Calixarenes 50th Anniversary: Commemorative Issue

407 Pages·1994·4.85 MB·English

by  Thomas Kappe (auth.)

CALIXARENES 50T H ANNIVERSARY:
COMMEMORATIVE ISSU E
Calixarenes 50th
Anniversary:
Commemorative
Issue
Edited by
J. VICENS, Z. ASFARI
Ecole Europeenne des Hautes
Etudes des Industries Chimiques
de Strasbourg (EHICS), France
and
J. M. HARROWFIELD
The University of Western
Australia, Perth, Australia
Reprinted from
Journal of Inclusion Phenomena and Molecular Recognition in Chemistry,
Volume 19, Nos. 1^(1994 )
SPRINGER SCIENCE+BUSINES S MEDIA , B.V.
Library of Congress Cataloging-in-Publication Data
Calixarene s 50t h anniversar y : commemorative issu e / edite d b y Jacque s
Vicens an d Zouhai r Asfar i an d Jac k McB. Harrowfie 1d.
p. cm .
Include s index .
ISBN 978-94-010-4118-8 ISBN 978-94-011-0267-4 (eBook)
DOI 10.1007/978-94-011-0267-4
1. Calixarenes . I . Vicens , J . II . Asfari, Zouhari .
III . Harrowfield , Jac k McB. IV . Title : Calixarene s fiftiet h
ann1versary .
QD341.P5C347 199 5
547* .632—dc2 0 95-400 9
ISBN 978-94-010-4118- 8
Printed on acid-free paper
All Rights Reserved
© 1994 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1994
Softcover reprint of the hardcover 1st edition 1994
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval system, without written permission from the copyright owner.
Table ofContents
Foreword
IntroducingPaper
T.KAPPE/TheEarlyHistoryofCalixareneChemistry 3
ReviewArticles
V.BOHMER,D.KRAFT,andM.TABATABAI/InherentlyChiralCalixarenes 17
Y. OKADA and J. NISHIMURA/ The Design ofCone-FixedCalix[4]areneAnalogs byTaking syn-
[2.n]MetacyclophanesasaBuildingBlock 41
P.E.GEORGHIOUandZ.LI/ConformationalPropertiesofCalix[4]naphthalenes 55
H.-J.SCHNEIDERandU.SCHNEIDER/TheHost-GuestChemistryofResorcinarenes 67
F.BOTTINOandS.PAPPALARDO/SynthesisandPropertiesofPyridinocalixarenes 85
D.M.ROUNDHILL,E.GEORGIEV,andA.YORDANOV/CalixareneswithNitrogenorPhosphorus
SubstituentsontheLowerRim lOl
G.BRODESSERandF.VOGTLE/HomocalixarenesandHomocalixpyridines 111
Z.ASFARI,S.WENGER,andJ.VICENS/CalixcrownsandRelatedMolecules 137
D.DIAMOND/Calixarene-BasedSensingAgents 149
GeneralPapers
P.TIMMERMAN,H.BOERRIGTER,W. VERBOOM,G.J.VANHUMMEL,S.HARKEMA,andD.
