Synthesis 2005(7): 1141-1147  
DOI: 10.1055/s-2005-861855
PAPER
© Georg Thieme Verlag Stuttgart · New York

Phthalocyanine Synthesis in Ionic Liquids: Preparation of Differently Substituted Phthalocyanines in Tetrabutylammonium Bromide

Pui-Chi Lo, Diana Y. Y. Cheng, Dennis K. P. Ng*
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong, P. R. China
Fax: +85226035057; e-Mail: dkpn@cuhk.edu.hk;
Further Information

Publication History

Received 24 November 2004
Publication Date:
10 March 2005 (eFirst)

Abstract

A series of alkylthio, alkoxy, and phenoxy phthalonitriles have been prepared by nucleophilic substitution reactions on suitable phthalonitrile precursors in molten tetrabutylammonium bromide. This readily available and inexpensive ionic liquid can also be used as a medium for the cyclization of these dinitriles giving the corresponding substituted phthalocyanines.

    References

  • 1a Phthalocyanines - Properties and Applications   Vol. 1-4:  Leznoff CC. Lever ABP. VCH; New York: 1989-1996. 
  • 1b McKeown NB. Phthalocyanine Materials: Synthesis, Structure and Function   Cambridge University Press; Cambridge: 1998. 
  • See for example:
  • 2a Perry JW. Mansour K. Lee I.-YS. Wu X.-L. Bedworth PV. Chen C.-T. Ng D. Marder SR. Miles P. Wada T. Tian M. Sasabe H. Science  1996,  273:  1533 
  • 2b Bao Z. Lovinger AJ. Dodabalapur A. Adv. Mater.  1997,  9:  42 
  • 2c Bao Z. Lovinger AJ. Brown J. J. Am. Chem. Soc.  1998,  120:  207 
  • 2d de la Torre G. Vázquez P. Agulló-López F. Torres T. J. Mater. Chem.  1998,  8:  1671 
  • 2e Crone B. Dodabalapur A. Lin Y.-Y. Filas RW. Bao Z. LaDuca A. Sarpeshkar R. Katz HE. Li W. Nature  2000,  403:  521 
  • 2f Schön JH. Kloc C. Bao Z. Batlogg B. Adv. Mater.  2000,  12:  1539 
  • 2g Dini D. Barthel M. Hanack M. Eur. J. Inorg. Chem.  2001,  3759 
  • See for example:
  • 3a Meunier B. Sorokin A. Acc. Chem. Res.  1997,  30:  470 
  • 3b Ito N. Etoh T. Hagiwara H. Kato M. Synthesis  1997,  153 
  • 3c Ravikanth M. Achim C. Tyhonas JS. Münck E. Lindsey JS. J. Porphyrins Phthalocyanines  1997,  1:  385 
  • 3d Oyaizu K. Haryono A. Natori J. Tsuchida E. J. Chem. Soc., Faraday Trans.  1998,  94:  3737 
  • 3e Bench BA. Brennessel WW. Lee H.-J. Gorun SM. Angew. Chem. Int. Ed.  2002,  41:  750 
  • 3f Tao X. Ma W. Zhang T. Zhao J. Chem. Eur. J.  2002,  8:  1321 
  • 4 Ali H. van Lier JE. Chem. Rev.  1999,  99:  2379 
  • 5 Erk P. Hengelsberg H. In The Porphyrin Handbook   Vol. 19:  Kadish KM. Smith KM. Guilard R. Academic Press; San Diego: 2003.  Chap. 119.
  • 6 Sharman WM. van Lier JE. In The Porphyrin Handbook   Vol. 15:  Kadish KM. Smith KM. Guilard R. Academic Press; San Diego: 2003.  Chap. 97.
  • 7a Maree MD. Nyokong T. J. Chem. Res., Synop.  2001,  68 
  • 7b Tolbin AY. Ivanov AV. Tomilova LG. Zefirov NS. J. Porphyrins Phthalocyanines  2003,  7:  162 
  • 7c Liu L.-C. Hu AT. J. Porphyrins Phthalocyanines  2003,  7:  565 
  • 8a Wöhrle D. Schmidt V. J. Chem. Soc., Dalton Trans.  1988,  549 
  • 8b Frick K. Ziener U. Hanack M. Eur. J. Inorg. Chem.  1999,  1309 
  • 8c Walsh CJ. Mandal BK. Chem. Mater.  2000,  12:  287 
  • 9a Welton T. Chem. Rev.  1999,  99:  2071 
  • 9b Wasser-scheid P. Keim W. Angew. Chem. Int. Ed.  2000,  39:  3772 
  • 9c Sheldon R. Chem. Commun.  2001,  2399 
  • 9d Dupont J. de Souza RF. Suarez PAZ. Chem. Rev.  2002,  102:  3667 
  • 9e Wasserscheid P. Welton T. Ionic Liquids in Synthesis   Wiley-VCH; Weinheim: 2003. 
  • 10a A room temperature phthalocyanine-based molten salt, however, has been reported: Dickinson E. Williams ME. Hendrickson SM. Masui H. Murray RW. J. Am. Chem. Soc.  1999,  121:  613 
  • 10b Catalytic oxidation of thiols by cobalt(II) phthalocyanines in ionic liquid has also been reported recently: Chauhan SMS. Kumar A. Srinivas KA. Chem. Commun.  2003,  2348 
  • 11a Kim DW. Song CE. Chi DY. J. Org. Chem.  2003,  68:  4281 
  • 11b Liu Z. Chen Z.-C. Zheng Q.-G. Synthesis  2004,  33 
  • 12a Gürol I. Ahsen V. Bekaroglu Ö. J. Chem. Soc., Dalton Trans.  1994,  497 
  • 12b Del Rey B. Keller U. Torres T. Rojo G. Agulló-López F. Nonell S. Martí C. Brasselet S. Ledoux I. Zyss J. J. Am. Chem. Soc.  1998,  120:  12808 
  • 13 In a study of conjugate addition of thiols to electron deficient alkenes in molten Bu4NBr, Ranu et al. have suggested that the bromide ions form hydrogen bondings with the thiols, leading to an increase in their nucleophilicity: Ranu BC. Dey SS. Hajra A. Tetrahedron  2003,  59:  2417 
  • See for example:
  • 14a Siegl WO. J. Heterocycl. Chem.  1981,  18:  1613 
  • 14b Wöhrle D. Eskes M. Shigehara K. Yamada A. Synthesis  1993,  194 
  • 14c Eberhardt W. Hanack M. Synthesis  1997,  95 
  • 14d Liu W. Lee C.-H. Chan H.-S. Mak TCW. Ng DKP. Eur. J. Inorg. Chem.  2004,  286 
  • 15a Wöhrle D. Schnurpfeil G. Knothe G. Dyes Pigments  1992,  18:  91 
  • 15b Gürek AG. Bekaroglu Ö. J. Chem. Soc., Dalton Trans.  1994,  1419 
  • 15c Lee C.-H. Ng DKP. Tetrahedron Lett.  2002,  43:  4211 
  • 16 Choi MTM. Li PPS. Ng DKP. Tetrahedron  2000,  56:  3881 
  • The following compounds have been described previously. See:
  • 17a

