Activation Methods E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 180

Veröffentlichungsjahr: 2019

Beschreibung

Activation Methods examines recent improvements in the utilization of ultrasonic waves and pressurized gases to generate reactions. A straightforward method to use, sonochemistry allows chemical reactions to be carried out under ultrasound without the need for external heat, reagents or catalysts leading to high yields and the production of a minimum amount of waste. This book presents an overview of the main applications of sonochemistry in green organic chemistry, with an emphasis on texts published within the last few years. High-pressure chemical reactions offer innovative solutions to problems relating to synthesis. They allow access to new products and a further understanding of reaction mechanisms. This book presents the characteristics of hyperbaric activation, which allow the integration of an arsenal of tools for green chemistry, such as the lowering of energy costs and of by-products, as well as the possibility of using substrates that are sterically congested and generally inert.

Leseprobe

Table of Contents

Cover

1 Organic Sonochemistry: Ultrasound in Green Organic Synthesis

1.1. Introduction: history of ultrasound, organic sonochemistry and early work

1.2. Some elements of ultrasound theory

1.3. Laboratory and industrial equipment

1.4. Green organic sonochemistry

1.5. Sonochemistry in unconventional environments

1.6. Conclusion

1.7. References

2 High-Pressure Synthesis: An Eco-friendly Chemistry

2.1. High pressures in synthetic chemistry

2.2. Important concepts

2.3. Instrumentation

2.4. Applications

2.5. Conclusion

2.6. References

List of Authors

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1. Yield of the β-elimination reaction of β-bromoacetals under various e...

Table 1.2. Synthetic yield of 14-(4-bromophenyl)-14-H-dibenzo[a,j]xanthene with ...

Chapter 2

Table 2.1. Some ΔV

‡

for different types of reactions

Table 2.2. Melting point of common solvents at different pressures

List of Illustrations

Chapter 1

Figure 1.1. Hypotheses of the mechanism of the sonolysis of haloalkanes

Figure 1.2. Hypothesis of the mechanism of transformation of dibutyl sulfide und...

Figure 1.3. Study of the sonolysis of organic compounds at a frequency of 800 kH...

Figure 1.4. Study of sonolysis products of 9 amino acids at a frequency of 800 k...

Figure 1.5. Reduction of α,α′-dibromoketones in acetic acid by mercury dispersed...

Figure 1.6. Coordination of mercury with the enolate anion

Figure 1.7. Proposed mechanism of the reduction of α,α’-dibromoketones by ultras...

Figure 1.8. Saponification of aromatic carboxylic acid esters under ultrasonic i...

Figure 1.9. Barbier reaction under ultrasonic irradiation

Figure 1.10. Propagation of a sound wave in a liquid medium. For a color version...

Figure 1.11. Scale of sounds as a function of frequency

Figure 1.12. Simplified representation of the acoustic cavitation phenomenon. Fo...

Figure 1.13. Different ultrasonic baths: (a) single-frequency bath; (b) single-f...

Figure 1.14. Ultrasonic probes (source: with the kind permission of SinapTec): (...

Figure 1.15. High frequency reactor. For a color version of this figure, see www...

Figure 1.16. Cup-horn reactor. For a color version of this figure, see www.iste....

Figure 1.17. Continuous reactor

Figure 1.18. Chemical reaction sites in an aqueous medium subjected to acoustic ...

Figure 1.19. β-elimination of β-bromoacetals in heterogeneous media

Figure 1.20. Ultrasound-assisted Bouveault reaction

Figure 1.21. Ultrasound-assisted bromination reaction of anisole

Figure 1.22. Condensation reaction between a benzaldehyde and acetophenone

Figure 1.23. Ultrasound-assisted reaction of Knoevenagel between benzaldehyde an...

Figure 1.24. Ultrasonic benzoin condensation reaction catalyzed by octylmethylim...

Figure 1.25. Proposed mechanism for the ultrasound-assisted oxidation of primary...

Figure 1.26. Example of an ultrasound-assisted oxidation reaction with supported...

Figure 1.27. Oxidative depolymerization reaction of lignin

Figure 1.28. Epoxidation of chalcones under ultrasonic activation

Figure 1.29. Epoxidation reaction of cyclooctene under ultrasonic irradiation

Figure 1.30. Reduction reaction of benzophenone under ultrasonic irradiation

Figure 1.31. Ultrasound-assisted reduction reaction of nitro-aryls to amino-aryl...

