Synthesis, Table of Contents Synthesis 2018; 50(19): 3897-3901DOI: 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 , Silvio E. Biali * Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel Email: silvio.biali@mail.huji.ac.il › Author Affiliations Recommend Article Abstract Buy Article All articles of this category 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. Key words Key wordscalixarenes - bromine - cleavage - ether - oxidation - phenols Full Text References References For reviews on calixarenes, see: 1a Gutsche CD. Calixarenes: An Introduction . Royal Society of Chemistry; Cambridge: 2008. 2nd Ed. 1b Böhmer V. Angew. Chem., Int. Ed. Engl. 1995; 34: 713 1c Böhmer V. In The Chemistry of Phenols . Rappoport Z. Wiley; Chichester: 2003. Chap. 19 1d Calixarenes and Beyond . Neri P. Sessler JL. Wang MX. Springer; Berlin: 2016 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. Supplementary Material Supplementary Material Supporting Information