N. REINHOUDT / Proximally Functionalized Cavitands and Synthesis of a Flexible
Hemicarcerand 167
H. TAKEMURA, T. SHINMYOZU, H. MIURA, I. U. KHAN, and T. UNAZU / Synthesis and
PropertiesofN-SubstitutedAzacalix[n]arenes 193
J.A.WYTKOandJ.WEISS/ArrangingCoordinationSitesaroundCyclotriveratrylene 207
H. IKI, T. KIKUCHI, H. TSUZUKI, and S. SHINKAI / X-Ray Crystallographic Studies ofTricar
bonylchromium Complexes of Calix[4]arene Conformers on an Unusual Conformation
whichAppearsinConeConformers 227
O. ALEKSIUK, F. GRYNSZPAN, and S. E. BIALI / Preparation, Structure and Stereodynamics of
Phosphorus-BridgedCalixarenes 237
1. M. HARROWFIELD, W. R. RICHMOND, and A. N. SOBOLEV / Inclusion of Quaternary
AmmoniumCompoundsbyCalixarenes 257
W. XU, R. J. PUDDEPHATT, L. MANOJLOVIC-MUIR, K. W. MUIR, and C. S. FRAMPTON /
Calixarenes: Structure of an Acetonitrile Inclusion Complex and Some Metal Rimmed
Derivatives 277
Z. ASFARI, J.-P. ASTIER, C. BRESSOT, J. ESTIENNE, G. PEPE, and J. VICENS / Synthesis,
Characterization,andX-RayStructureof1,2-Bis-crown-5-calix[4]arene.ModelingofMetal
Complexation 291
T.SAWADA,A.TSUGE,T.THIEMANN,S.MATAKA,andM.TASHIRO/ComplexationProperties
andCharacterizationofFourConformersofa[2.1.2.I]Metacyclophane 30I
vi TABLEOFCONTENTS
T. YAMATO, M. YASUMATSU, Y. SARUWATARI,andL. K. DOAMEKPORISynthesisand Ion
SelectivityofMacrocyclicMetacyclophanesAnalogoustoSpherand-TypeCalixarenes 315
Y. SHIBUTANI, H. YOSHINAGA, K. YAKABE, T. SHONO, and M. TANAKA I Polymeric
MembraneSodium-SelectiveElectrodesBasedonCalix[4)areneIonophores 333
P. D. BEER,Z. CHEN,P. A. GALE, J. A. HEATH, R. J. KNUBLEY, M. I. OGDEN, and M. G. B.
DREW I Recognition by New Diester and Diamide-Calix[4)arene Diquininones and a
Diamide-Benzo-15-Crown-5Calix[4)arene 343
L.ZHANG,A.MACIAS,R.ISNIN,T.LU,G.W.GOKEL,andA.E.KAIFERITheComplexationof
FerroceneDerivativesbyaWater-SolubleCalix[6)arene 361
A.F.DANILDENAMOR,J.WANG,I.GOMEZORELLANA,F.J.SUEROSVELARDE,andD.A.
PACHECO TANAKA I Thermodynamic and Electrochemical Aspects of p-lert-butyl-
calix(n)arenes(n- 4,6,8)andTheirInteractionswithAmines 371
AdvancedMaterials
T.M.SWAGERandB.XUILiquidCrystallineCalixarenes 389
C. HILL,J.-P. DOZOL,V. LAMARE,H. ROUQUETTE.S. EYMARD,B. TOURNOIS,J.VICENS,
Z. ASFARI,C.BRESSOT,R.UNGARO,andA.CASNATIINuclearWasteTreatmentby
MeansofSupportedLiquidMembranesContainingCalixcrownCompounds 399
ConferenceDiary 409
AuthorIndex 411
SubjectIndex 415
JournalofInclusionPhenomenaandMolecularRecognitioninChemistry 19:1,1994. 1
©1994KluwerAcademicPublishers.
Foreword
This issue is to celebrate the 50th anniversary ofthe proposal of a macrocyclic
structure for the calixarenes. In February 1944, Zinke and Ziegler published an
article entitled: 'ZurKenntnis des Hartungsprozessesvon Phenol-Formaldehyde
Harzen' inChemischeBerichte,volume77,page264.Here,theyproposedacyclic
tetrameric structure (Cl1H140)4 for an oligomerextractedfrom the condensation
product mixtureobtainedbyreactingp-tert-butylphenolwithformaldehyde inthe
presenceofsodiumhydroxide.
OH H0
I I
A
/~
II n-CH2-11 ~Il
~/ ,,~
~(CH3J3 ~ J
ICH 1
33
CH H C
l2 2
f"lCH313 ICH3J3f
(
/~
II _11 I
,,..r--cH
2 ,,~
I I
OH HO
Fifty years on, calixarenes are the basis of many different areas ofchemical
research occurring at an increasing pace over the past decade in particular. The
presentvolume is not intendedto providean overview ofthe developmentsbutis
ratheracelebrationofsomeofthehighlights.Itishopedthatthisselectionfromthe
intricate mosaicofdiversity thatcharacterizescalixarenechemistry will stimulate
andfosterfurtherdevelopmentofthisfascinating field.