Figure 1.32. Example of reduction of double bond under ultrasonic irradiation

Figure 1.33. Reduction of (2-nitro)ethylbenzene to 2-phenylethan-1-amine

Figure 1.34. Synthesis of pyrrole under ultrasonic irradiation

Figure 1.35. Ultrasound-assisted synthesis of 1,2,3-triazoles in the presence of...

Figure 1.36. Ultrasound-assisted condensation reaction between naphthols and ald...

Figure 1.37. Example of solvent-free ultrasonic synthesis of arylcoumarin under ...

Figure 1.38. Examples of anions and cations common in ionic liquid chemistry

Figure 1.39. Synthesis of [C

8

MIM][OTf] without solvent and under ultrasonic irra...

Figure 1.40. Proposed mechanism for ultrasound-assisted oxidation of benzyl alco...

Figure 1.41. Ultrasound-assisted Heck reaction in ionic liquids based on imidazo...

Figure 1.42. Synthesis without a catalyst and in water of heterocycles via the a...

Figure 1.43. Basic hydrolysis of benzonitrile under ultrasonic activation

Figure 1.44. Hydrolysis of esters under ultrasonic irradiation

Figure 1.45. Ultrasound-assisted transesterification of mangiferin, troxerutin a...

Figure 1.46. Enantiospecific biocatalytic reduction of HPMAE to (R)-phenylephrin...

Figure 1.47. Biocatalyzed one-pot synthesis of indolizines by cyclo-addition

Chapter 2

Figure 2.1. Pressures encountered in the universe

Figure 2.2. If V

A

+ V

B

> V

‡

> V

AB

, then the reaction is accelerated under pressu...

Figure 2.3. Graphical representation of the activation volume V

‡

Figure 2.4. Reaction rates as a function of pressure

Figure 2.5. Typical diagram of the piston-cylinder equipment

Figure 2.6. Typical diagram of the sealing system

Figure 2.7. Typical diagram of Teflon reactors used under pressure

Figure 2.8. Diels-Alder cycloaddition involving a pyrrole under high pressure. S...

Figure 2.9. Diels-Alder cycloaddition involving a benzofuran under high pressure

Figure 2.10. Diels-Alder cycloaddition involving a tetrasubstituted dienophile u...

Figure 2.11. Functionalization of gold nanoparticles by cycloaddition (4+2)

Figure 2.12. Intramolecular [4+2] cycloaddition promoted under high pressure

Figure 2.13. Organocatalyzed heterodiels-Diels-Alder reaction under high pressur...

Figure 2.14. Hetero-Diels-Alder reaction catalyzed by a Lewis acid under high pr...

Figure 2.15. Cycloadditions (3+2) between a nitrone or azide and a dipolarophili...

Figure 2.16. (3+2) Annulation between a cyclopropane diester and a tetrasubstitu...

Figure 2.17. Cycloaddition (2+2) of an isocyanate and an enol ether under high p...

Figure 2.18. Multi-component (4+2)/(3+2) high-pressure cycloaddition

Figure 2.19. Creation of vicinal quaternary centers by Michael addition under hi...

Figure 2.20. Organocatalyzed desymmetrization of cyclohexadienones

Figure 2.21. Double addition of nitromethane anion to β,β–disubstituted Michael ...

Figure 2.22. Enantioselective organocatalyzed conjugate addition of nitromethane...

Figure 2.23. Organocalatyzed conjugate addition of enamines on Michael acceptors...

Figure 2.24. Conjugate addition of chiral imines to pressurized crotonates

Figure 2.25. Conjugate addition of anilines under pressure in the presence of he...

Figure 2.26. Baylis-Hillman reaction under high pressure

Figure 2.27. Oxy-Michael reaction under pressure

Figure 2.28. Addition of indoles to trifluoromethyl ketones under high pressure....