    For 2a and 2e: Ref. 12b.

  • 17b

    For 2b and 3b: Ref. 12a.

  • 17c Torres Cebada T, Sastre Santos A, and Del Rey Alvarez B. inventors; Spanish Patent ES  2116867. For 2c and 3c: 1998; Chem. Abstr. 1999, 130, 261059
  • 17d Taniguchi M, Narizuka T, and Tomita H. inventors; Jpn. Kokai Tokkyo Koho JP  08269004. For 2d: 1996; Chem. Abstr. 1997, 126, 46981
  • 17e Duggan PJ, and Gordon PF. inventors; Eur. Pat. Appl. EP  155780. For 2f: 1985; Chem. Abstr. 1986, 105, 70242
  • 17f Yamada A, Shigehara J, Kurata R, and Hikosaka M. inventors; Jpn. Kokai Tokkyo Koho JP  61207365. For 2g: 1986; Chem. Abstr. 1987, 106, 32617
  • 17g

    For 2i: Ref. 14b.

  • 17h For 2j: Cook MJ. Dunn AJ. Howe SD. Thomson AJ. Harrison KJ. J. Chem. Soc., Perkin Trans. 1  1988,  2453 
  • 17i For 3a: Suda Y. Shigehara K. Yamada A. Matsuda H. Okada S. Masaki A. Nakanishi H. Proc. SPIE-Int. Soc. Opt. Eng.  1991,  1560:  75 
  • 17j For 3d: Shigehara K. Takizawa M. Takeda K. Synth. Met.  1995,  71:  2303 
  • 17k For 3e and 4d: Eichhorn H. Wöhrle D. Pressner D. Liq. Cryst.  1997,  22:  643 
  • 17l Ozawa H, and Oshima K. inventors; Jpn. Kokai Tokkyo Koho JP  62139157. For 3f: 1987; Chem. Abstr. 1988, 108, 66063
  • 17m

    For 3g: Ref. 15c.

  • 17n

    For 4b: Ref. 16.

  • 17o For 4c: Ozoemena K. Westbroek P. Nyokong T. Electrochem. Commun.  2001,  3:  529 
  • 17p For 4e: Nicolau M. del Rey B. Torres T. Mingotaud C. Delhaes P. Cook MJ. Thorpe SC. Synth. Met.  1999,  102:  1462