Calix[4]arenes
Substituted on the Narrow Rim with Malononitrile and Cobalt Bis(dicarbollide)
Anion
Junmei Zhaoa, Michael Bolteb, Crenguţa Dordeaa, Bohumir Grünerc, Volker Böhmer*a a Abteilung Lehramt Chemie, Fachbereich Chemie,
Pharmazie und Geowissenschaften, Johannes
Gutenberg-Universität Mainz, Duesbergweg
10-14, 55099 Mainz, Germany Fax: +49(6131)3925419; e-Mail: vboehmer@mail.uni-mainz.de; b Fachbereich Chemie und Pharmazeutische Wissenschaften,
Institut für Anorganische Chemie, Johann
Wolfgang Goethe-Universität, Max-von-Laue-Str.
7, 60438 Frankfurt/Main, Germany c Institute of Inorganic Chemistry, AS ČR, Area of Research Institutes
1001, 25068 Husinec-Øe˛, Czech Republic
Weitere Informationen
Publikationsverlauf
Received
26 May 2009 Publikationsdatum: 19. Oktober 2009 (online)
Nitrile groups are suitable precursors for amino functions to
which various other groups can be attached. Thus, the reaction of
the 1,3-bis(3-bromopropyl ether) or 1,3-bis(4-bromobutyl ether)
of tert-butylcalix[4]arene
with methylmalononitrile has been studied in order to attach four
nitrile groups to the narrow rim. Bimacrocyclic dinitriles were
formed in 70% yield with malononitrile, and tetranitriles
in 85% yield with methylmalononitrile. Subsequent alkylation
of the tetranitriles with cobalt dioxane-bis(dicarbollide) gave
dianionic calix[4]arenes, isolated as the cesium
salts in 68% and 89% yield. Two compounds were
characterized by single crystal X-ray analysis.
1aCalixarenes
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Böhmer V.
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1bBöhmer V.
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Wiley & Sons;
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Grüttner C.
Jakobi RA.
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Saadioui M.
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3aBarboso S.
Garcia Carrera A.
Matthews SE.
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Böhmer V.
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Rouquette H.
Schwing-Weill M.-J.
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1999,
719
3bCasnati A.
Fontanella M.
Sansone F.
Ungaro R.
Böhmer V.
Saadioui M.
Liger K.
Dozol J.-F.
Tetrahedron
2006,
62:
6749
5Mikulášek L.
Grüner B.
Dordea C.
Rudzevich V.
Böhmer V.
Haddaoui J.
Hubscher-Bruder V.
Arnaud-Neu F.
Čáslavský J.
Selucký P.
Eur.
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4772
7 Dendritic octa-CMPO derivatives of
calix[4]arenes with nitrogen atoms as branching
points showed only weak extractabilities, probably due to a protonation
of the tertiary amines in acidic media; see: Wang P.
Saadioui M.
Schmidt C.
Böhmer V.
Host V.
Desreux JF.
Dozol
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2004,
60:
2509
A reaction of 5b with
malononitrile in THF at -78 ˚C using LDA
as base led to a complicated mixture from which the expected tetranitrile
could be isolated in 12% yield.
Crystal data for 6a:
C53H66N2O4×2MeCN, M = 877.19, monoclinic, a = 13.8422(4) Å, b = 18.3275(6) Å, c = 42.7189(11) Å, β = 97.642(2)˚, V = 10741.2(5) ų, T = 173(2)
K, space group P21/c, Z = 8, µ(Mo Kα) = 0.068 mm-¹,
95208 reflections measured, 19962 unique reflections which were
used in all calculations. The final wR(F²)[I > 2σ(I)] was 0.2685. Crystallographic
data in CIF format have been deposited with the Cambridge Crystallographic
Data Centre, reference no. CCDC 642222, and can be obtained on application
to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(1223)336033;
E-mail: deposit@ccdc.cam.ac.uk.
Crystal data for 7a:
C58H72N4O4, M = 889.20,
triclinic, a = 10.3770(4) Å, b = 13.3048(6) Å, c = 20.2318(9) Å, α = 92.798(3)˚, β = 90.151(3)˚, γ = 93.368(3)˚, V = 2785.1 (2) ų, T = 173 (2)
K, space group P1, Z = 2, µ(Mo Kα) = 0.066
mm-¹, 77572 reflections measured, 11334
unique reflections which were used in all calculations. The final wR(F²)[I > 2σ(I)] was 0.1509. Crystallographic
data in CIF format have been deposited with the Cambridge Crystallographic
Data Centre, reference no. CCDC 642221.
