Crown ethers and analogs

568 Pages·2016·9.98 MB·English

by  Patai S.

Crown Ethers and Analogs
Edited by Saul Patai and Zvi Rappoport
Copyright 0 1989 by John Wiley & Sons Ltd
Crown ethers and analogs
THE CHEMISTRY FUNCTIONAL GROUPS
OF
A series of advanced treatises under the general editorship of
Professor Saul Patai
The chemistry of alkenes (2 volumes)
The chemistry of the carbonyl group (2 volumes)
The chemistry of the ether linkage
The chemistry of the amino group
The chemistry of the nitro and nitroso groups (2 parts)
The chemistry of carboxylic acids and esters
The chemistry of the carbon-nitrogen double bond
The chemistry of amides
The chemistry of the cyano group
The chemistry of the hydroxyl group (2 parts)
The chemistry of the azido group
The chemistry of acyl halides
The chemistry of the carbon-halogen bond (2 parts)
The chemistry of the quinonoid compounds (2 volumes, 4 parts)
The chemistry of the thiol group (2 parts)
The chemistry of the hydrazo, azo and azoxy groups (2 parts)
The chemistry of amidines and imidates
The chemistry of cyanates and their thio derivatives (2 parts)
The chemistry of diazonium and diazo groups (2 parts)
The chemistry of the carbon-carbon triple bond (2 parts)
The chemistry of ketenes, allenes and related compounds (2 parts)
The Chemistry of the sulphonium group (2 volumes)
Supplement A: The chemistry of double-bonded functional groups (2 parts)
Supplement The chemistry of acid derivatives (2 parts)
B:
Supplement C: The chemistry of triple-bonded functional groups (2 parts)
Supplement D: The chemistry of halides, pseudo-halides and azides (2 parts)
Supplement E: The chemistry of ethers, crown ethers, hydroxyl groups and
their sulphur analogues (2 parts)
Supplement F: The chemistry of amino, nitroso and nitro compounds
and their derivatives (2 parts)
The chemistry of the metal-carbon bond (4 volumes)
The chemistry of peroxides
The chemistry of organic selenium and tellurium compounds (2 volumes)
The chemistry of the cyclopropyl group (2 parts)
The chemistry of sulphones and sulphoxides
The chemistry of organic silicon compounds (2 parts)
Updates
The chemistry of a-haloketones, a-haloaldehydes and a-haloimines
Nitrones, nitronates and nitroxides
Crown ethers and analogs
The formation of carbon-halogen bonds (in press)
Crown ethers and analogs
EDW IN WEBER
University of Bonn
JOHNL . TONER
Kodak Research, New York
ISRAELG OLDBERC
Tel Aviv University
FRITZV OGTLE
University of Bonn
DALEA . LAIDLER
ICI, Runcorn, Cheshire
J. FRASERST ODDART
University of Sheffield
RICHARDA . BARTSCH
Texas Technical University
CHARLELS. LIOTTA
Georgia Institute of Technology
Edited by
SAULP ATAaI nd Zvr RAPPOPORT
The Hebrew University of Jerusalem
Updates from the Chemistry of Functional Groups
1989
JOHN WILEY & SONS
CHICHESTER.NEW
YORK.BRISBANE.TORONTO.SINGAPORE
An Intersciences Publication
Copyright 0 1989 by John Wiley & Sons Ltd.
All rights reserved.
No part of this book may be reproduced by any means, or
transmitted, or translated into a machine language without
the written permission of the publisher
Library of Congress Cataloging-in-Publication Data:
Crown ethers and analogs
(Updates from the Chemistry of the functional groups)
'An Interscience publication.'
I. Ethers. I. Weber, Edwin. 11. Patai, Saul.
111. Rappoport, Zvi. IV. Series.
QD305.E7C76 1989 547.035 87-25350
ISBN 0 471 91707 9
British Library Cataloguing in Pubkcation Data:
Crown ethers and analogs-(Updates from the
chemistry of functional groups).
I. Ethers 2. Cyclic compounds
I. Weber, Edwin 11 Patai, Saul
111. Rappoport, Zvi IV. Series
547'.035 QD341.E7
ISBN 0 471 91707 9
Phototypesetting by Thomson Press (India) Ltd, New Delhi
Printed in Great Britain at The Bath Press, Avon
List of contributors
R. A. Bartsch Department of Chemistry and Biochemistry, Texas Technical
University, Box 4260, Lubbock, Texas 79409, USA.
I. Goldberg School of Chemistry, Tel Aviv University, Ramat Aviv 69978
Tel Aviv, Israel.
