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Synthesis 2008(18): 2968-2976  
DOI: 10.1055/s-2008-1067250
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Convenient Preparation of C-Silylated Calixarenes

Paul F. Hudrlik*, Anne M. Hudrlik, Wondwossen D. Arasho, Raymond J. Butcher
Department of Chemistry, Howard University, Washington, DC 20059, USA
Fax: +1(202)8065442; e-Mail: phudrlik@howard.edu;
Further Information

Publication History

Received 20 March 2008
Publication Date:
04 September 2008 (online)

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Abstract

Calix[4]arenes having multiple silyl groups on the upper (wide) rim were prepared from the corresponding bromocalixarenes by halogen-metal exchange with t-BuLi followed by silylation. The best results were obtained using the clear supernatant from a mixture of chlorosilane and triethylamine. With the higher molecular weight chlorosilanes, an aqueous workup was replaced by a filtration through a column of silica gel. p-(Trimethylsilyl)calixarene 17, the silicon analogue of the well-studied p-tert-butylcalixarene 1, formed a crystalline complex with toluene having a toluene molecule in the cone cavity with the toluene methyl protruding out at an angle.

Key words

calixarenes - silicon - halogen-metal exchange

    References

  • 1a Gutsche CD. Calixarenes, In Monographs in Supramolecular Chemistry   Stoddart JF. The Royal Society of Chemistry; London: 1989. 
    Google Scholar
  • 1b Böhmer V. Angew. Chem., Int. Ed. Engl.  1995,  34:  713 
    Google Scholar
  • 1c Gutsche CD. Calixarenes Revisited, In Monographs in Supramolecular Chemistry   Stoddart JF. The Royal Society of Chemistry; London: 1998. 
    Google Scholar
  • 1d Calixarenes in Action   Mandolini L. Ungaro R. Imperial College Press; London: 2000. 
    Google Scholar
  • 1e Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht: 2001. 
    Google Scholar
  • 2a Chuit C. Corriu RJP. Reye C. Young JC. Chem. Rev.  1993,  93:  1371 
    Google Scholar
  • 2b Chuit C. Corriu RJP. Reye C. In Chemistry of Hypervalent Compounds   Akiba K. Wiley-VCH; New York: 1999.  p.81-146  
    Google Scholar
  • 2c Kira M. Zhang LC. In Chemistry of Hypervalent Compounds   Akiba K. Wiley-VCH; New York: 1999.  p.147-169  
    Google Scholar
  • Recognition of anions:
  • 3a Beer PD. Gale PA. Angew. Chem. Int. Ed.  2001,  40:  486 
    Google Scholar
  • 3b Matthews SE. Beer PD. In Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht: 2001.  p.421-439  
    Google Scholar
  • 4 Blanda MT. Frels J. Lewicki J. Supramol. Chem.  1998,  9:  255 
    CrossrefGoogle Scholar
  • 5a

    Hudrlik, P. F.; Hudrlik, A. M.; Arasho, W. D.; Zhang, L.; Cho, J. Abstracts of Papers, 60th Southwest Regional Meeting of the American Chemical Society, Fort Worth TX, Sept 29-Oct 5, 2004; American Chemical Society: Washington DC, 2004, Abstract 301.

