Chemistry In Alternative Reaction Media / Edition 1

Paperback (Print)
Buy New
Buy New from
Used and New from Other Sellers
Used and New from Other Sellers
from $26.60
Usually ships in 1-2 business days
(Save 78%)
Other sellers (Paperback)
  • All (11) from $26.60   
  • New (6) from $88.40   
  • Used (5) from $26.60   


The use of organic solvents and their emissions has been at the centre of major environmental concern in recent years, and there is currently a great deal of interest in finding alternatives to halogenated and volatile organic solvents for synthesis. Chemistry in Alternative Reaction Media explores why solvents are used and the problems associated with them. It describes the state-of-the art in solvent replacement technologies. Supercritical fluids, biphasic reactions, ionic and fluorous liquids, and aqueous chemistry are brought together in a single textbook, which explains how they may be used to increase reaction efficiency, improve separation and catalyst recovery, and reduce emissions to the environment. As well as describing the principles behind these methods, and the environmental, economic and chemical advantages that these alternatives can bring, numerous examples of applications are given including most major reaction types, and consideration is given to potential scale-up and industrial use. This book will appeal to anyone with an interest in organic synthesis; reaction chemistry; catalysis; and process development, and to undergraduate and graduate students of organic chemistry; catalysis; green chemistry; clean technology and environmental chemistry courses.

Read More Show Less

Editorial Reviews

From the Publisher
"…a convenient and effective book giving a good introduction to the possibilities and problems of new reaction media…" (Angewandte Chemie International Edition, 2004/43)

"...a well-written and timely piece of work for any scientists and engineers who work with solvents...and will be a valuable addition to their bookshelves." (Energy Sources, Vol. 26, 2004)

"...well written and easy to read, very useful for a student audience...will introduce the subject to a wider audience..." (Organic Process Research & Development, Dec 2003)

Read More Show Less

Product Details

  • ISBN-13: 9780471498490
  • Publisher: Wiley
  • Publication date: 12/1/2003
  • Edition number: 1
  • Pages: 272
  • Product dimensions: 6.06 (w) x 9.07 (h) x 0.63 (d)

Table of Contents


Abbreviations and Acronyms.

1 Chemistry in Alternative Reaction Media.

1.1 Economic and Political Considerations.

1.2 Why Do Things Dissolve?

1.3 Solvent Properties and Solvent Classification.

1.3.1 Density.

1.3.2 Mass Transport.

1.3.3 Boiling Point, Melting Point and Volatility.

1.3.4 Solvents as Heat-Transfer Media.

1.3.5 Cohesive Pressure, Internal Pressure, and Solubility Parameter.

1.4 Solvent Polarity.

1.4.1 Dipole Moment and Dispersive Forces.

1.4.2 Dielectric Constant.

1.4.3 Electron Pair Donor and Acceptor Numbers.

1.4.4 Empirical Polarity Scales.

1.4.5 ENT and ET(30) Parameters.

1.4.6 Kamlet–Taft Parameters.

1.4.7 Hydrogen Bond Donor (HBD) and Hydrogen Bond Acceptor (HBA) Solvents.

1.5 The Effect of Solvent Polarity on Chemical Systems.

1.5.1 The Effect of Solvent Polarity on Chemical Reactions.

1.5.2 The Effect of Solvent Polarity on Equilibria.

1.6 W hat is Required from Alternative Solvent Strategies?


2 Multiphasic Solvent Systems.

2.1 An Introduction to Multiphasic Chemistry.

2.1.1 The Traditional Biphasic Approach.

2.1.2 Temperature Dependent Solvent Systems.

2.1.3 Single- to Two-Phase Systems.

2.1.4 Multiphasic Systems.

2.2 Solvent Combinations.

2.2.1 Water.

2.2.2 Fluorous Solvents.

2.2.3 Ionic Liquids.

2.2.4 Supercritical Fluids and Other Solvent Combinations.

2.3 Benefits and Problems Associated with Multiphasic Systems.

2.3.1 Partially Miscible Liquids.

2.4 Kinetics of Homogeneous Reactions.

2.4.1 Rate is Independent of Stoichiometry.

2.4.2 Rate is Determined by the Probability of Reactants Meeting.

2.4.3 Rate is Measured by the Concentration of the Reagents.

2.4.4 Catalysed Systems.

2.5 Kinetics of Biphasic Reactions.

2.5.1 The Concentration of Reactants in Each Phase is Affected by Diffusion.

2.5.2 The Concentration of the Reactants and Products in the Reacting Phase is Determined by Their Partition Coefficients.

