Synthesis 2018; 50(19): 3897-3901
DOI: 10.1055/s-0037-1609574
paper
© Georg Thieme Verlag Stuttgart · New York

An Expedient Synthesis of Ketocalix[6]arene Hexamethyl Ether

Norbert Itzhak
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel   Email: silvio.biali@mail.huji.ac.il
,
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel   Email: silvio.biali@mail.huji.ac.il
› Author Affiliations
This work was supported by Israel Science Foundation (ISF) (Grant No. 223/14).
Further Information

Publication History

Received: 28 May 2018

Accepted after revision: 12 June 2018

Publication Date:
05 July 2018 (eFirst)

Abstract

p-tert-Butylcalix[6]arene hexamethyl ether was oxidized in one step to the corresponding ketocalix[6]arene via photochemical bromination (100 W spot lamp) with NBS in a chloroform/water mixture. A pentamethyl ketocalix[6]arene derivative was obtained by reaction of the ketocalix[6]arene hexamethyl ether with boron tribromide dimethyl sulfide complex, and characterized by X-ray crystallography. In the presence of base, the compound undergoes an intramolecular nucleophilic aromatic substitution reaction.

Supporting Information

 
  • References

    • 2a Gutsche CD. Iqbal M. Org. Synth. 1989; 68: 234
    • 2b Gutsche CD. Dhawan B. Leonis M. Stewart D. Org. Synth. 1989; 68: 238
    • 2c Munch JH. Gutsche CD. Org. Synth. 1989; 68: 243

      See, for example:
    • 3a Morita Y. Agawa T. Kai Y. Kanehisa N. Kasai N. Nomura E. Taniguchi H. Chem. Lett. 1989; 1349
    • 3b Morita Y. Agawa T. Kai Y. Nomura E. Taniguchi H. J. Org. Chem. 1992; 57: 3658
    • 3c Reddy PA. Kashyap RP. Watson WH. Gutsche CD. Isr. J. Chem. 1992; 32: 89
    • 3d Casnati A. Comelli E. Fabbi M. Bocchi V. Mori G. Ugozzoli F. Lanfredi AM. M. Pochini A. Ungaro R. Recl. Trav. Chim. Pays-Bas 1993; 112: 384
    • 3e Reddy PA. Gutsche CD. J. Org. Chem. 1993; 58: 3245
  • 4 Troisi F. Mogavero L. Gaeta C. Gavuzzo E. Neri P. Org. Lett. 2007; 9: 915
    • 5a Neri P. Bottino A. Cunsolo F. Piattelli M. Gavuzzo E. Angew. Chem. Int. Ed. 1998; 37: 166
    • 5b Bottino A. Cunsolo F. Piattelli M. Garozzo D. Neri P. J. Org. Chem. 1999; 64: 8018
  • 6 For a review on spirodienone calixarene derivatives, see: Biali SE. Synlett 2003; 1

    • For reviews on methylene-functionalized calixarenes, see:
    • 7a Simaan S. Biali SE. J. Phys. Org. Chem. 2004; 17: 752
    • 7b Sliwa W. Deska M. ARKIVOC 2012; (i): 173
    • 7c Deska M. Dondela B. Sliwa W. ARKIVOC 2015; (i): 29
    • 7d Biali SE. In Calixarenes and Beyond . Neri P. Sessler JL. Wang MX. Springer; Berlin: 2016. Chap. 4
    • 8a Görmar G. Seiffarth K. Schultz M. Zimmerman J. Flämig G. Macromol. Chem. 1990; 191: 81

    • See also:
    • 8b Ninagawa A. Cho K. Matsuda H. Makromol. Chem. 1985; 186: 1379
    • 8c Ito K. Izawa S. Ohba T. Ohba Y. Sone T. Tetrahedron Lett. 1996; 37: 5959
    • 8d Matsuda K. Nakamura N. Takahashi K. Inoue K. Koga N. Iwamura H. J. Am. Chem. Soc. 1995; 117: 5550
    • 9a Seri N. Simaan S. Botoshansky M. Kaftory M. Biali SE. J. Org. Chem. 2003; 68: 7140
    • 9b Seri N. Thondorf I. Biali SE. J. Org. Chem. 2004; 69: 4774
    • 9c Kuno L. Seri N. Biali SE. Org. Lett. 2007; 9: 1577
    • 9d Kogan K. Biali SE. Org. Lett. 2007; 9: 2393
    • 9e Kuno L. Biali SE. J. Org. Chem. 2009; 74: 48
    • 9f Shalev O. Biali SE. J. Org. Chem. 2014; 79: 8584
    • 9g Itzhak N. Biali SE. Synthesis 2015; 47: 1678
  • 10 For a recent example of the selective oxygenation of the methylene groups of calixarenes yielding derivatives with methylene groups hydroxylated, see: Shalev O., Biali S. E.; Org. Lett.; 2018, 20: 2324.
    • 11a Andreetti GD. Ungaro R. Pochini A. J. Chem. Soc., Chem. Commun. 1979; 1005
    • 11b Gutsche CD. Bauer LJ. Tetrahedron Lett. 1981; 22: 4763
  • 12 Poms D. Itzhak N. Kuno L. Biali SE. J. Org. Chem. 2014; 79: 538
  • 13 Fischer C. Lin G. Seichter W. Weber E. Tetrahedron Lett. 2013; 54: 2187
  • 14 He C. Zhang X. Huang R. Pan J. Li J. Ling X. Xiong Y. Zhu X. Tetrahedron Lett. 2014; 55: 4458
  • 15 For a recent work on the transition-metal-free oxidation of diarylmethanes to benzophenones see: Li J.-S. Yang F. Yang Q. Li Z.-W. Chen G.-Q. Da Y.-D. Huang P.-M. Chen C. Zhang Y. Huang L.-Z. Synlett 2017; 28: 994
  • 16 Jaime C. de Mendoza J. Prados P. Nieto PM. Sanchez C. J. Org. Chem. 1991; 56: 3372
  • 17 Itzhak N. Biali SE. Eur. J. Org. Chem. 2015; 3221
  • 18 Gutsche CD. Dhawan B. Levine JA. No KH. Bauer LJ. Tetrahedron 1983; 39: 409
  • 19 CCDC 1845591 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.