm/s in responses to 100-dB SPL tones in the frequency range 500-6000 Hz; vibration velocity diminishes toward lower frequencies with a slope of about 6 dB/oct. Opening the bulla widely increases the responses to low-frequency stimuli by as much as 16 dB. At low frequencies, malleus response sensitivity with either open or intact bullas far exceeds all previous measurements in cats and matches or exceeds such measurements in guinea pigs. Whether measured in open or intact bullas, phase-versus-frequency curves closely approximate those predicted from the magnitude-versus-frequency curves by minimum phase theory. The stapes responses are similar to those of the malleus, except that stapes response magnitude is lower, on the average, by 7.5 dB at frequencies below 2 kHz and 10.7 dB at 2 kHz and above. Comparison of the responses of the middle ear with those of the basilar membrane at a site 3.5 mm from the stapes indicates that, at frequencies below 150 Hz, the basilar membrane displacement is proportional to stapes acceleration. At frequencies between 150 and 2000 Hz, basilar membrane displacement is proportional to stapes velocity.     

Cochlear microphonics and the initiation of spikes in the auditory nerve: correlation of single-unit data with neural and receptor potentials recorded from the round window

On the basis of comparisons of responses of guinea pig ganglion cells and inner hair cells to intense low-frequency tones, Sellick et al. [Hear. Res. 7, 199-221 (1982)] have proposed that basal inner hair cells can be depolarized (and thus, VIII-N. spikes generated) by the extracellular microphonic generated during hyperpolarization of outer hair cells. VIII-N. data for the chinchilla have been presented that, to a first approximation, support such a hypothesis [Ruggero and Rich, J. Acoust. Soc. Am. 73, 2096-2108 (1983)]. However, an apparent discrepancy exists in our results, vis à vis Sellick et al.'s hypothesis, in that basal fiber near-threshold responses precede maximal negativity of the round window microphonic (i.e., maximal hyperpolarization of outer hair cells) by up to 90 degrees (but generally less than 45 degrees), depending on frequency. It is shown here that the discrepancy is resolved if certain nonlinear phase changes and overall distortion of the microphonic waveshapes, both of which occur at intense stimulus levels, are taken into account. It is also shown that compound action potentials (AP's), superimposed on the round window microphonics, can be identified at multiple times within each stimulus cycle, closely matching the near-threshold response phases of single-unit excitation. AP1 is nearly synchronous with the negative-to-positive transition of round window microphonics and with the excitation of fibers innervating apical-to-middle cochlear regions. AP2 is synchronous with the positive-to-negative transition of the microphonics and with the excitation of basal fibers. One or two other AP's probably reflect "peak splitting" in the responses of both basal and apical fibers.     

The observation of a large gauche preference when 2-fluoroethylamine and 2-fluoroethanol become protonated

The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference.