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Chemical processes and reactions under extreme or non-classic conditions: Chemical effects and applications of high pressures, high temperatures, ionising radiations, microwaves, plasmas, supercritical media, ultrasounds
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ISSN 1018-5593
EUROPEAN
COMMISSION
SCIENCE
RESEARCH
DEVELOPMENT
Practical information and programmes
CHEMICAL PROCESSES
AND REACTIONS UNDER EXTREME
OR NON-CLASSIC CONDITIONS
COST ACTION D6
EUR 18024 EN EUROPEAN COMMISSION
Edith CRESSON, Member of the Commission
responsible for research, innovation, education, training and youth
DG XII/B.1 — RTD actions: Cooperation with non-member countries
and international organisations — European Economic Area, COST,
Eureka and international organisations
Contact: Mr Bernd Reichert
Address: European Commission, rue de la Loi 200 (SDME 1/98),
B-1049 Brussels — Tel. (32-2) 29-54617; fax (32-2) 29-93960
Cover picture: B. Fleuret, courtesy of the Tourism Office of Chambéry. EUROPEAN COMMISSION
CHEMICAL PROCESSES
AND REACTIONS UNDER EXTREME
OR NON-CLASSIC CONDITIONS
COST ACTION D6
Chemical effects and applications of
high pressures, high temperatures, ionising radiations, microwaves,
plasmas, supercritical media, ultrasounds
Chambéry (France), 29 November to 1 December 1996
Edited by
J. L. Luche, C. Balny, S. Benefice, J. M. Denis, C. Pétrier
Directorate-General
Science, Research and Development
1998 EUR 18024 EN LEGAL NOTICE
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of the following information.

A great deal of additional information on the European Union is available on the Internet.
It can be accessed through the Europa server (http://europa.eu.int).
Cataloguing data can be found at the end of this publication.
Luxembourg: Office for Official Publications of the European Communities, 1998
ISBN 92-828-1986-8
© European Communities, 1998
Reproduction is authorised provided the source is acknowledged.
Printed in Belgium ORGANIZATION
The Conference was organized by a Committee composed of
Dr. J.L. Luche, University of Chambéry, Chairman
Dr. C. Balny, INSERM, Montpellier
Dr. S. Benefice, COST Secretariat, Brussels
Dr. J.M. Denis, University of Rennes
Prof. C. Petrier,y of Chambéry
locally helped by
Dr. B. David
Dr. N. Monnier
I. Bruni (Secretary)
ACKNOWLEDGEMENTS
The Organizers thank warmly the following Institutions for their financial support
the COST bureau of the European Community (Bruxelles)
the "Institut National de la Santé et de la Recherche Médicale" (Paris)
Université de Savoie (Chambéry)
Electricité de France (Paris) FOREWORDS
Chemistry, the Science which can be seen as the daughter of the Arabic Al-Khimi, has
the purpose of transforming matter. Not in the manner by which Lead could become
Gold, but in the manner by which a raw, useless material can become a highly
valuable one, a medical drug, a fuel, a plastic, or all what we use day after day,
sometimes without taking care of it.
These trivial statements lead to a less trivial consideration : the economical weight of
chemical industry. Its considerable importance in each country makes necessary a
strong research effort, in order to solve the continuously renewed problems. Let us
think of only two examples, the existence of new antibiotic-resistant strains of
bacteria, making urgent the synthesis of new active molecules, and the problems of
atmospheric ozone, which should stimulate the development of less potentially
dangerous processes. Many other examples could be chosen, but the conclusion to
which we are invariably led is that a considerable effort has to be undertaken to face
all these challenges.
In order to make this goal attractive and efficient,, a programme of concerted research
was proposed, and launched by the European Communities in 1993 under the
auspices of the COST Organisation. Seven items recognised as scientifically
significant and, in the future, able to provide industrial developments, were selected.
Among these items, one appeared especially open, giving to the creativity and
imagination of the researchers wide opportunities to express, the development of
new methods for the activation of chemical processes. The community of european
chemists responded very favourably and a number of networks were created. Some
of these preexisted, but in all the cases, the COST Chemistry programmes revealed
the strong will of cooperation between european researchers.
