Title:
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Continuous Organic Reactions in Supercritical Fluids
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This Thesis describes how continuous flow reactors and heterogeneous catalysts have
been used in conjunction with supercritical fluid solvents to develop a new process for
carrying out catalytic organic reactions. The process exploits both the advantages of
supercritical fluids (e.g. solvent tunability allowing facile product separation from the
solvent) and heterogeneous catalysts and can be considered a 'Green' method of
chemistry.
Various reaction types have been explored, namely noble-metal catalysed
hydrogenation reactions, supported-acid catalysed Friedel-Crafts alkylation reactions
and supported-acid catalysed Friedel-Crafts acylation reactions.
Chapter 1: Introduction
This Chapter begins with an introduction to the concept of 'Green Chemistry' and its
significance at the present time. The problems with the use of conventional solvents
are highlighted, and examples of two 'greener' solvent systems - ionic liquids and
supercritical fluids - are described. For each of these solvent systems, a brief review
.of their use in more recent reaction chemistry is included.
Chapter 2: Experimental
This Chapter begins by describing the supercritical flow equipment developed at
Nottingham in some detail, and includes equipment modifications which were made
both to improve the effectiveness and safe operation of the equipment. The final
sections of the Chapter describe the catalysts and analytical techniques used during
the course of the research.
Chapter 3: Continuous Hydrogenation in Supereritical Fluids
This Chapter opens with a summary of some initial hydrogenation work carried out at
Nottingham prior to this research. The results section reports a range of non-selective
hydrogenation reactions, commencing with a detailed study of the hydrogenation of
cyclohexene which was used to explore the capabilities of the equipment. Chapter 4: Continuous Selective Hydrogenation in Supercritical Fluids
This Chapter is a continuation of Chapter 3 and begins with an introduction to
different types of selective hydrogenation, then highlights some literature examples of
selective hydrogenations conducted in supercritical fluids. The results section reports
several selective hydrogenation reactions conducted at Nottingham.
Chapter 5: Continuous Friedel-Crafts Alkylation and Acylation Reactions
This Chapter begins with a discussion of the problems associated with conventional
Friedel-Crafts chemistry, most of which are associated with the homogeneous
catalysts normally used. A review of the use of various solid acid materials
investigated for Friedel-Crafts type activity follows and this section concludes with
literature examples of some supercritical Friedel-Crafts processes. The results section
begins by reporting Friedel-Crafts alkylation reactions and closes with a brief amount
ofFriedel-Crafts acylation.
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