Figure 2.29. Organocatalyzed aldolization reaction under pressure

Figure 2.30. Organocatalytic Mannich reaction involving acetone under pressure

Figure 2.31. Strecker reaction of acetone and aniline under pressure

Figure 2.32. Dissymmetric urea formation under high pressure

Figure 2.33. Transesterification of hindered esters under high pressure

Figure 2.34. Cyanation of acetals under high pressure in nitromethane

Guide

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Eco-compatibility of Organic Synthesis Set

coordinated by

Max Malacria

Volume 2

Activation Methods

Sonochemistry and High Pressure

Edited by

Jean-Philippe Goddard

Max Malacria

Cyril Ollivier

First published 2019 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:

ISTE Ltd

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London SW19 4EU

UK

www.iste.co.uk

John Wiley & Sons, Inc.

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Hoboken, NJ 07030

USA

www.wiley.com

© ISTE Ltd 2019

The rights of Jean-Philippe Goddard, Max Malacria and Cyril Ollivier to be identified as the authors of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.

Library of Congress Control Number: 2019948627

British Library Cataloguing-in-Publication Data

A CIP record for this book is available from the British Library

ISBN 978-1-78630-510-7

1Organic Sonochemistry: Ultrasound in Green Organic Synthesis

The evolution of chemistry, particularly organic chemistry, has had a serious impact in the 20th Century, from the health sector for the production of medicines, to the perfumes and clothing sector for the manufacture of dyes and textiles. While chemistry is at the root of extraordinary improvements in people’s living conditions, its image has gradually deteriorated as a result of incidents and accidents with dramatic ecological and/or human consequences. A global awareness of the impact of human activities on the environment has given rise to the neologism of sustainability. The concept of “green chemistry” or “sustainable chemistry” was first developed in the United States in the early 1990s with the objective of defining rules to pollution prevention related to chemical activities. These concepts led to the edition of 12 principles – often refered to as “the twelve principles of Green Chemistry”.

Among the activation techniques available to meet this new paradigm, the extraordinary properties of ultrasound and sonochemistry play an important role. Indeed, sonochemistry is simple to use, and allows chemical reactions to be carried out under ultrasound, sometimes preventing the need for external heat, reagents or catalysts, leading to high yields and the production of a minimum amount of waste.

From the discovery of ultrasound to its use in green organic chemistry, this chapter provides an overview of the main applications of sonochemistry in organic chemistry and especially in “green organic chemistry”, with a particular focus on the work published in the literature in recent years including some elements on ultrasound theory and the equipment used to produce it.

1.1. Introduction: history of ultrasound, organic sonochemistry and early work

While some butterflies imagine escaping their vampire predators by engaging in complicated aerial figures, others produce ultrasounds that repel these fearsome chiroptera, thus informing them that dinner looks detestable (Gouaillier 2001). While this story is 56 million years old between butterflies and bats, humankind did not learn to use ultrasound reliably until the early 20th Century.

1.1.1. The history of ultrasound and organic sonochemistry

Between 1793 and 1798, Father Lazzaro Spallanzani (1729–1799) and his colleague Doctor Louis Jurine (1751–1819) suspected the existence of ultrasound by observing that bats orient themselves in darkness without any difficulty. In 1880, Marcellin Berthelot wrote that “a multitude of chemical transformations are attributed today to the energy of ethereal matter, animated by these vibratory and other movements that produce calorific, luminous and electrical phenomena” (Berthelot 1880). In 1883, physiologist Francis Galton (1822–1911) discovered them by inventing the “ultrasonic whistle”. Nevertheless, it was the discovery of piezoelectricity in 1880 by the brothers Pierre (1859–1906) and Jacques (1856–1941) Curie, which made it possible after 1883 to produce and to use ultrasound easily and repeatedly. Paul Langevin (1872–1946) then had the idea of applying the phenomenon of piezoelectricity to the production and reception of ultrasound. After the tragedy of the Titanic in 1912, he proposed their use for iceberg detection. Then, in 1915, during the First World War, he developed a way to detect submarines by means of ultrasound; and in 1917, together with the engineer Constantin Chilowski, he invented the ASDIC (Anti-Submarine Detection Investigation Committee), an ancestor of Sonar, thus opening a field of industrial applications to these vibrations undetected by the human ear. The large number of fundamental discoveries between 1920 and 1939, as well as the technical improvements made, particularly concerning vibration converters, paved the way for the industrial development of ultrasound in cleaning, welding, drilling and medical applications. In 1951, J.J. Wild (1914–2009) and J. Reid (1926) developed the first ultrasound scanner for brain tumor research; it is now mainly used in obstetrics.

