No abstract

Acetonitrile is regarded as a key solvent in the pharmaceutical industry. However, the volatility in acetonitrile supply in recent years, coupled with its relatively poor environmental profile, has presented significant challenges to its use in manufacturing processes and laboratories. This study investigates the importance of acetonitrile in the pharmaceutical industry and critically examines several options for reducing the exposure of the industry to future supply problems whilst also improving its life cycle management. The physicochemical properties of acetonitrile were compared with other typical process solvents and the Conductor-like Screening Model (COSMO) surfaces and sigma profiles were used to help explain the favourable solvation behaviour of acetonitrile. Several options for the replacement or recovery and recycle of acetonitrile were critically examined in the contexts of environmental, technical and economic feasibility. Azeotropic distillation was found to be the most likely approach to recovering acetonitrile from aqueous waste streams. Several potential breaking agents were assessed against a range of selection rules based on residue curve maps, determined using the Universal Functional Activity Coefficient (UNIFAC) method, and potential processing issues. A range of ionic liquids were screened via the predictive Conductor-like Screening Model for Realistic Solvation (COSMO-RS) approach and several promising candidates were identified. Experimental vapour-liquid equilibria studies were carried out, confirming the feasibility of ionic liquid-enhanced azeotropic distillation as a novel approach to acetonitrile recovery.

Palladium(II) acetate microencapsulated in polyurea (MC-[Pd]) is an economical and versatile heterogeneous catalyst for a range of phosphine-free cross-coupling reactions in both conventional solvents and supercritical carbon dioxide (scCO2); the catalyst can be recovered by a simple filtration and recycled up to four times.

A new polymer-supported chromium porphyrin has been prepared and fully characterised; its catalytic activity and recyclability were investigated for the ring-opening copolymerisation of 1,2-cyclohexene oxide (CHO) and carbon dioxide (CO2).

Heck and Suzuki reactions proceed in good yield in supercritical carbon dioxide in the presence of palladium acetate and tri-tert-butylphosphine with both free and polymer-tethered substrates.