D. A. Laidler New Business Planning Group, ICI plc, P.O. Box 11, The Heath,
Runcorn, Cheshire WA7 4QE, UK.
C. L. Liotta School of Chemistry, Georgia Institute of Technology, Atlanta,
Georgia 30332, USA.
J. F. Stoddart Department of Chemistry, University of Shefield, Shefield S3
7HF, UK.
J. L. Toner Exploratory Sciences Division, Life Science Research Labora-
tories, Eastman Kodak Company, Kodak Park, Rochester, New
York 14650, USA.
F. Vogtle Institut fur Organische Chemie und Biochemie der Universitat,
Gerhard-Domagk-Strasse 1, D-5300 Bonn 1, RFG.
E. Weber Institut fur Organische Chemie und Biochemie der Universitat,
Gerhard-Domagk-Strasse 1, D-5300 Bonn 1, FRG.
Foreword
This is the third volume published in the new series entitled ‘Updates from the
Chemistry of the Functional Groups’.
The main volume on The ether linkage in the Functional Groups series appeared in
1967. This book did not even mention crown ethers, while Sgppfement E which appeared
in 1980 already contained three full chapters (a total 174 pages) on crown ethers, while a
fourth chapter also dealt mainly with the structural aspects of the same class of
compounds. Now, less than ten years after the appearance of Supplement E, the present
volume again contains a very substantial part describing material which was unknown or
at least unpublished ten years ago. Indeed, the four updated chapters in the present
volume deal not only with new material in the field of crown ethers, but with a variety of
analogous types of compounds which were developed and for which important new uses
were found only recently.
Chapters 1,2,4 and 6 were originally published in Supplement E (1980), while Chapter 8
is reprinted from Supplement C (1983). Chapters 7 and 9 are essentially updates of some of
the reprinted chapters although they too contain much novel material. Chapter 5 is
almost wholly devoted to new types of complexes and, finally, Chapter 3 is a review
emphasizing modern methods of molecular modelling as applied to host-guest chemistry.
As always, the editors will be grateful to readers who would call their attention to
mistakes or omissions in this volume as well as in other volumes of the series.
SAUL PATAI
ZVI RAPPOPORT
JERUSALEM
March 1989
vii
Contents
Synthesis of crown ethers and analogues
1
D. A. Laidler and J. F. Stoddart
Organic transformations mediated by macrocyclic multidentate ligands
59
C. L. Liotta
Modern aspects of host-guest chemistry: molecular modeling and conform-
ationally restricted hosts 11
J. L. Toner
Crown ethers-complexes and selectivity 201
F. Vogtle and E. Weber
New developments in crown ether chemistry: lariat, spherand and second-
sphere complexes
305
E. Weber
Geometry of the ether, sulphide and hydroxyl groups and structural chemistry
of macrocyclic and non-cyclic polyether compounds
35 9
I. Goldberg
Structural chemistry of crown ethers
399
1. Goldberg
Complexation of aryldiazonium ions by polyethers 477
R. A. Bartsch
Appendix to complexation of aryldiazonium ions by polyethers
505
R. A. Bartsch
Author index 519
Subject index 549
ix
Crown Ethers and Analogs
Edited by Saul Patai and Zvi Rappoport
Copyright 0 1989 by John Wiley & Sons Ltd
CHAPTER 1
Synthesis of crown ethers and
analogues
DALE A. LAIDLER and J. FRASER STODDART
New Business Planning Group, ICI pic, Runcorn, England and
University of Sheffield, England
I. HISTORICAL BACKGROUND . . 2
11. FACTORS INFLUENCING YIELDS IN SYNTHESIS . . 3
.
A. The Template Effect . 3
.
B. The Gauche Effect . 9
.
C. Other Effects , 1s
111. DESIGN AND STRATEGY .
. * 15
IV. SYNTHESES EXEMPLIFIED . * 16
A. M1. oAnollc-yocxlyicg eMn uslytsidteemntsa t.e Ligands *. 1176
2. All-nitrogen systems. . . 19
. .
3. All-sulphur systems 20
4. Oxygen and nitrogen systems . . 21
. .
5. Oxygen and sulphur systems 22
6. Nitrogen and sulphur systems . . 23
. .
7. Oxygen, nitrogen and sulphur systems 24
. .
B. Crown Compounds Incorporating Aromatic Residues 24
. .
1. Systems fused to benzene rings 24
. .
2. Systems fused to furan rings . . 27
3. Systems fused to pyridine rings 29
. .
4. Systems fused to thiophene rings 30
C. Macrocyclic Diester, Dithioester and Diamide Compounds . 31
. .
