Phase-Transfer Catalysis. Mechanisms and Syntheses

308 Pages·1997·25.21 MB·English

by  Marc E. Halpern (Eds.)

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In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
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In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
659
ACS SYMPOSIUM SERIES
Phase-Transfer Catalysis
Mechanisms and Syntheses
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http://puebruary Developed from a symposium sponsored by the
009 | ate: F International Chemical Congress of Pacific Basin Societies at the
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American Chemical Society, Washington, DC
American Chemical Society
Library
1155 16th St., N.W.
In Phase-Transfer Catalysis; Halpern, M.;
ACS SymposiumW Saesrihesin; gAtmoneri,c Dan. CChe.m 2i0c0al3 S6o ciety: Washington, DC, 1997.
QD 505 .P488 1997 Copy 1
Phase-transfer catalysis
Library of Congress Cataloging-in-Publication Data
Phase-transfer catalysis: mechanisms and syntheses/ Marc E. Halpern,
editor.
p. cm.—(ACS symposium series, ISSN 0097-6156; 659)
"Developed from a symposium sponsored by the International
Chemical Congress of Pacific Basin Societies at the 1995 International
Chemical Congress of Pacific Basin Societies, Honolulu, Hawaii,
December 17-22, 1995."
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0 Includes bibliographical references and indexes.
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9.f ISBN 0-8412-3491-4
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7-0 1. Phase-transfer catalysis—Congresses.
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1 I. Halpern, Marc, 1954- . II. International Chemical Congress of
bk- Pacific Basin Societies (1995: Honolulu, Hawaii). III. Series
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02 QD505.P488 1996
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0. 547'.1395—dc21 96-49775
oi: 1 CIP
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In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
Foreword
THE ACS SYMPOSIUM SERIES was first published in 1974 to
provide a mechanism for publishing symposia quickly in book
form. The purpose of this series is to publish comprehensive
books developed from symposia, which are usually "snapshots
in time" of the current research being done on a topic, plus
1 some review material on the topic. For this reason, it is neces
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bs.ac1, 19 mendations of both the reviewers and the editors, prepare
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In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
Preface
CHARLES STARKS
predicted 10 years ago that a vast number of new
applications and more complex catalyst systems based on phase-transfer
catalysis (PTC) await discovery and exploitation. Starks made this predic
tion 10 years ago in his overview in ACS Symposium Series 326, Phase-
Transfer Catalysis: New Chemistry, Catalysts, and Applications. In his pre
1 face, Dr. Starks noted the exponential growth of PTC up to 1986. A
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pr decade has passed, and Dr. Starks's predictions have come true. The
9.
5 exponential growth of PTC continues in the laboratory synthesis and
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7- commercial manufacture of organic chemicals and polymers. This growth
9
9 appears to sustain itself as a result of strong fundamental driving forces
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bk- for high yield, short reaction time, replacement or elimination of solvent,
1/
2 and much more, all of which PTC provides. The driving forces of indus
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0. try in the mid-1990s coincide with the capabilities of PTC to deliver the
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org 7 | d This book documents the research of many top contributors to the
cs.99 growth of PTC. Tracking down and recruiting these scientists was no
a1
bs.1, easy task. Martin O'Donnell from Purdue University performed an out
2009 | http://puDate: February ssHaticuaaanmwddea,i miniu,gi pc D osaenenrc vedwimc hienbi cde(hruin svtt1rhe7isias-tli2 n 2Pbg,To oCt1kr 9u c9lo5iysm. embxTaeusmhneedipt ,yl as prabeytya k Ppoelarragcsnia fninrciinehzceginrm ugai ntte9hdd5e e bfiPfnyoT r CHtP) r osoyntfomoe lspustoholur e,
22, on O'Donnell and the papers presented addressed most of the major areas of
October Publicati PsyTnCth einsinso voatfi ono,r ginancliucd icnhge mmieccahlsa,n ismmos,d irfiecsaetaiorcnh gouf idpeloinlyems,e rcsh,i ratrl ipPhTaCsé,
catalysis, and new catalysts. Several chapters in this book are landmarks
in the field, including the chapters by Professor O'Donnell and coworkers.
Other chapters provide excellent and unique historical and scientific per
spective, particularly the mechanistic chapters in this book written by the
founders of PTC.
Acknowledgments
The credit for this book goes to the authors, who invested great effort
and elegant creativity; to Professor O'Donnell, who made it all happen;
xi
In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
and to the many reviewers, who executed the peer-review process with
dedication and effort.
MARC E. HALPERN
PTC Technology
1040 North Kings Highway
Suite 627
Cherry Hill, NJ 08034
September 4, 1996
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xii
In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
Chapter 1
Recent Trends in Industrial and Academic
Phase-Transfer Catalysis
Marc E. Halpern1
PTC Technology, 1040 North Kings Highway, Suite 627,
Cherry Hill, NJ 08034
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ch Phase-Transfer Catalysis ("PTC") continued to grow significantly
59. during the past decade. The driving forces for industrial and
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7-0 academic PTC research are stronger than ever. Even in light of the
99 impressive growth of PTC, much progress has yet to be made both
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k- in the fundamentals of PTC and its industrial application. Chemical
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1 prevention have much to gain by implementing PTC to reap great
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s.org 97 | d
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bs.a1, 1 The last ACS Symposium Series book published on the subject of phase-transfer
009 | http://puate: February cccahhtatteaaamnnlggypeesitsss ,ti ionn" Pt chtThheaCe rs ,at"cac httieeesr m iozafieb ct oahsuloe tmi naardet u odoseftfrc ytPah,dTe eCc ph. oarTonldgghre.ie ssDs psuai nrpoi enfar gPc raTetdhpCeirm seo siedvcnee tcrcsa h tdhaeeem ,n ioltcahnase-tlcr oredeme schepaaardvreceheh e wb naeshnieivlndee
2, 2n D stimulating thought about how PTC has or has not meshed with the needs of the
October 2Publicatio changinEgx eancvtliyro n1m0e yneta irns t haeg och, eDmri.c aCl hinadrluesst rSyt aanrkds ,a cwahdeom cioai.n ed the term "Phase-

