Bruce S. Holden

Aqueous Suzuki Coupling Reactions of Basic Nitrogen-Containing Substrates in the Absence of Added Base and Ligand: Observation of High Yields under Acidic Conditions.

A series of aqueous heterogeneous Suzuki coupling reactions of substrates containing basic nitrogen centers with phenylboronic acid in the absence of added base and ligand is presented. High yields of products were obtained by employing aryl bromides containing aliphatic 1°, 2°, and 3° amine substituents, and good to high yields were obtained by employing a variety of substituted bromopyridines. In the former series, the pH of the aqueous phase changed from basic to acidic during the course of the reaction, while in the latter series the aqueous phase was on the acidic side of the pH scale throughout the entire course of reaction. A mechanistic interpretation for these observations, which generally preserves the oxo palladium catalytic cycle widely accepted in the literature, is presented.

Pd-Catalyzed Suzuki coupling reactions of aryl halides containing basic nitrogen centers with arylboronic acids in water in the absence of added base

The Pd-catalyzed Suzuki coupling reactions of a series of aryl chlorides and aryl bromides containing basic nitrogen centers with arylboronic acids in water in the absence of added base are reported. The reactions proceed either partially or entirely under acidic conditions. After surveying twenty-two phosphorus ligands, high yields of products were obtained with aryl chlorides only when a bulky ligand, 2-(di-tert-butyl-phosphino)-1-phenyl-1H-pyrrole (cataCXium®PtB) was used. In contrast, aryl bromides produced high yields of products in the absence of both added base and added ligand. In order to explore the Suzuki coupling process entirely under acidic conditions, a series of reactions were conducted in buffered acidic media using several model substrates. 4-Chlorobenzylamine, in the presence of cataCXium®PtB, produced high yields of product at buffered pH 6.0; the yields dropped off precipitously at buffered pH 5.0 and lower. The fall-off in yield was attributed to the decomposition of the Pd–ligand complex due to the protonation of the ligand in the more acidic aqueous media. In contrast, in the absence of an added ligand, 4-amino-2-chloropyridine produced quantitative yields at buffered pH 3.5 and 4.5 while 4-amino-2-bromopyridine produced quantitative yields in a series of buffered media ranging from pH 4.5 to 1.5. These substrates are only partially protonated in acidic media and can behave as active Pd ligands in the Suzuki catalytic cycle.

Hydrogen reduction in heat transfer fluid in parabolic trough CSP plants

Hydrogen (H2) has been found to be generated in very small proportions when diphenyl oxide/ biphenyl heat transfer fluid (HTF) is operated at temperatures close to 400°C. At such temperatures, H2 can permeate through steel walls to the vacuum space of parabolic trough (PT) solar receivers, where it increases heat losses that can significantly impact the economics of PT concentrated solar power plants. A novel process for the reduction of the H2 concentration in HTF via stripping and gas separation has been simulated for the operation in PT CSP plants. Applying the proposed process, the concentration of H2 in HTF can be reduced down to 1 ppb. A cost comparison between the H2 separation process and frequent PT receivers replacement was conducted and found that proposed H2 removal process is more economic.Hydrogen (H2) has been found to be generated in very small proportions when diphenyl oxide/ biphenyl heat transfer fluid (HTF) is operated at temperatures close to 400°C. At such temperatures, H2 can permeate through steel walls to the vacuum space of parabolic trough (PT) solar receivers, where it increases heat losses that can significantly impact the economics of PT concentrated solar power plants. A novel process for the reduction of the H2 concentration in HTF via stripping and gas separation has been simulated for the operation in PT CSP plants. Applying the proposed process, the concentration of H2 in HTF can be reduced down to 1 ppb. A cost comparison between the H2 separation process and frequent PT receivers replacement was conducted and found that proposed H2 removal process is more economic.