Solvents, alternative reaction media

As will happen, for example, with perfluorotriethylamine, a substance that is a good alternative reaction medium may be found for reactions and it can be easily recycled by simple extractive workup (Nakano and Kitazume, 1999). One of the most important issues in twenty-first century scientific society is the environmental problem. Thus far, there have been increasing demands for substitutes for toxic and/or harmful solvents like CH2CI2. Recently, inert and less toxic fluorous (perfluorinated) fluids have been recognized and are attracting attention as new alternative solvents (Fish, 1999). This fact shows the need to survey the scope and limitations of the utility of these liquids as alternative reaction media for reactions, which are of great current interest due to their unique reactivities and selectivities. 

Supercritical fluids, another class of alternative reaction medium, have been used as solvents in catalysis for many years. Ipatiev reported the isomerisation of cyclohexane to methylcyclopentane under supercritical conditions using A1203 as the catalyst1151 and shortly afterwards communicated the oligomerisation of supercritical ethylene catalysed by AICI3.1161 However, it took another 60 years before supercritical fluids were used as solvents for... 

Normally, the solvent of choice for bromination of alkenes is carbon tetrachloride which has the disadvantage of high toxicity and destruction of the ozone layer. Despite that, an international agreement for the production of reduced amounts of carbon tetrachloride exists and there is still a need for an alternative reaction medium. Savage et al. have performed the bromination reaction of functionalized olefins in perfluorohexanes [11]. With only one equivalent of... 

Dense carbon dioxide represents an excellent alternative reaction medium for a variety of polymerization processes. Numerous studies have confirmed that CO2 is a potential solvent for many chain growth polymerization methods, including free-radical, cationic, and ring-opening metathesis polymerizations. Carbon dioxide has also been demonstrated to be an effective solvent for step-growth polymerization techniques. Advances in the design and synthesis of surfactants for use in CO2 will allow compressed CO2 to be utilized for a wide variety of polymerization systems. These advances may enable carbon dioxide to replace hazardous VOCs and CFCs in many industrial applications, making CO2 an enviromentally responsible solvent of choice for the polymer industry. 

Reacting lipophilic substrates with hydrophilic compounds, as in the case of most transesteriflcation reactions, is one of the major difficulties in lipase-catalyzed reactions. Several parameters need to be considered to overcome this immiscibility problem. One commonly proposed strategy is the use of a nonaqueous medium. In this chapter, the advantages of using nonaqueous media in biochemical synthesis reactions, over aqueous and solvent-free systems, are discussed. The use of hydrophobic solvents is also discussed, followed by a presentation of the alternatives that can overcome the limitations of solvents. The focus of this chapter is mainly on the use of supercritical fluids (SCFs) as a green alternative reaction medium. The chapter also discusses ionic liquids (ILs) as another alternative. These solvents and the factors affecting their physical properties and their effect on the activity and stability of lipase are also discussed. 

The photolysis of chlorinated aromatic compounds occurs by several processes which follow predictable routes 13). They frequently undergo photochemical loss of chlorine by dissociation of the excited molecule to free radicals or, alternatively, through a nucleophilic displacement reaction with a solvent or substrate molecule. Either mechanism is plausible, and the operation of one or the other may be influenced by the reaction medium and the presence of other reagents. 

Initial preparative work with oxynitrilases in neutral aqueous solution [517, 518] was hampered by the fact that under these reaction conditions the enzymatic addition has to compete with a spontaneous chemical reaction which limits enantioselectivity. Major improvements in optical purity of cyanohydrins were achieved by conducting the addition under acidic conditions to suppress the uncatalyzed side reaction [519], or by switching to a water immiscible organic solvent as the reaction medium [520], preferably diisopropyl ether. For the latter case, the enzymes are readily immobilized by physical adsorption onto cellulose. A continuous process has been developed for chiral cyanohydrin synthesis using an enzyme membrane reactor [61]. Acetone cyanhydrin can replace the highly toxic hydrocyanic acid as the cyanide source [521], Inexpensive defatted almond meal has been found to be a convenient substitute for the purified (R)-oxynitrilase without sacrificing enantioselectivity [522-524], Similarly, lyophilized and powered Sorghum bicolor shoots have been successfully tested as an alternative source for the purified (S)-oxynitrilase [525],... 

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