Thus, research was developed on the uses of high-temperatures and pressures,
microwaves, plasmas, supercritical media, ultrasonic waves. Since in most cases,
little was known about many fundamental aspects, this COST Action stimulated
cooperative works in the 2 main directions of Scientific Research, the progress of
knowledge in rarely explored domains, and its use to a common benefit. This book
containing contributions from various European laboratories will constitutes a
testimony of the dynamism of european research in these fields.
G. Balavoine
Chairman of^tìrféeOSTOhemistry Technical Committee
IV INTRODUCTION
One of the objectives of the methodological research in chemistry consists in finding
conditions under which a given transformation can be accomplished with minimal
expenses of matter and energy. Concerning this latter point, the use of experimental
conditions as close as possible to the so-called "normal", essentially temperature and
pressure under which we live, is highly desirable. However, it is well known that
this "spontaneous" chemistry is limited to systems with a relatively high degree of
reactivity and selectivity, and many useful transformations cannot be performed
simply by "letting things go". Activation is necessary among which heating,
application of pressure, catalysis, i.e. the use of physical or chemical agents, are the
most common means. Useful chemical transformations, many of these of industrial
importance, were thus found and developed under these conditions, which are not
the so-called normal ones, but remain "classical".
During the last 20-25 years, a research was initiated using what is named now "non-
classical" or "extreme" conditions, but it remained marginal and dispersed. The
objectives were, in most cases, the discovery of new selective procedures, and for
some others probably less numerous, the simple scientific curiosity. By the
denomination of "extreme" or "non-classical", one should understand conditions
which are clearly far from the normal. A few examples will help to define more
accurately the distinction.
While classical heating in organic chemistry implies temperatures of up to 250°C
reached in, and maintained for relatively long times, some reactions were tried at
much higher temperatures, say 1000°C during a few milliseconds, or with systems
providing heating rates of several tens of degrees per second. Thus came familiar to
the community of chemists high-temperature chemistry and microwave heating,
two non-conventional methods.
Similar examples can be found with the application of high pressures. Catalysis (e.g.
hydrogénation, carbonylation, polymerisation, etc..) makes use of pressures of tens or
hundreds of bars. But what can be expected under > 10000 bars ? Will these pressures
force unreactive, uncatalysed systems to react ? Furthermore, all these conditions are
supposed to be largely far from compatible with life. A second important question
comes then, concerning the effect of such high temperatures and pressures on the
living organisms, or, since this is a too large and difficult question, on some proteins,
enzymes etc ? A third case is found with the recent development of sonochemistry, in which
ultrasound is used to produce chemical reactions. A priori the interaction of acoustic
waves with matter seems improbable. In fact, via the phenomenon of cavitation,
high energy phenomena occur during microseconds or even less, and many
molecules can be split into reactive fragments. Despite a still controversial theoretical
understanding, applications of sonochemistry have been burgeoning in these last 15
years.
Since the non-classical and extreme conditions were (this is almost a definition) not
extensively studied, their recent development raised among the community of
chemists, the interest for all what is new from the fundamental and applied
viewpoints. Applications were found in organic or inorganic chemistries, life
sciences (biochemistry, biology), environmental protection, polymer science, food
technology, even in the industry.
The frame under which the COST D6 Action was created and has developped its
activities during the last 4 years is thus defined. However one could object that the
sub-disciplines which compose this action have just but little overlap. This was
certainly the situation at the beginning of the Action. After 4 years of common work,
this judgement should be revised, at least in part. Recent research established that the
unusual methodologies rely on unusual phenomena. Out-of-equilibrium states
inducing non-classical mechanisms, original reactivity pathways, uncommon
geometrical or electronic states, were shown to result (or their existence can be
suspected) from the application of non-classical activation methods, and could be
common between the chemistries induced by ultrasound, high pressures, high
temperatures, plasmas, microwaves, etc. But this link is still tenuous, and future
research will probably deepen some of these fundamental aspects. What is however
beyond doubt, and clearly results from these years of research, is that now the new
methodologies are no longer simple techniques, but distinct fields of chemistry.