Transfer Catalysis," wrote in the preface to ACS Symposium Series 326 on PTC
that in the previous 15 years PTC "expanded greatly." Dr. Starks estimated that the
"volume of phase-transfer catalysts totaled about 40,000 lb of catalysts per year in
1980 but grew to more than one million lbs of catalyst per year in 1985." In 1996,
there are several commercial processes which use approximately one million lbs per
year each of phase-transfer catalyst and I estimate that the non-captive market for
phase-transfer catalysts is over $25 million per year. I estimate that the number of
commercial PTC applications grew each year by 10-20%, although it should have
been growing even faster due to industry trends for process requirements
(described below). Ten years ago, Dr. Starks noted that Chemical Abstracts just
1E-mail address: [email protected]
© 1997 American Chemical Society
In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
2 PHASE-TRANSFER CATALYSIS
started to issue CA Selects - Phase-Transfer Catalysis, which has since been very
successful and useful to PTC chemists and casual PTC browsers. During the past
six years, specialized courses on industrial PTC have been offered and provided to
chemists at well over 100 companies and a new journal "Phase-Transfer Catalysis
Communications" was launched (1994) with 1200 subscribers and growing rapidly.
Today, you can search Phase-Transfer Catalysis on the Internet (which hardly
existed 10 years ago) and find references to the work of many of the authors in this
book (there is even one web site dedicated to PTC, which will seem trivial to a
reader of this book 10 years from now).
Indeed, PTC is alive, well and growing because it provides benefit to
chemists and engineers. Much has been written over the years about the multitude
of advantages which PTC offers,1'2 including increasing yield, reducing reaction
01 time and/or temperature, eliminating or solvent, using alternate raw materials,
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ch enhancing selectivity and safety and more. An informal non-scientific survey3 of
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5 chemists and engineers at 38 industrial sites in 1995/6 suggested that the primary
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7-0 driving force for considering PTC at the outset of a project is usually productivity
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9 and sometimes replacement or elimination of solvent. The most desired PTC
1
k- outcome in both lab and plant in 1985 was increasing or achieving high yield. In
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21/ 1996, this has been supplemented by PTC driving forces for reducing cycle time (to
0
1 squeeze more profit from a fixed plant) and eliminating, reducing or replacing
0.
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c9
http://pubs.aebruary 1, 1 toadhfese l oisyvreeeg trda rnuibinvceikn nnaegnof idwfto nprcio neclyos mmtahnepedre t lricaneobagnc sttaiiedoncenhdrsni n,o pgPlloTa tgnhCyta tii wsnP inT ltlohC te p ilrisnko eeabalpayrpb ltlfioyuca tubbarelsees .t u otroTtea hl sleutyh c aarhbet pi alli aatdynci oveotedhfr es bPeryT Ar Csaon CmgtSoee
009 | ate: F Symposium Series on PTC will be published within another decade.
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2o The key barriers to executing PTC projects are usually cited to be (1) lack
October Publicati roefa ctitmione otor pdroevceeslosp p/oapratimmeitzeers c hoor ic(2e) olafc cka otafl ycsotn, ficdaetnaclyes t( i.see.p, aerxaptieornti sea)n dth aott hthere
reaction or process (including related unit operations) will actually work. As a
general observation, it may be stated that deadlines and project overload are
responsible for an enormous amount of non-optimized processes being
commercialized, whether they involve PTC or not.
The economic conditions and massive R&D layoffs in the chemical industry
in the early 1990's have created very strong conflicting needs which are relevant to
PTC development. Chemists have always felt project pressures, however the
demands on chemists in the mid-1990's are quite different from the demands in the
mid-1980's. The number of R&D scientists and engineers in the US chemical
industry (non-pharmaceutical) dropped from 46,100 in 1990 to 41,200 in 1995.4 In
this work environment, chemists are required to develop much more cost efficient
manufacturing processes than ever and have less time and more workload than
In Phase-Transfer Catalysis; Halpern, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1997.