Industrial and Laboratory Nitrations

362 Pages·1976·4.91 MB·English

by  Lyle F. Albright and Carl Hanson (Eds.)

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76- Industrial and Laboratory
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
Industrial and Laboratory
Nitrations
Lyle F. Albright, EDITOR
Purdue University
Carl Hanson, EDITOR
1 University of Bradford, England
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k- A symposium sponsored by
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April 7-8, 1975.
22
ACS SYMPOSIUM SERIES
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1976
In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
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un Library of Congress CIP Data
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Date: Ind(uAsCtrSia ls yamndp olsaibuomra tsoerryie sn;i t2ra2ti oISnSs.N 0097-6156)
n Papers presented at a symposium held in Philadelphia,
o Apr. 7 and 8, 1975, as part of the 169th annual meeting
ati of the American Chemical Society, under the sponsorship
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bli of the Division of Industrial and Engineering Chemistry.
Pu Includes bibliographical references and index.

1. Nitration—Congresses. I. Albright, Lyle Frederick,
1921- II. Hanson, Carl. III. American Chemical
Society. Division of Industrial and Engineering Chemis
try. IV. Series: American Chemical Society. ACS sym
posium series; 22.
TP156.N5152 660.2'844'6 75-38712
ISBN 0-8412-0306-7 ACS MC8 22-1-357(1975)
Copyright © 1975
American Chemical Society
All Rights Reserved
PRINTED IN THE UNITED STATES OF AMERICA
In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
ACS Symposium Series
Robert F. Gould,
Series Editor
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
FOREWORD
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w The ACS SYMPOSIUM SERIES was founded in 1974 to provide
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6- format of the SERIES parallels that of its predecessor, ADVANCES
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19 IN CHEMISTRY SERIES, except that in order to save time the
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02 mitted by the authors in camera-ready form. As a further
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0. means of saving time, the papers are not edited or reviewed
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oi: except by the symposium chairman, who becomes editor of
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6 | the book. Papers published in the ACS SYMPOSIUM SERIES
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9 are original contributions not published elsewhere in whole or
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1, major part and include reports of research as well as reviews
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
PREFACE
his book contains the full manuscripts of the 23 papers presented
•*· during the symposium "Advances in Industrial and Laboratory Nitra
tions" held in Philadelphia on April 7 and 8, 1975, as part of the 169th
Annual Meeting of the American Chemical Society, under the sponsor
ship of the Division of Industrial and Engineering Chemistry. The Edi
tors had the honor of acting as cochairmen of the symposium. Publication
of the proceedings will make the papers available to an even wider audi
ence than the large and international one present in Philadelphia.
1 Why should a meeting on industrial nitration chemistry have been
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pr timely? Nitration, particularly of aromatic hydrocarbons, was one of the
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2 earliest unit processes to be operated on a large scale when the heavy
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6- organic chemical industry first developed last century. It has played an
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19 equally important part in the development of our present understanding
bk- of the mechanism of organic reactions, offering an ideal example of elec-
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2 trophilic substitution and being most elegantly researched during the
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0. 1940's and 1950s in the classic investigations of Professor C. K. Ingold
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oi: and his associates at University College, London (J. Chem. Soc. (Brit.)
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6 | 1950, 2400-2473; 1950, 2628-2684; 1952, 28-32; and 1958, 4357-4374).
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9 Despite a long history of industrial application and the extensive study
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1, of nitration mechanisms, many questions remain to be answered, and the
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un last decade has seen a resurgence of interest in the chemistry of the
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e: process, particularly under the conditions employed in industry.
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n Having worked together for a considerable number of years, we
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ati came to the conclusion that the time was ripe on both sides of the
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bli Atlantic Ocean for a major international meeting aimed at reviewing our
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engineers, from both industrial and academic establishments, who have
been working on the subject. The Philadelphia symposium was the result.
We were particularly concerned about providing a medium for inter
action among all scientists—of whatever discipline or employment—who
had something to offer toward a better understanding of nitration reac
tions under industrial conditions. There have been previous meetings
on nitrations, but we feel this to be the first at which such a wide spec
trum of sources was sought and obtained.
The first group of papers, Chapters 1-10 of this book, emphasize
various aspects of the chemistry and the mechanism of different nitra
tions. Information on side reactions, including oxidation, and on ipso
ix
In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
nitrations is discussed by several authors; such information should be
most helpful in clarifying certain features of the overall process. During
the symposium, the results of Ingold and associates were referred to on
numerous occasions; they had clearly shown that the nitronium ion,
N02+, is an excellent nitrating agent. They also indicated the nitro-
sonium ion, NO+, can be used in the nitration of easily nitratable aro-
matics including phenols or phenol ethers. Other ions which result in
nitrations have also now been reported in Chapter 1.
The second broad grouping of papers (Chapters 11-16) considers
both the chemistry and physical transfer steps between phases which
often occur during nitration. In aromatic nitrations using mixed acids,
for example, the presence of two immiscible liquid phases complicates
the nitration reaction. Agitation to emulsify the two phases is necessary
to obtain adequate contact between the hydrocarbon and the nitrating
01 species. Transfer of reactants and products, heat transfer, nature of
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pr emulsion, etc. are key factors.
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02 Chapters 17-24 consider various aspects of plant operation. Process
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6- improvements, safety features, and new processes are discussed; in several