  • 5b Hudrlik PF. Arasho WD. Hudrlik AM. J. Org. Chem.  2007,  72:  8107 
    Google Scholar
  • 5c Hudrlik PF. Hudrlik AM. Zhang L. Arasho WD. Cho J. J. Org. Chem.  2007,  72:  7858 
    Google Scholar
  • 6 Billo F. Musau RM. Whiting A. ARKIVOC  2006,  (x):  199 
    Google Scholar
  • For examples, see:
  • 7a Shang S. Khasnis DV. Burton JM. Santini CJ. Fan M. Small AC. Lattman M. Organometallics  1994,  13:  5157 
    Google Scholar
  • 7b Neda I. Plinta H.-J. Sonnenburg R. Fischer A. Jones PG. Schmutzler R. Chem. Ber.  1995,  128:  267 
    Google Scholar
  • 7c Fan M. Zhang H. Lattman M. Organometallics  1996,  15:  5216 
    Google Scholar
  • 7d Martz J. Graf E. Hosseini MW. De Cian A. Fischer J. J. Mater. Chem.  1998,  8:  2331 
    Google Scholar
  • 7e Fan M. Shevchenko IV. Voorhies RH. Eckert SF. Zhang H. Lattman M. Inorg. Chem.  2000,  39:  4704 
    Google Scholar
  • 7f Anwander R. Eppinger J. Nagl I. Scherer W. Tafipolsky M. Sirsch P. Inorg. Chem.  2000,  39:  4713 
    Google Scholar
  • 7g Sood P. Zhang H. Lattman M. Organometallics  2002,  21:  4442 
    Google Scholar
  • 8a Wright A. J. Organomet. Chem.  1978,  145:  307 
    Google Scholar
  • 8b Olah GA. Bach T. Prakash GKS. J. Org. Chem.  1989,  54:  3770 
    Google Scholar
  • 8c Keay BA. In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations   Vol. 4:  Fleming I. Georg Thieme Verlag; Stuttgart: 2001.  p.685-712  
    Google Scholar
  • 9 Ihm H. Paek K. Bull. Korean Chem. Soc.  1995,  16:  71 
    Google Scholar
  • 10a Gutsche CD. Iqbal M. Org. Synth., Coll. Vol. 8   Wiley; New York: 1993.  p.75 
    Google Scholar
  • 10b Percec V. Bera TK. De B B. Sanai Y. Smith J. Holerca MN. Barboiu B. Grubbs RB. Fréchet JMJ. J. Org. Chem.  2001,  66:  2104 
    Google Scholar
  • 11 Arduini A. Casnati A. In Macrocycle Synthesis: A Practical Approach   Parker D. Oxford University Press; Oxford: 1996.  p.145-173  
    Google Scholar
  • 12 Gutsche CD. Lin L.-G. Tetrahedron  1986,  42:  1633 
    CrossrefGoogle Scholar
  • 13 G utsche CD. Dhawan B. Levine JA. No KH. Bauer LJ. Tetrahedron  1983,  39:  409 
    CrossrefGoogle Scholar
  • 14a Groenen LC. Ruël BHM. Casnati A. Timmerman P. Verboom W. Harkema S. Pochini A. Ungaro R. Reinhoudt DN. Tetrahedron Lett.  1991,  32:  2675 
    Google Scholar
  • 14b Gutsche CD. Reddy PA. J. Org. Chem.  1991,  56:  4783 
    Google Scholar
  • 15 Iwamoto K. Araki K. Shinkai S. J. Org. Chem.  1991,  56:  4955 
    CrossrefGoogle Scholar
  • 16 Larsen M. Jørgensen M. J. Org. Chem.  1996,  61:  6651 
    CrossrefPubMedGoogle Scholar
  • 17 Gutsche CD. Pagoria PF. J. Org. Chem.  1985,  50:  5795 
    CrossrefGoogle Scholar
  • 18 Conner M. Janout V. Regen SL. J. Org. Chem.  1992,  57:  3744 
    CrossrefGoogle Scholar
  • 19 van Loon J.-D. Arduini A. Coppi L. Verboom W. Pochini A. Ungaro R. Harkema S. Reinhoudt DN. J. Org. Chem.  1990,  55:  5639 
    Google Scholar
  • 20 Shimizu S. Moriyama A. Kito K. Sasaki Y. J. Org. Chem.  2003,  68:  2187 
    CrossrefPubMedGoogle Scholar
  • 21a For a recent example of halogen-metal exchange on a calixarene, see: Gagnon J. Vézina M. Drouin M. Harvey PD. Can. J. Chem.  2001,  79:  1439 
    Google Scholar
  • 21b

    See also references 9, 16, and 17.

