Abstract
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
C.D. Gutsche: Calixarenes, The Royal Society of Chemistry, Cambridge, UK (1989), pp. 149-185.
C.D. Gutsche, B. Dhawan, J. A. Levine, K.H. No, and L.J. Bauer: Tetrahedron 39, 409 (1983).
F.C.J.M. van Veggel: in L. Mandolini, R. Ungaro (eds.), Calixarenes in Action, Imperial College Press, London, UK (2000), pp. 11-84.
C.D. Gutsche and L.J. Bauer: Tetrahedron Lett. 48, 4763 (1981).
C.D. Gutsche: Calixarenes Revisited, The Royal Society of Chemistry, Cambridge, UK (1998), pp. 79-145.
M. Perrin and D. Oehler: in K. Vicens and V. Böhmer (eds.), Calixarenes: A Versatile Class of Macrocyclic Compounds, Kluwer Academic Publishers, Dordrecht (1991), pp. 65-85.
V. Böhmer: Angew. Chem. 107, 785 (1995); Angew. Chem. Int. Ed. Engl. 34, 713 (1995).
Calixarenes 2001, in Z. Asfari, V. Böhmer, J. M. Harrowfield, and J. Vicens (eds.), Kluwer Academic Publishers, Dordrecht (2001).
K. Iwamoto, K. Araki, and S. Shinkai: J. Org. Chem. 56, 4955 (1991).
K. Iwamoto and S. Shinkai: J. Org. Chem. 57, 7066 (1992).
R.M. Izatt, J.D. Lamb, R.T. Hawkins, P.R. Brown, S.R. Izatt, and J.J. Christensen: J. Am. Chem. Soc. 105, 1782 (1983).
A. Yamada, T. Murase, K. Kikukawa, T. Arimura, and S. Shinkai: J. Chem. Soc., Perkin Trans. 2, 793 (1991).
K. Iwamoto, K. Araki, and S. Shinkai: Tetrahedron 47, 4325 (1991).
J.-D. van Loon, A. Arduini, W. Verboom, R. Ungaro, G.J. van Hummel, S. Harkema, and D.N. Reinhoudt: Tetrahedron Lett. 30, 2681 (1989).
L.C. Groenen, B.H.M. Ruël, A. Casnati, P. Timmerman, W. Verboom, S. Harkema, A. Pochini, R. Ungaro, and D.N. Reinhoudt: Tetrahedron Lett. 32, 2675 (1991).
E.M. Collins, M.A. McKervey, E. Madigan, M.B. Moran, M. Owens, G. Ferguson, and S.J. Harris: J. Chem. Soc., Perkin Trans. 1, 3137 (1991).
A. Soi, W. Bauer, H. Mauser, C. Moll, F. Hampel, and A. Hirsch: J. Chem. Soc., Perkin Trans 2, 1471 (1998).
L.C. Groenen, J.-D. van Loon, W. Verboom, S. Harkema, A. Casnati, R. Ungaro, A. Pochini, F. Ugozzoli, and D.N. Reinhoudt: J. Am. Chem. Soc. 113, 2385 (1991).
D. Couton, M. Mocerino, C. Rapley, C. Kitamura, A. Yoneda, and M. Ouchi: Aust. J. Chem. 52, 227 (1999).
C.D. Gutsche and J.A. Levine: J. Am. Chem. Soc. 104, 2652 (1982).
J.-D. van Loon, A. Arduini, L. Coppi, W. Verboom, A. Pochini, R. Ungaro, S. Harkema, and D.N. Reinhoudt: J. Org. Chem. 55, 5639 (1990).
Z.-C. Ho, M.-C. Ku, C.-M. Shu, and L.-G. Lin: Tetrahedron 52, 13189 (1996).
E.M. Collins, M.A. McKervey, and S.J. Harris: J. Chem. Soc., Perkin Trans. 1, 372 (1989).
S.K. Sharma and C.D. Gutsche: Tetrahedron 50, 4087 (1994).
G.M. Sheldrick: SHELXS-97: Program for Crystal Structure Solution, University of Göttingen, Germany (1997).
G.M. Sheldrick: SHELXL-97: Program for the Refinement of Crystal Structures, University of Göttingen, Germany (1997).
G.D. Andreetti, R. Ungaro, and A. Pochini: J. Chem. Soc., Chem. Comm., 1005 (1979).
P.D.J. Grootenhuis, P. A. Kollman, L.C. Groenen, D.N. Reinhoudt, G.J. van Hummel, F. Ugozzoli, and G.D. Andreetti: J. Am. Chem. Soc. 112, 4165 (1990).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Stumpf, S., Goretzki, G., Gloe, K. et al. Solution and X-Ray Crystal Structures of the Di- and Tetra-allyl Ether of tert- utylcalix[4]arene. Journal of Inclusion Phenomena 45, 225–233 (2003). https://doi.org/10.1023/A:1024568408356
Issue Date:
DOI: https://doi.org/10.1023/A:1024568408356