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1 cases nitration chemistry is also presented.
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1/b The present volume contains two papers in addition to those formally
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0 presented at the symposium. The first (Chapter 24) concerns develop
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10. ment of an industrial nitration plant employing injectors for mixing the
oi: liquid streams. While an offer of this paper was received prior to the sym
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19 program. Nevertheless, we feel it to be of interest and direct relevance
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e to the symposium and so have included it for the benefit of the reader.
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Ju The second paper (Chapter 25) is devoted to vapor phase nitrations and
ate: was presented at an earlier American Chemical Society meeting. Since
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n the papers presented at the symposium were concerned primarily with
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ati liquid phase processes, we thought that, because of their industrial im
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bli portance, vapor phase nitrations should be included also.
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In conclusion, we would like to thank all who made possible the sym
posium and this subsequent publication: firstly, the Division of Indus
trial and Engineering Chemistry for sponsorship; equally important, the
authors, without whom it could never have existed; and finally, those who
have worked behind the scenes, particularly our two secretaries, Mrs.
Diane Kneile (West Lafayette) and Mrs. P. A. Matthews (Bradford),
who have been burdened with considerably more than their normal duties
as a result.
LYLE F. ALBRIGHT CARL HANSON
West Lafayette, Ind. USA Bradford
October 1975 England
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
1
Preparative and Mechanistic Aspects of
Electrophilic Nitration
GEORGE A. OLAH
Case Western Reserve University, Cleveland, Ohio 44106
Electrophilic nitration of aromatics is the most studied,
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00 and supposedly best understood of organic reactions (1). Culmin
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c ating their work, Ingold, Hughes, and their associates in 1950
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2 published simultaneously a series of papers (2) which rightfully
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97 standing of electrophilic nitration reactions. Thus, not unex
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k- pectedly, for years following these publications the general view
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oi: the 1950's from a scientific point of view the study of nitration
76 | d Ilono kae dw alyik, en oa sg roenaete or f cothmep lmimoesntt uonfa ttthrea caticvheie vaenmde nintsa cotifv eI nagroeldas a.n d
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1 his group could have been made than the generally accepted view,
e 1, that their work indeed, completed what there was worthwhile to
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u study in nitration. Any further research, indeed, seemed to be
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Dat reviews in text books and scientific monographs.
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ati In 1975, a quarter of a century after the appearance of the
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bli Ingold papers, the field of electrophilic nitration, as testified
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interest and activity. This is the case both as far as the more
practical, preparative and technical aspects of nitration are
concerned, and equally so concerning the mechanistic and basic
aspects of the field. It is, of course, an old cliché to say
that each generation of chemists feels that their work is the
last word in their field, and nothing new ever will be added. I
for one, however, strongly feel that chemistry is certainly not a
closed-end chapter, and we are just starting to realize and ex
plore in many areas how limited our knowledge still is. The re
newed interest in nitration clearly testifies to this point. With
my group, we have had the good fortune to be able to contribute
something in the last two decases to rekindle interest in nitra
tion reactions. It is thus a great pleasure and privilege to be
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In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.
2 INDUSTRIAL AND LABORATORY NITRATIONS
able at this Symposium, to briefly summarize some of our own re
search and its more recent aspects, as well as to try at the end
of my lecture to indicate some of the areas where I think contin
ued work would promise significant new advances and results. It
certainly would be most fascinating to foresee what a future
symposium on nitration would present in another quarter of a
century, heralding in the new millennium. But, many of us may not
be around any more for the occasion. However, maybe some of the
younger generation will look up at the time the published volume
of this Meeting, and glancing over what we were interested in,
studying and projecting, compare it with the obviously vastly
more fundamental knowledge acquired by the year 2000. For the
record then let's try to give you a brief account of what I have
to present in 1975 with some comparison of where our knowledge
stood in 1950. I hope that the symposium of 2000 will look back
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00 at our present limited efforts with some degree of acknowledgment
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2 tinued progress of a clearly fascinating and very practical
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k- Preparative Aspects
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10 Nitration with Nitronium Salts (Olah-Kuhn Nitration). The
10. Ingold group (2) clarified the nature of the salt obtained by
oi: Hantsch (3) from nitric and perchloric acids as a mixture of nit
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7 prepared, and studied (by Raman spectroscopy) pure nitronium per
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1, 1 chlorate (2). This was a significant step, because even if in a
e separate system, but it directly proved the existence of the
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u nitronium ion suggested by their kinetic studies. Nitronium per
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cati morning shattered. This was very much the end of interest at
bli University College in what was considered an unstable, dangerous
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My own research work on electrophilic nitration, which star
ted in Hungary in the early 1950's, showed, however, that any
difficulty connected with nitronium perchlorate was not at all
the fault of the cation, but of the rather unsuitable perchlorate
anion. As it is well recognized now, perchlorate salts generally
are rather unstable and susceptible to explosive behavior because
of their ability to form covalent esters. In the case of nitron
ium perchlorate the isolated crystalline nitronium salt can form,
in equilibrium, small amounts of the covalent nitryl perchlorate
ester which then could be susceptible to explosive decomposition.
N0OCL0^=i NO+C10"
2 3 2 4
To prepare nitronium salts as stable nitrating reagents thus
In Industrial and Laboratory Nitrations; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1976.