2.5.3 The Partition Coefficients of the Reactants and Products May Alter the Position of the Equilibrium.

2.5.4 Effect of Diffusion on Rate.

2.5.5 Determining the Rate of a Reaction in a Biphasic System.

2.6 Conclusions.


3 Reactions in Fluorous Media.

3.1 Introduction.

3.2 Properties of Perfluorinated Solvents.

3.3 Designing Molecules for Fluorous Compatibility.

3.4 Probing the Effect of Perfluoroalkylation on Ligand Properties.

3.5 Partition Coefficients.

3.6 Liquid–Liquid Extractions.

3.7 Solid Separations.

3.8 Conclusions.


4 Ionic Liquids.

4.1 Introduction.

4.1.1 The Cations and Anions.

4.1.2 Synthesis of Ionic Liquids.

4.2 Physical Properties of Ionic Liquids.

4.3 Benefits and Problems Associated with Using Ionic Liquids in Synthesis.

4.4 Catalyst Design.

4.5 Conclusions.


5 Reactions in Water.

5.1 The Structure and Properties of Water.

5.1.1 The Structure of Water.

5.1.2 Near-Critical Water.

5.1.3 The Hydrophobic Effect.

5.1.4 The Salt Effect.

5.2 The Benefits and Problems Associated with Using Water in Chemical Synthesis.

5.3 Organometallic Reactions in Water.

5.4 Aqueous Biphasic Catalysis.

5.4.1 Ligands for Aqueous–Organic Biphasic Catalysis.

5.5 Phase Transfer Catalysis.

5.5.1 The Transfer of Nucleophiles into Organic Solvents.

5.5.2 Mechanisms of Nucleophilic Substitutions Under Phase Transfer Conditions.

5.5.3 The Rates of Phase Transfer Reactions.

5.5.4 Using Inorganic Reagents in Organic Reactions.

5.6 Organometallic Catalysis under Phase Transfer Conditions.

5.7 Triphase Catalysis.

5.7.1 Mixing Efficiency in Solid–Liquid Reactions.

5.8 Conclusions.


6 Supercritical Fluids.

6.1 Introduction.

6.2 Physical Properties.

6.3 Local Density Augmentation.

6.4 Supercritical Fluids as Replacement Solvents.

6.5 Reactor Design.

6.6 Spectroscopic Analysis of Supercritical Media.

6.6.1 Vibrational Spectroscopy.

6.6.2 NMR Spectroscopy.

6.7 Reactions in Supercritical Media.

6.8 Conclusions.


7 Diels–Alder Reactions in Alternative Media.

7.1 Diels–Alder Reactions in Water.

7.2 Diels–Alder Reactions in Perfluorinated Solvents.

7.3 Diels–Alder Reactions in Ionic Liquids.

7.4 Diels–Alder Reactions in Supercritical Carbon Dioxide.

7.5 Conclusions.


8 Hydrogenation and Hydroformylation Reactions in Alternative Solvents.

8.1 Introduction.

8.2 Hydrogenation of Simple Alkenes and Arenes.

8.2.1 Hydrogenation in Water.

8.2.2 Hydrogenation in Ionic Liquids.

8.2.3 Hydrogenation in Fluorous Solvents.

8.2.4 Hydrogenation in Supercritical Fluids.

8.3 Hydroformylation Reactions in Alternative Media.

8.3.1 Hydroformylation in Water.

8.3.2 Hydroformylation in Ionic Liquids.

8.3.3 Hydroformylation in Fluorous Solvents.

8.3.4 Hydroformylation in Supercritical Fluids.

8.4 Conclusions.


9 FromAlkanestoCO2: Oxidation in Alternative Reaction Media.

9.1 Oxidation of Alkanes.

9.2 Oxidation of Alkenes.

9.3 Oxidation of Alcohols.

9.4 Oxidation of Aldehydes and Ketones.

9.5 Destructive Oxidation.

9.6 Conclusions.


10 Carbon–Carbon Bond Formation, Metathesis and Polymerization.

10.1 Carbon–Carbon Coupling Reactions.

10.1.1 Heck Coupling Reactions.

10.1.2 Suzuki Coupling Reactions.

10.1.3 Reactions Involving the Formation of C=C Double Bonds.

10.2 Metathesis Reactions.

10.2.1 Ring Opening Metathesis Polymerization.

10.2.2 Ring Closing Metathesis.

10.3 Polymerization Reactions in Alternative Reaction Media.

10.3.1 Polymerization Reactions in Water.

10.3.2 Polymerization Reactions in Supercritical Carbon Dioxide.

10.3.3 Polymerization in Fluorous Solvents.

10.4 Conclusions.


11 Alternative Reaction Media in Industrial Processes.

11.1 Obstacles and Opportunities for Alternative Media.

11.2 Reactor Considerations for Alternative Media.

11.2.1 Batch Reactors.

11.2.2 Flow Reactors.

11.2.3 New Technology Suitable for Multiphasic Reactions.

11.3 Industrial Applications of Alternative Solvent Systems.

11.3.1 The Development of the First Aqueous–Organic Biphasic Hydroformylation Plant.

11.3.2 Other Examples of Processes Using Water as a Solvent.

11.3.3 Scale-Up of PTC Systems.

11.3.4 Thomas Swan Supercritical Fluid Plant.

11.3.5 Other Applications of Supercritical Carbon Dioxide.

11.4 Outlook for Fluorous Solvents and Ionic Liquids.

11.5 Conclusions.



Read More Show Less

Customer Reviews

Be the first to write a review
( 0 )
Rating Distribution

5 Star


4 Star


3 Star


2 Star


1 Star


Your Rating:

Your Name: Create a Pen Name or

Barnes & Review Rules

Our reader reviews allow you to share your comments on titles you liked, or didn't, with others. By submitting an online review, you are representing to Barnes & that all information contained in your review is original and accurate in all respects, and that the submission of such content by you and the posting of such content by Barnes & does not and will not violate the rights of any third party. Please follow the rules below to help ensure that your review can be posted.

Reviews by Our Customers Under the Age of 13

We highly value and respect everyone's opinion concerning the titles we offer. However, we cannot allow persons under the age of 13 to have accounts at or to post customer reviews. Please see our Terms of Use for more details.

What to exclude from your review:

Please do not write about reviews, commentary, or information posted on the product page. If you see any errors in the information on the product page, please send us an email.

Reviews should not contain any of the following:

  • - HTML tags, profanity, obscenities, vulgarities, or comments that defame anyone
  • - Time-sensitive information such as tour dates, signings, lectures, etc.
  • - Single-word reviews. Other people will read your review to discover why you liked or didn't like the title. Be descriptive.
  • - Comments focusing on the author or that may ruin the ending for others
  • - Phone numbers, addresses, URLs
  • - Pricing and availability information or alternative ordering information
  • - Advertisements or commercial solicitation


  • - By submitting a review, you grant to Barnes & and its sublicensees the royalty-free, perpetual, irrevocable right and license to use the review in accordance with the Barnes & Terms of Use.
  • - Barnes & reserves the right not to post any review -- particularly those that do not follow the terms and conditions of these Rules. Barnes & also reserves the right to remove any review at any time without notice.
  • - See Terms of Use for other conditions and disclaimers.
Search for Products You'd Like to Recommend

Recommend other products that relate to your review. Just search for them below and share!

Create a Pen Name

Your Pen Name is your unique identity on It will appear on the reviews you write and other website activities. Your Pen Name cannot be edited, changed or deleted once submitted.

Your Pen Name can be any combination of alphanumeric characters (plus - and _), and must be at least two characters long.

Continue Anonymously

    If you find inappropriate content, please report it to Barnes & Noble
    Why is this product inappropriate?
    Comments (optional)