D. Crown Compounds Con.ta ining Carbonyl Groups 34
1. Oxocrownethers . 34
2. Crown ethers incorporating'p-dikeione re'sidues . 34
E. Crown Compounds Incorporating lmine and Oxime Functions . 36
1. Manocycles from Schiff-base condensations . . 36
2. Oxime linkages in macrocycles . . 38
F. Acyclic Crown Compounds . . 38
.
G. Macrobicyclic, Macrotricyclic and Macropolycyclic Ligands 40
1. Systems with nitrogen bridgeheads . . 40
2. Systems with carbon bridgeheads . . 43
3. A system with nitrogen and carbon bridgeheads. . . 43
1
2 Dale A. Laidler and J. Fraser Stoddart
.
H. Chiral Crown Ethers . . 44
1. Meso compounds and racemic modifications . . 44
2. Optically-active crown ethers from natural products . 47
3. Optically-active crown ethers from resolved precursors. . . 49
TOXICITY . . 51
V. AND HAZARDS
REFERENCES . . 52
VL
I. HISTORICAL BACKGROUND
It is interesting to reflect upon the fact that, although linear compounds containing
sequential ether have occupied an important position in chemistry for
many years, it is only during the last decade or so that macrocyclic polyethers and
their analogues have made their major impact upon the scientific community. Alas,
the fascinating complexing properties of macrocyclic polyethers were not antici-
pated from the comparatively mundane chemical behaviour of cyclic ethers
containing up to seven atoms in their rings4 . Indeed, often happens in science,
s5 as
serendipity played6 an important role in the discovery of the so-called crown ethers
and the appreciation of their somewhat intriguing characteristics. Although the
early literature was not devoid of reports on the synthesis of macrocyclic poly-
ethers, their value and potential was not realized by those involved. it is easy to feel
with hindsight that it should have been; but it is difficult to envisage how it could
have been!
The first macrocyclic polyethers were reported by Luttringhaus’ in 1937 as part
of an investigation of medium- and large-sized rings. For example, he obtained the
20-membered ring compound 1 in low yield after reaction of the monosubstituted
resorcinol derivative 2 with potassium carbonate in pentan-1-01. Later, the tetra-
furanyl derivative 3 was isolated* after acid-catalysed condensation of furan with
acetone and the cyclic tetramers 4 and 5 of ethylene9 and propyleneI0 oxides,
respectively, were reported.
(1)
(4) R = H
(5) R = Me
1. Synthesis of crown ethers and analogues 3
Several acyclic polyethers, as well as compound (S), were found' to dissolve
small quantities of potassium metal and sodium-potassium alloy giving unstable
blue solutions of solvated electrons and solvated cations. However, it was not until
1967 that Pedersen" reported on the formation of stable complexes between
macrocyclic polyethers and salts of alkali and alkaline earth metals. During an
attempted preparation of the diphenol from the dichloride 7 and the mono-
6
protected catechol derivative 8, the presence of 10% of catechol(9) as an impurity
led6 to the isolation (see Scheme 1) of the unexpected by-product which was
identified the macrocyclic polyether 10. Given the trivial name dibenzo-18-
as
crown-6 by Pedersed it was found to be insoluble in methanol by itself, but
v1 z,
became readily soluble on the addition of sodium salts. Furthermore, it was
obtained in 45% yield when pure catechol (9) was employed6 in its synthesis.
p1
(81 R =
(9) R = H (10% present as an impurity)
SCHEME 1
This amazingly yield for a macrocycle obtained on condensation of four
high
molecules raises questions of fundamental importance which will be discussed in
Section 11. Following upon initial discoveries, Pedersen' prepared more than
his
60 compounds in order to ascertain the optimum ring size and the preferred
constitutional arrangement of oxygen atoms in the macrocycles for them to
complex with a wide variety of cationic species. Those compounds which contain
between five and ten oxygen atoms, each separated from its nearest neighbour by
two carbon bridges, were found to be the most effective complexing agents. These
observations have led to the synthesis of many crown ethers and analogues. This
chapter is devoted to a review of the general principles and fundamental concepts
governing this kind of macrocyclic ring formation as well to a summary of the
as
methodology and reaction types employed in the synthesis of these macrocycles.
II. FACTORS INFLUENCING YIELDS IN SYNTHESIS
A. The Template Effect
The isolation of dibenzo-18-crown-6 (10) in 45% yield under the conditions
given in Scheme 1 prompted Pedersen6 to observe that 'the ring-closing step, either
by a second molecule of catechol or a second molecule of bis(2-chloroethyl) ether,