J. Vicens
Z. Asfari
J. Harrowfield
JournalofInclusionPhenomenaandMolecularRecognitioninChemistry 19:3-15,1994. 3
©1994KluwerAcademicPublishers.
The Early History of Calixarene Chemistry*
THOMAS KAPPE
InstituteofOrganicChemistry, Karl-Franzens-University,A-BOJOGraz, Austria
(Receivedinfinal form: 25May 1994)
Abstract.Thehistoryofcalixarenechemistryfromthemid-thirtiesuntil 1978isdescribed.
Keywords: Historyofchemistry,calixarenes,Zinke,Ziegler,H(jnel.
1. Introduction
Fifty years ago, in 1944,Alois Zinke andErich Zieglerpresentedthe constitution
(Figure 1) ofacyclictetramer, obtained intwo stepsfrom p-tert-butylphenol and
formaldehyde and which is calledtodayp-tert-butylcalix[4]arene, in Berichteder
Deutschen Chemischen Gesellschaft [1] and in a review [2]. They had already
described the synthesis ofthis compound (or was it the calix[8]arene?) in 1941
without, however, assigning a structure to it [3]. In 1941 they wrote: "Die erhal
tenen Produkte sind offenbar ziemlich hochmolekular, denn vorHiufige, mit dem
AcetylderivatausgefiihrteMolekulargewichtsbestimmungenergabeneinenDurch
schnittswert von 1725. Es durfte sich urn Verbindungen (oder ein Gemisch von
Verbindungen) handeln,dieausetwa8Butylphenolkernenaufgebautsind. Ather
artigeStrukturscheintnichtvorzuliegen,dennVersuche,eineSpaltungmitBrom
wasserstoff zu erreichen, verliefen negativ." According to presentknowledge [4,
5] it is very likely that Zinke and Ziegler indeed had the acetyl derivative ofthe
octamerat hand in 1941. But why did they propose the calix[4]arene structure in
1944 (without giving further experimental evidence for this conclusion)? Before
answering this question we should take a short look at the circumstances ofthe
discovery, the curricula vitae ofZinke and Ziegler, and ofa third person (whose
name has been mentioned in connection with calixarene chemistry so far only in
footnotes [6]): HerbertHonel.
2. People,Time,and Circumstances
Graz, the second-largestcity ofAustria, is locatedin the south-easternpartofthe
country,about50kmawayfromtheSlovenianandHungarianborders,respectively.
Since Graz is somewhat off the beaten track, the city is not so well known to
tourists as, for instance Vienna, Salzburg and Innsbruck. However, its university
* Thispaperisdedicatedtothecommemorativeissueonthe50thanniversaryofcalixarenes.
4 THOMASKAPPE
Fig. 1. Calix[4]areneasshowninRef.[1,2].
was founded more than 400years agoand five Nobel prize winners have worked
here. The names of Fritz Pregel (who developed the microanalysis of organic
compounds), Otto Loewi (the pharmacologist who discovered acetylcholine as a
neurotransmitter)andErwinSchrOdinger,thephysicist,shouldbefamiliartoevery
chemist.
Alois Zinke was born in 1892in the small villageofBambach, located 20km
westofGraz, where his father was adirectorofa glass factory. At the age often
he wassentto highschool('Landesoberrealschule')inGraz,andhestayedinthat
cityfortherestofhislife. Hecontinuedhisstudiesatthe 'TechnischeHochschule'
ofGraz, but after two years he changed to the University where he received his
Ph.D.in 1915underthetutelageofRolandScholl.Hewasassistantatthechemical
institute from 1914to 1922. In 1920he became 'Privat-Dozent' (unpaidlecturer)
in organic chemistry, and in 1922 he was appointed Professorat the 'Technische
Hochschule' in Graz, but only three years later he returned to the university as
'auBerordentlicherProfessor'. In 1941 hebecamefullprofessoranddirectorofthe
InstituteofOrganicandPharmaceuticalChemistryofthe University,apositionhe
helduntilhisdeath in 1963[7].
