The Reaction of Ketenylidenetriphenylphosphorane (Ph3P˭C˭C˭O) with Acidic H‒E (E˭O,N) Bonds

Abstract

The reactivity of ketenylidenetriphenylphosphorane (1) with the protic reagents 2,4,6-trimethylphenol (7), 2,6-di-tert-butyl-4-methylphenol (8), and diphenylamine (9) has been explored. Three novel carbonyl-stabilized ylides have been synthesized and characterized. Crystal structures were obtained for Ph₃PCHC(O)O(C₆H₂Me₃) (11), Ph₃PCHC(O)O(C₆H₂t-Bu₂Me) (12), and Ph₃PCHC(O)NPh₂ (13), respectively. These products were then methylated in an attempt to develop a new route to low-valent carbon compounds. Crystals of [Ph₃PCH(CH₃)C(O)O(C₆H₂Me₃)]I (14) were isolated and characterized but this route did not prove to be synthetically useful, at least toward the goal of preparing low-valent carbon-centered materials. Finally, 1 was also reacted with the bulky tin reagent, bis[bis(trimethylsilyl)amido]tin(II), in the presence of 2,4,6-trimethylphenol. A complex mixture of products was obtained, from which crystals of an unusual chelated tin compound (15) were isolated and characterized using X-ray crystallography.     

A programmed polymer folding: click and clip construction of doubly fused tricyclic and triply fused tetracyclic polymer topologies

A tandem alkyne-azide addition, i.e., click, and an olefin metathesis condensation, i.e., clip, reactions in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process, have been demonstrated as effective means to produce constructions of programmed folding of polymers having doubly fused tricyclic and triply fused tetracyclic topologies. Thus, a series of cyclic poly(tetrahydrofuran), poly(THF), precursors having an allyloxy group and an alkyne group (Ia), an allyloxy group and an azide group (Ib), and two alkyne groups (Ic) at the opposite positions was prepared by means of the ESA-CF method. The subsequent click reactions of Ia with a linear telechelic poly(THF) precursor having azide end groups (Id) and of Ib with Ic afforded a bridged dicyclic polymer (IIa) and a tandem spiro tricyclic precursor (IIb), respectively, both having two allyloxy groups at the opposite positions of the ring units. Finally, the intramolecular metathesis condensation reaction of IIa and of IIb in the presence of a Grubbs catalyst was performed to construct effectively a doubly fused tricyclic and a triply fused tetracyclic polymer topologies (III and IV), respectively.     

Intracellular pH mapping with SNARF-1 and confocal microscopy. II: pH gradients within single cultured cells

Using the pH-sensitive dual-emission fluorophore, carboxy-seminaphthorhodaflour-1 (SNARF-1) coupled with a laser-scanning confocal microscope system it is now possible to map intracellular pH. We have applied this combination to investigate the pH levels and distribution within single isolated cultured proximal tubule, bovine aortic endothelial and rat aortic smooth muscle cells. The majority of cells showed a uniform cytosolic pH. However, pH gradients were evident between the cytosol and nuclear regions with the nuclear regions having a predominantly higher pH than the cytosol. High concentrations of nigericin removed this gradient and indicated that active control of intranuclear pH by the nuclear membrane occured, possibly via the K⁺/H⁺ exchangers.     

Conformational studies on poly(ethacrylic acid) in aqueous salts by potentiometric,viscometric, optical and1H-NMR measurements

The conformation of poly(ethacrylic acid) was studied in aqueous salts by means of potentiometric, viscometric, optical and¹H-NMR measurements. The modified potentiometric titration curves in aqueous NaCl at ionic strengths 0.01–0.3 and 5–35 °C indicated the pH-induced conformational transition from the compact to extended coil. The standard free energy changes and the difference in molar heat capacity between the two conformers were estimated from the potentiometric data. The viscometric and optical behaviours did also show the existence of the compact form at acid pH's and the pH-induced conformational transition to the extended coil in aqueous NaCl and NaClO₄. From comparison with the data for poly(methacrylic acid), the results were concluded to be consistent with the existence of the compact form stabilized by hydrophobic interaction between ethyl groups. The methyl widths in 400 MHz¹H-NMR spectra indicated that the side chains in the polymer in the compact form are in a more restricted motional state than in the coil form. Intermolecular aggregations were found at very low degrees of ionization of carboxyl groups.     

Excimer laser assisted selective epitaxy of GaP

An ArF excimer laser has been used to achieve homoepitaxy of GaP at 500° C using trimethylgallium and tertiarybutylphosphine as the precursor gases. Dependence of epitaxial growth on several parameters is examined. The crystalline properties of the films are determined using cross-sectional transmission electron microscopy. It is found that at 500° C, in the presence of laser radiation, higher growth rate and superior crystalline properties of GaP are achieved compared to purely thermal metalorganic vapor phase epitaxy under the same conditions. Electrical properties of p-n diodes fabricated via Zn doping have also been examined.     

Conformational transition of copolymer of maleic acid and styrene in aqueous solution. III

Kinetic studies of the pH-induced conformational transition of the hydrophobic copolyelectrolyte of maleic acid and styrene in aqueous NaCl at ionic strength 0.09 were performed by an optical method at 25.0°C with a rapid reaction analyzer of high resolving power. A pH jump applied to a solution, in which the molecule is in the compact form, gives a kinetic trace from which, by appling the general kinetic theory of cooperative transitions, two mean relaxation times are determined. Plots of these relaxation times against the degree of ionization of the primary carboxyl groups of the maleic acid units agree well with theoretical predictions from the linear Ising model, where the molecule in the compact form is described as a random coil with hydrophobic “pockets.” The initiation parameter for a pocket obtained from the kinetic data is 0.036. On the other hand, the parameter calculated from the previous pH-titration results by applying Zimm–Rice theory is 0.015 at the ionic strength 0.09 and 25.0°C. Such values are compared with those determined from pH-titration data on other hydrophobic polyelectrolytes.