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

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.

phthalonitriles - phthalocyanines - ionic liquids - nucleophilic substitution reactions

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: ; Chem. Abstr. 1999, 130, 261059

17d Taniguchi M, Narizuka T, and Tomita H. inventors; Jpn. Kokai Tokkyo Koho JP  08269004. For 2d: ; Chem. Abstr. 1997, 126, 46981

17e Duggan PJ, and Gordon PF. inventors; Eur. Pat. Appl. EP  155780. For 2f: ; Chem. Abstr. 1986, 105, 70242

17f Yamada A, Shigehara J, Kurata R, and Hikosaka M. inventors; Jpn. Kokai Tokkyo Koho JP  61207365. For 2g: ; 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: ; 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