Zinke'scontributiontoorganicchemistryincluderesearchonnaturalresins,e.g.
theisolationofsiaresinolandsumaresinolacidswhichheshowedtobetriterpenes.
Most of his research, however, was devoted to highly condensed aromatic ring
systems (today called PAHs), particularly perylene. He became acquainted with
these ring systemsduring his workonalizarines withR. Scholl,and interestingly,
the last three papers he published in the 'sixties also dealt with 'perylene and its
derivatives', namely parts64-66ofthisseries.
However,forabouttwodecades- from1936to1956- Zinkedevotedalargepart
ofhisresearchtoexploringthechemistryofphenol-formaldehyderesinformation.
This excursion into a new field of research brought about - among many other
most valuableresults- the discoveryofcalix[n]arenes.We willcomebacktothis
THEEARLYHISTORYOFCALIXARENECHEMISTRY 5
point.
AloisZinke,1892-1963.
Erich Zieglerwas born in Marburg atthe river Drau in 1912. This city is located
70 km south ofGraz, and was incorporated into the territory ofYugoslavia after
the First World War in 1919. In 1923 the family moved to Graz. His father had
decidedthatErichZieglershouldbecomeadruggist, butduringhisapprenticeship
he was so much attracted by chemistry that in 1933 he enrolled for chemistry at
the university ofGraz. HejoinedZinke's groupjustatthe time when the phenol
formaldehyde project started. He obtained his Ph.D. in 1938 with a thesis on the
reactionproducts ofcresols with formaldehyde. He workedas an unpaidassistant
forZinkeuntilhe obtainedaformal appointmentin 1940.He wascalledupto the
army from August1939to February 1940,andagainfrom January 1942toMarch
1944.Thelast18monthsofthisperiodhespentin variousarmyhospitals,sincehe
hadbeenseriouslyinjuredduringthe warinRussia. Imentionthesecircumstances
alsoasoneexplanationofthelongintervalbetweenthefirstandsecondpublication
on cyclic phenol-formaldehyde products by Zinke and Ziegler, referred to in the
introduction.
Ziegler'sfurtheracademiccareerprogressedsmoothly: afterhisdismissalfrom
the army, he completedhis habilitation with his inaugurallecture as 'docent' (the
experimentalworkhadalreadybeencompletedbefore 1942).He workedforsome
timestillinthefieldofphenolicalcohols,andinvestigatedespeciallytheirreactions
witharomaticdiazoniumsalts.Intheearly'fiftieshisinterestturnedtoheterocyclic
6 THOMASKAPPE
chemistry (he published more than 200 papers in a series 'Synthesis of Hetero
cycles'), and made Graz a well-known centerofheterocyclic chemistry. In 1963,
afterthe death ofAlois Zinke, his mentor and finally his good friend, he became
full professoranddirectorofthe InstituteofOrganicChemistry.ZinkeandZiegler
had both planneda new building for the institute, butit was notbefore the spring
of 1969 thatit was ready for occupancy. Ten years later, Zieglerhad to retire for
healthreasons,butuntilabout1990hevisitedtheinstituteregularly, workedinthe
laboratory and published papers in his new fields ofinterest: the reactivity ofthe
C=N double bond, the chemistry of betaines, S- and N-ylids. He died on March
27, 1993[8].
ErichZiegler. 1912-1993.
WhileZinkehadneverheardaboutthefutureofhiscyclicphenol-formaldehyde
products, Zieglerwas informed about 'calixarenes' by Hermann Kammererfrom
Mainz, Germany. Ziegler had given a lecture in Mainz on February 4, 1954,
withthetitle 'UbercyclischePhenol-Formaldehyd-Kondensate' [9]. This wasata
time when he had already abandoned research in this area. Nevertheless, Ziegler
regularly received reprints ofKammerer's work in this field, and they exchanged
Christmaslettersforthe restofZiegler's life.
As indicated in the introduction, we must mention the name of a third person,