At the same time, studies have shown that ultrasound can change the medium in which it propagates and the work of Robert William Wood (1868–1955) and Alfred Lee Loomis (1887–1975) in biology and that of Theodore William Richards (1868–1928) and Alfred Lee Loomis in chemistry are generally considered as the first sonochemical experiments (Richards and Loomis 1927; Woods and Loomis 1927).

In 1928, Edmund Newton Harvey (1887–1959) and Alfred Lee Loomis observed, among other things, the destruction of frog blood cells irradiated by high frequency ultrasound (Harvey and Loomis 1928).

In 1933, Sándor Szalay showed that at an ultrasound frequency of 722 kHz can depolymerize starch, gum arabic and gelatin, thus reducing their viscosity (Szalay 1933; Szent-György 1933).

The same year, Earl Flosdorf and Leslie Chambers (1933) described the action of ultrasound for instant coagulation of proteins, oxidation of inorganic halides to dihalogens and hydrogen sulfide to sulfur by molecular oxygen.

They continued this work by studying the denaturation of proteins under ultrasound (Chambers and Flosdorf 1936), which they explained via the direct transfer of energy from the gases present to the protein molecules, without chemical intervention.

One year later, H. Frenzel and H. Schultes observed the luminescence emitted by water subjected to ultrasound during an experiment on Sonar (Frenzel and Schultes 1934).

E. Newton Harvey (Harvey 1939), P.O. Prudhomme (Prudhomme 1957) and R.H. Busso (Prudhomme and Busso 1952) and many others (for instance Griffing and Sette 1955) later carried out research dedicated to understanding this phenomenon.

In 1937, Sven Brohult carried out the partial fractionation of the hemocyanins of Helix pomatia, a Burgundy snail, by subjecting diluted solutions of their metalloproteins to ultrasound at a frequency of 250 kHz. He thus obtained uniform fragments 1/2 and 1/8 length of the initial molecule and observed an increase in the temperature of the medium (Brohult 1937).

In 1960, J. Giuntini and his collaborators (Hannoun et al. 1960) studied the action of ultrasound on the influenza virus, inactivating its infectious power while activating the vaccinating power.

1.1.2. Pioneering work in organic sonochemistry

It was not until the 1950s, with the development of more reliable ultrasonic generators, that researchers became interested in the effect of ultrasound for organic synthesis. Indeed, the main objective of the first studies carried out in organic sonochemistry was to study the effect of ultrasound on organic molecules in an aqueous medium (Zechmeister and Wallcave 1955; Zechmeister and Curelle 1958; Currelle et al. 1963) and not their use for organic chemical reactions.

For example, S. Prakash and J.D. Pandey (Prakash and Pandey 1965) studied the sonolysis of aliphatic and aromatic halogen compounds. They observed that iodobenzene and ortho-dichlorobenzene produce hydrogen halides while ethyl iodide releases molecular iodine. They also studied the kinetics of ultrasonic cleavage reactions and showed that the amount of halogen released increases with the duration of ultrasonic irradiation. In addition, the amount of free halogen increases up to a certain irradiation time beyond which a plateau is reached or a decrease is observed. Based on the knowledge of the phenomenon of transient acoustic cavitation (section 1.2.1.2), the authors proposed a mechanism for the formation of the various products of halocarbon sonolysis in aqueous media (Figure 1.1). The decomposition of water molecules is the main cause of the transformation of solute molecules. When ethyl iodide, iodobenzene and orthodichlorobenzene are decomposed, two primary reactions occur simultaneously (1). The decomposition of water mainly leads to the production of H. and OH. radicals. (1). Hydrogen peroxide is formed by the recombination of OH. radicals but also via the mechanism (2) in an oxygenated environment. The release of halogen radicals can occur according to mechanisms (3), (4) and (5). Since the energy of the C-I bond is lower than the ones of the C-Br and C-Cl bonds, the C-I bond is probably easily cleaved by the available ultrasonic energy. The activated oxygen generated oxidizes the alcohol to an aldehyde, which is then over-oxidized to a carboxylic acid (6). Acetylene and diacetylene being formed, as already observed by other authors (Zechmeister and Wallcave 1955; Zechmeister and Curelle 1958; Currell et al. 1963), are from the decomposition, caused by acoustic cavitation, of iodobenzene, phenol and o-dichlorobenzene, or from their depolymerization (7). Dichlorobenzene leads to the formation of chlorophenol, hydrochloric acid and catechol (5).

