Synthesis and cross coupling of a highly substituted 2-pyridylboronate: application to the large scale synthesis of a mineralocorticoid antagonist

The large scale synthesis of functionalized 2-pyridylboronate 8 and optimization of its Suzuki-Miyaura coupling to chloropyrazoline (R)-7 to provide a scalable synthesis of mineralocorticoid antagonist (R)-1 is described.     

Synthesis, structure, and properties of a T-shaped 14-electron stiboranyl-gold complex

A cyclic stiboranyl-gold complex (1) supported by two 1,8-naphthalenediyl linkers has been synthesized and structurally characterized. The gold atom of this complex adopts a T-shaped geometry and is separated from the antimony center by only 2.76 ?. Surprisingly, the trivalent gold atom of this complex is involved in an aurophilic interaction, a phenomenon typically only observed for monovalent gold complexes. This phenomenon indicates that the stiboranyl ligand possesses strong σ-donating properties making the trivalent gold atom of 1 electron rich. This view is supported by DFT calculations as well as Au L(3)- and Sb K-edge XANES spectra which reveal that 1 may also be described as an aurate-stibonium derivative. In agreement with this view, complex 1 shows no reactivity toward the halides Cl(-), Br(-), and I(-). It does, however, rapidly react with F(-) to form an unprecedented anionic aurate fluorostiborane complex ([2](-)) which has been isolated as the tetra-n-butylammonium salt. The increased coordination number of the antimony center in this anionic complex ([2](-)) does not notably affect the Au-Sb separation (2.77 ?) or the geometry at the gold atom which remains T-shaped.     

Infrared emission following photolysis of methylisothiocyanate and methylthiocyanate

Methylisothiocyanate (CH(3)NCS) was photolyzed at 193 and 248 nm, and the resulting time-resolved infrared emission was observed. Similar experiments were performed on methylthiocyanate (CH(3)SCN) photolyzed at 193 nm. Previous work suggested that these isomers undergo excited-state isomerization prior to dissociation, but other experiments have contradicted this claim. In the infrared emission experiments, we observed the same products from both starting materials, supporting the theory of excited-state isomerization prior to dissociation. Methylisothiocyanate is the active ingredient in a widely used pesticide and has been observed to form highly toxic methyl isocyanate (CH(3)NCO) under environmental conditions. The mechanism for this formation has been unclear, but must involve some oxygen-containing species. At 248 nm, methylisothiocyanate was photolyzed alone and with three atmospheric oxidizers: O(2), NO, and NO(2). No chemical reaction was observed with O(2), whereas secondary reactions were observed with NO and NO(2). When methylisothiocyanate was photolyzed with NO(2), methyl isocyanate (CH(3)NCO) was observed, suggesting a likely environmental mechanism for methyl isocyanate formation.     

Processes limiting the rate of response in photorefractive composites

The processes limiting the rate of response of highly diffractive, reorientationally enhanced photorefractive polymer composite materials are identified from a series of degenerate four wave mixing and Mach–Zehnder interferometric measurements. In the regime of low intensity writing beams charge generation limits the rate of holographic grating formation, but at higher intensities charge transport or reorientation of dye molecules can restrict the rate of grating formation more strongly. A grating risetime of 540 ms is observed in a composite of high dye content with high reorientational mobility of the dye molecules. In this case it is proposed that the charge carrier mobility of the doped poly(N-vinylcarbazole):2,4,7-trinitro-9-fluorenone (PVK:TNF) matrix is the principal limiting factor in grating response rates.     

Effects of inorganic salts on the properties of aqueous poly(ethylene oxide) solutions

Cloud-point curves have been determined for aqueous solutions of poly(ethylene oxide) (PEO) at several concentrations for a variety of inorganic salts (sulfates, carbonates, nitrates, and chlorides). From these, theta conditions have been determined. The resulting dependences of the critical temperature θ (mostly between 300 and 360°K) on the molar concentrations (or ionic strengths) of the salts in solution cannot wholly be summarized in sequences of ion effects. The major findings are that sulfates and carbonates are much more effective in reducing θ than the chlorides and nitrates at the same concentrations. The trends found depend on salt concentration, i.e., certain plots of the data cross over, but they broadly agree with those found for comparable systems by other workers. Exceptional are the chlorides of Group II and LiCl which show minima when θ is plotted against molar salt concentration. While interpretations based on solvent structure-breaking are not adequate, there are similarities in behavior with the structure-breaking attributes of the ions based on independent studies (infrared). The results are briefly discussed in terms of current postulates: a more detailed discussion will accompany further experimental studies on these systems.     

In search of photon’s elementary axial magnetostatic field

 Experimental investigations of the photon’s B ⁽³⁾-field (third longitudinal polarization) are reported. The existence of an “axial magnetostatic field of photon” has been predicted in B _π or B ⁽³⁾-theory as the fundamental property of the circularly polarized light, and reported in numerous papers and monographs. High-sensitivity detection has been employed in photomagnetic induction, Faraday, and inverse Faraday effects (IFE) originating from such a field. The results of all three experiments clearly disprove the claims of B _π-theory. Putting together these results and theoretical calculations in perspective, it is concluded that such fields are non-existent. Received: 25 January 1996 / Revised version: 24 May 1996     

A direct method for measuring adsorption from solution onto solids

A direct method of measuring solution adsorption onto a solid has been developed. The results are exactly the same as those given by the conventional method of measuring the change in composition of the solution upon contacting the adsorbent. The development is cast in the terms of Gibbsian surface concepts, from which the correct thermodynamic significance of adsorption measurements made by directly analyzing material adsorbed on the solid can be understood. The method was tested for the adsorption of Na-Laurate and n-hexanol from aqueous and n-decane solutions, and typical isotherms are presented. The various realized and potential advantages of the method are discussed. The most important of these are the ability to measure adsorption in complex systems with a negligible change in solution composition, and the possibility of ameliorating in certain situations some of the difficulties in measuring adsorption at high concentrations or on low surface area solids.