  • 22a Arduini A. Fabbi M. Mantovani M. Mirone L. Pochini A. Secchi A. Ungaro R. J. Org. Chem.  1995,  60:  1454 
    Google Scholar
  • 22b Scheerder J. Vreekamp RH. Engbersen JFJ. Verboom W. van Duynhoven JPM. Reinhoudt DN. J. Org. Chem.  1996,  61:  3476  
    Google Scholar
  • 23a For many years we have used mixtures of Me3SiCl and Et3N to trap enolates to prepare silyl enol ethers: Hudrlik PF. Ph.D. Thesis   Columbia University; New York/ NY: 1968.  p.70 
    Google Scholar
  • 23b See also: Hudrlik PF. Organosilicon Compounds in Organic Synthesis, In New Applications of Organometallic Reagents in Organic Synthesis   Seyferth D. Elsevier; Amsterdam: 1976.  p.127-159  
    Google Scholar
  • 24 As expected, the excess t-BuLi appeared to have decomposed by the time of workup. For information on the stability of various alkyllithiums in common solvents, see: Clayden J. Organolithiums: Selectivity for Synthesis   Pergamon; Amsterdam: 2002.  p.5-7  
    Google Scholar
  • 26a Ungaro R. In Calixarenes in Action   Mandolini L. Ungaro R. Imperial College Press; London: 2000.  p.1-10  
    Google Scholar
  • 26b Jaime C. de Mendoza J. Prados P. Nieto PM. Sánchez C. J. Org. Chem.  1991,  56:  3372 
    Google Scholar
  • 27a Timko JM. Moore SS. Walba DM. Hiberty PC. Cram DJ. J. Am. Chem. Soc.  1977,  99:  4207 
    Google Scholar
  • 27b Ayling AJ. Broderick S. Clare JP. Davis AP. Pérez-Payán MN. Lahtinen M. Nissinen MJ. Rissanen K. Chem. Eur. J.  2002,  8:  2197 
    Google Scholar
  • 28a Kelly TR. Kim MH. J. Am. Chem. Soc.  1994,  116:  7072 
    Google Scholar
  • 28b Dicker IB. Cohen GM. Farnham WB. Hertler WR. Laganis ED. Sogah DY. Macromolecules  1990,  23:  4034 
    Google Scholar
  • 29a The apparent pK a (first proton) of 1 in THF was found to be 4.11, while that of the tetrakis(tert-butyl) analogue of 25 to be 12.2: Araki K. Iwamoto K. Shinkai S. Matsuda T. Bull. Chem. Soc. Jpn.  1990,  63:  3480 
    Google Scholar
  • 29b See also: Cunningham ID. Woolfall M. J. Org. Chem.  2005,  70:  9248 
    Google Scholar
  • 30a Andreetti GD. Ungaro R. Pochini A. J. Chem. Soc., Chem. Commun.  1979,  1005 
    Google Scholar
  • 30b Brouwer EB. Enright GD. Ratcliffe CI. Ripmeester JA. Supramol. Chem.  1996,  7:  79 ; Chem. Abstr. 1997, 126, 317157
    Google Scholar
  • 30c Arduini A. Caciuffo R. Geremia S. Ferrero C. Ugozzoli F. Zontone F. Supramol. Chem.  1998,  10:  125 ; Chem. Abstr. 1999, 130, 146515
    Google Scholar
  • 30d Brouwer EB. Ripmeester JA. Adv. Supramol. Chem.  1999,  5:  121 
    Google Scholar
  • 30e Enright GD. Brouwer EB. Udachin KA. Ratcliffe CI. Ripmeester JA. Acta Cryst.  2002,  B58:  1032 
    Google Scholar
  • 30f Atwood JL. Barbour LJ. Jerga A. Schottel BL. Science  2002,  298:  1000 
    Google Scholar
  • 31a Gutsche CD. Calixarenes Revisited, In Monographs in Supramolecular Chemistry   Stoddart JF. The Royal Society of Chemistry; London: 1998.  p.169 
    Google Scholar
  • 31b Brouwer EB. Ripmeester JA. Adv. Supramol. Chem.  1999,  5:  128 
    Google Scholar
  • 32 Gardiner MG. Koutsantonis GA. Lawrence SM. Nichols PJ. Raston CL. Chem. Commun.  1996,  2035 
    CrossrefGoogle Scholar
  • For examples, see: refs 30d, 32, and:
  • 33a Olmstead MM. Sigel G. Hope H. Xu X. Power PP. J. Am. Chem. Soc.  1985,  107:  8087 
    Google Scholar
  • 33b Bott SG. Coleman AW. Atwood JL. J. Am. Chem. Soc.  1986,  108:  1709 
    Google Scholar
  • 33c Giannini L. Caselli A. Solari E. Floriani C. Chiesi-Villa A. Rizzoli C. Re N. Sgamellotti A. J. Am. Chem. Soc.  1997,  119:  9709 
    Google Scholar
  • 33d Zanotti-Gerosa A. Solari E. Giannini L. Floriani C. Re N. Chiesi-Villa A. Rizzoli C. Inorg. Chim. Acta  1998,  270:  298 
    Google Scholar
  • 33e Guillemot G. Solari E. Floriani C. Rizzoli C. Organometallics  2001,  20:  607 
    Google Scholar
  • 34 Andreetti GD. Pochini A. Ungaro R. J. Chem. Soc., Perkin Trans. 2  1983,  1773 
    Google Scholar
  • 35 Ohtsuchi M. Suzuki K. Armah AE. Yamagata Y. Fujii S. Tomita K. Asfari Z. Vicens J. Acta Crystallogr.  1993,  C49:  639 
    Google Scholar
  • 37a Sakurai H. Ebata K. Kabuto C. Sekiguchi A. J. Am. Chem. Soc.  1990,  112:  1799 
    Google Scholar
  • 37b Yamakawa T. Kagechika H. Kawachi E. Hashimoto Y. Shudo K. J. Med. Chem.  1990,  33:  1430 
    Google Scholar
  • 37c Rim C. Son DY. Org. Lett.  2003,  5:  3443 
    Google Scholar
  • 37d Beckmann J. Duthie A. Reeske G. Schürmann M. Organometallics  2004,  23:  4630 
    Google Scholar
  • 38a Kim C. Jung I. J. Organomet. Chem.  2000,  599:  208 
    Google Scholar
  • 38b Meijboom R. Hutton AT. Moss JR. Organometallics  2003,  22:  1811 
    Google Scholar
  • 38c Itami Y. Marciniec B. Majchrzak M. Kubicki M. Organometallics  2003,  22:  1835 
    Google Scholar
  • 38d See also: Rim C. Son DY. Macromolecules  2003,  36:  5580 
    Google Scholar
  • 39 Moores A. Defieber C. Mézailles N. Maigrot N. Ricard L. Le Floch P. New J. Chem.  2003,  27:  994 
    CrossrefGoogle Scholar
25

The cone assignments were confirmed by the appearance of ArCH 2Ar in the ¹H NMR spectra¹³,²6a (one pair of doublets at δ = 4.0-4.5 and 2.8-3.6; J = 13-14 Hz), and the position of the ArCH2Ar (δ = 31-32) in the ¹³C NMR spectra.²6

36

Crystallographic data (excluding structure factors) for the structure in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 658532. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.ac.UK).