Synthesis of tetrazolopiperazine building blocks by a novel multi-component reaction

A novel Ugi-five-centre-four-component reaction (U-5C-4CR) of aldehydes, primary amines, trimethylsilylazide and 2-isocyanoethyltosylate yielding tetrazolopiperazine building blocks is described.     

Synthesis and reactions of halogenated thiazole isocyanates

A synthesis of 2-chloro-4-(trifluoromethyl)-5-isocyanatothiazole and 2,5-dichloro-5-isocyanatothiazole is described via the “Curtius Rearrangement” performed under anhydrous conditions. The synthetic procedure described allows for the isolation, storage, and manipulation of these highly reactive isocyanates. A number of derivatives of the above isocyanates were prepared. These include: carbamates, thiocarbamates, ureas, amines, amidines, and amides.     

The intersection of Brownian paths as a case study of a renormalization group method for quantum field theory

A new approach is presented for the study of the probability that the random paths generated by two independent Brownian motions in ^d intersect or, more generally, are within a short distancea of each other. The well known behavior of that function ofa-above, below, and at the critical dimensiond=4, as well as further corrections, are derived here by means of a single renormalization group equation. The equation's derivation is expected to shed some light on the -function of the _d ⁴ quantum field theory.Sloan Foundation Research Fellow. Research supported in part by NSF grant PHY-8301493     

Infrared absorption by collisional CH4+X pairs, with X=He, H2, or N2

Existing measurements of the collision-induced rototranslational absorption spectra of gaseous mixtures of methane with helium, hydrogen, or nitrogen are compared to theoretical calculations, based on refined multipole-induced and dispersion force-induced dipole moments of the interacting molecular pairs CH4-He, CH4-H2, and CH4-N2. In each case the measured absorption exceeds the calculations substantially at most frequencies. We present the excess absorption spectra, that is the difference of the measured and the calculated profiles, of these supramolecular CH4-X systems at various gas temperatures. The excess absorption spectra of CH4-X pairs differ significantly for each choice of the collision partner X, but show common features (spectral intensities and shape) at frequencies from roughly 200 to 500 cm(-1). These excess spectra seem to defy modeling in terms of ad hoc exchange force-induced dipole components attempted earlier. We suggest that besides the dipole components induced by polarization in the electric molecular multipole fields and their gradients, and by exchange and dispersion forces, other dipole induction mechanisms exist in CH4-X complexes that presumably are related to collisional distortion of the CH4 molecular frame.     

Miniature electrophoresis for speed and productivity

Attempts to miniaturize electrophoresis (EP) to save time or enhance productivity and efficiency remains a challenge for science and industry. Other advantages of miniaturization include: increased sensitivity, saving of reagents, greater yield of data, and enabling studies where only small samples are available. Since electrophoresis that takes hours may be reduced to a matter of minutes, the limitations of miniaturization in clinical, industrial, and research applications are evaluated. Clinical electrophoresis (EP) on cellulose acetate media can be performed in 3.5 min instead of 20–45 min and on SDS polyacrylamide gels in 15–30 min compared with conventional 3–8 h.     

Syntheses and structures of structurally diverse potassium beta-diketiminates derived from the ligand [(N(SiMe3)C(Ph))2CH

The compounds [K((mu-N(SiMe3)C(Ph))2CH)(thf)2]infinity 1, [K(mu-N(SiMe3)C(Ph)C(H)C(Ph)NH)L]2 [L = (thf)2 2, tmen 3], [K(mu-NSi(Me)2C(Ph)C(H)C(Ph)N)(thf)3]2 4 and [K(N(H)C(Ph))2CH](thf)0.5 5 have been prepared from K[(N(SiMe3)C(Ph))2CH] and the X-ray structures of 1-4 are reported.     

Azetidinyl ketones. Synthesis of 1-Alkyl-2,4-diphenyl-3-benzoylazetidines

α-(α'-Bromobenzyl)chalcone ( 3 ) reacts with primary amines (t-butyl, isopropyl,cyclohexyl) to give α-(α'-alkylaminobenzyl)chalcones ( 4, 5 and 6 ). When these allylic amines are treated with hydrogen bromide followed by reaction with base, they produce l-alkyl-2,4-diphenyl-3-benzoyl-azetidines ( 7,8 and 9 ). These azetidines were readily converted to their 3-deuterio derivatives ( 10 , 11 and 12 ) by treatment with sodium methoxide in deuteriomethanol. The configurations were assigned primarily by pmr spectra and mass spectra in reference to analogous compounds.     

Equilibrium interaction of solid surfaces across a polymer melt

Forces across polymer melts are poorly understood despite their importance for adhesion and fabricating composite materials. Using an atomic force microscope (AFM), this interaction was measured for poly(dimethyl siloxane) (PDMS). The structure of the polymer at the surface changed during the first approximately 10 h. Afterward, short-range attractive forces were observed with short-chain PDMS (M(w) = 4200 g/mol). Using PDMS with a molecular weight (M(w) = 18 000 g/mol) above the entanglement limit, we measured a monotonically decaying repulsive force, which indicates that a quasi-immobilized layer had formed at the solid surface. Due to the small radius of curvature of the tip, forces could be measured in equilibrium.     

Two unusual, competitive mechanisms for (2-ethynylphenyl)triazene cyclization: pseudocoarctate versus pericyclic reactivity

The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 degrees C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 degrees C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.