VI Table of Contents
1. Basic aspects
1.1. Water and carbon dioxide at high pressures : properties and applications
G. Wiegand ρ 3
1.2.Freeradicalformation in water by ionising radiation and by ultrasound
C.VonSonntag,G. Mark, H.P Schuchmann, J. von Sonntag, and A Tauber ρ 11
1.3.Dosimetryofthe mechanical and radical effects of ultrasound
G.Portenlänger,Η. Heusingerρ 19
1.4.Standingwaves in a high frequency sonoreactor, visualisation and effects
E.Gonze,Y.Gonthier, P. Boldo, A. Bernis ρ 25
1.5. Estimation of free radicalsgenerationfromair­water cavitation bubbles
S. Sochard, A.M.Wilhelm, Η.Delmasρ 29
1.6. Effect of ultrasound on solid­liquidmasstransfer
F. Burdin, A.M. Wilhelm, Η. Delmasρ 33
1.7. Acoustic cavitation field prediction for a simple configuration of sonication
J.L. Laborde, C. Bouyer, J.P. Calta girone, A. Gérard ρ 39
1.8. Plasma chemistry in gases at atmosphericpressure
J.P. Borra, A. Goldman, M. Goldmanρ 43
1.9. Variable pressure NMR : techniques andexamples
U. Frey, A. Merbach ρ 51
2. PhysicalChemistry
2.1. Spectroscopyinsupercritical fluids
M.W. George,S.M.Howdle, M. Poliakoffρ 59
2.2. Time­resolvedresonanceRaman spectroscopy in supercritical fluids
J. McGarvey,J.N.MartinHegarty, S.E.J. Bell, CG. Coates ρ 67
2.3. Energy vs volume of conformers : theoreticalinvestigation of their relative
contribution in the high pressure induced Michaeladditionof amine to
stereogenic crotonates
F. Dumas, C. Fressigné, J. Langlet, C. Giessner­Prettre ρ 71
2.4. Short­lived species in photochemical systemsgeneratingtransition metal
complex exciplexes
A. Horvath, L. Fodor, K.L. Stevenson ρ 75
VII 2.5. Photons applications in CO2
M.L. Viriot, M.C. Carré, S. Akhlus, C. Zetzl ρ 79
2.6. Sonoelectrochemistry : the effectsofultrasoundupon electroorganic synthetic
reactions and electropolymerisations
D.J. Walton, U. Geissler, S.S. Phull,T.J.Mason,J.P.Lorimer, C. Campbell, J. Evans
p83
2.7. Investigations on ultrasonic degradationofdextran in aqueous solutions :
preliminary results
S. Marsteau, A. Simon, A. Loge, Ν. Gondrexon, S. Taha, G. Dorange, C. Petrier ρ 87
2.8. Sonochemistry in aqueous media : effect of n-butanol and sucrose concentration
on hydrogen peroxide formation and phenol degradation
C. Petrier, Y. Jiang, D. Joannard, N. Monnier, S. Brochette, Y. Queneau, A. Bouchu,
G. Descotes ρ 91
3. ApplicationsinOrganic Chemistry
3.1.TheMichaelreaction using chiral imines under high pressure : easy access to
highlysubstitutedadducts
E.RolimdeOliveira,C. Miet, J. DAngelo, F. Dumas ρ 97
3.2. High pressure induced Wittig reactionofmonothioimides
E. Rolim de Oliveira, F. Dumas, J. DAngeloρ 101
3.3. High-pressure influence on selectivities in [4+2]cycloadditions of activated
dienes and bis-dienes.
A. Guillain, C. Martin, J. Maddaluno, L. Duhamel ρ 103
3.4. Spiroaziridine synthesis under highpressure
A.Yu. Rulev, J. Maddaluno, J.C. Plaquevent,L.Duhamelρ 107
3.5. The application of microwave irradiation tothesynthesis of [60] fullerene
derivatives
F. Langa, P. de la Cruz, A. de la Hoz, Ν. Martin ρ 111
3.6. Synthesis of 2-cyanobenzothiazoles,quinazolines,3,1-benzoxazines and 3,1-
benzothiazines from N-arylimino-l,2,3-dithiazolesunder microwave irradiation
V. Beneteau, T. Besson, M.J. Dozias,J.Guillard,P.Jacquault, C. Lamazzi, C.W.
Rees ρ 115
3.7.Ultrasound assisted reactions of organofluorine compounds
D.Peters,A.O. Miller, C. Zur, R. Miethchen ρ 119
3.8.Dehydration of 4-methyloxazole-5-carboxylicacidamide to 4-methyloxazole-5-
carbonitrile
F. Aquino, W. Bonrath, H. Paulingρ 123
VIII