Subsequently, experiments were carried out by L.A. Spurlock and S.B. Reifsneider (1970) to investigate and understand the mechanisms of chemical transformations of simple molecules such as dibutyl sulfide when subject to ultrasound. The irradiation of dibutyl sulfide, in water and under argon atmosphere, at a frequency of 800 kHz primarily leads to the formation of dibutylsulfoxide, n-butane-sulfonic acid and traces of butanoic acid in the aqueous phase. The analysis of the gas phase reveals the presence of carbon monoxide, methane, ethylene and acetylene, of which butanal would be the probable precursor. The authors were able to propose a mechanism for the transformation of dibutyl sulfide under ultrasonic irradiation (Figure 1.2).

Figure 1.1.Hypotheses of the mechanism of the sonolysis of haloalkanes

(adapted from Prakash and Pandey 1965)

The authors then continued their research by studying the behavior of a series of aliphatic aldehydes and carboxylic acids, irradiated at a frequency of 800 kHz and an intensity of 9.4 W/cm2, in the presence of argon or molecular oxygen (Reifsneider and Spurlock 1973) (Figure 1.3).

Figure 1.2.Hypothesis of the mechanism of transformation of dibutyl sulfide under ultrasonic irradiation

(adapted from Spurlock and Reifsneider 1970)

Figure 1.3.Study of the sonolysis of organic compounds at a frequency of 800 kHz and an acoustic power of 9.4 W/cm2

(adapted from Reifsneider and Spurlock 1973)

The results showed that, in water and under ultrasonic irradiation, aliphatic aldehydes were both oxidized to carboxylic acids and fragmented into C1 and C2 volatile organic compounds (VOC). Aliphatic carboxylic acids, which are more stable under the action of ultrasound, fragmented in a smaller proportion. The authors attempted to draw a parallel with their previous study on dibutyl sulfide. The molecules studied contained from 1 to 10 carbons and were sometimes branched or di-functionalized; reactions that took place under ultrasound followed different simultaneous reaction paths and were therefore extremely complex. However, they noted the influence of the nature of the chemical function of the molecule or family that it belonged to on its stability under ultrasound irradiation.

In conclusion, this study made it possible to define certain guidelines for greater predictability of the mechanisms induced by ultrasound during the irradiation of organic molecules in an aqueous medium.

W.H. Staas and L.A. Spurlock (Staas and Spurlock 1975) then investigated the effects of ultrasound on amino acids and performed a detailed analysis of their sonolysis products. Thus, nine amino acids were irradiated at a frequency of 800 kHz under Ar atmosphere for six hours (Figure 1.4).

Figure 1.4.Study of sonolysis products of 9 amino acids at a frequency of 800 kHz and a power of 85 W

(adapted from Staas and Spurlock 1975)

Glycine and alanine are the most stable amino acids under ultrasonic irradiation, resulting in ammonia, carbon monoxide and formaldehyde. The formation of glycolic and lactic acids is attributed to the deamination of glycine and alanine. The presence of acetaldehyde in alanine and phenylacetaldehyde samples in phenylalanine samples after irradiation suggests the formation of aldehydes by irradiation of amino acids in general, via deamination and decarboxylation. The glutamine amide unit appears to be very stable against ultrasound and a very low proportion of glutamic acid deamination is observed. Similarly, the loss of a CH2 from the distant carboxylic functional group of glutamic acid that leads to aspartic acid is very slow. Sulfur-containing amino acids undergo the expected reactions under oxidizing conditions. Cysteine is converted into cystine and cysteic acid is formed from both cysteine and cystine. The quantities of these sonolysis products are in accordance with the usual oxidation sequence of thiols to sulfonic acids. Hydrogen sulfide and serine are formed from cysteine. Surprisingly, methionine is only slightly more unstable under ultrasonic irradiation than histidine and phenylalanine. Formaldehyde production is higher from methionine than from any other amino acid. Formaldehyde could be formed by hydroxylation and removal of the terminal S-methyl group. The methane and methanol observed appear to come from the same source. The authors also observe polymer formation as a result of the pH of the aqueous phase.

In conclusion, given the high stability of the amide bond of glutamide, the authors planned to investigate the stability of the peptide bond in future work.