Download PDF
Synlett 2006(10): 1604-1606  
DOI: 10.1055/s-2006-944186
LETTER
© Georg Thieme Verlag Stuttgart · New York

Highly Efficient One-Pot Synthesis of Metalloporphyrazines under Mild Conditions

L. Giribabu*a, M. Chandrasekharama, S. Madan Mohana, Ch. Srinivasa Raoa, M. Lakshmi Kantama, M. Ramesh Reddyb, P. Yella Reddyb, Takeshi Torub
a Nanomaterials Laboratory, Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
e-Mail: giribabu@iict.res.in;
b Department of Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 446-8555, Japan
Further Information

Publication History

Received 14 March 2006
Publication Date:
26 June 2006 (online)

    Permissions and Reprints All articles of this category

Abstract

A novel single-step preparation of free-base and metalloporphyrazines from maleonitriles was accomplished for the first time by treatment with metal salts, hexamethyldisilazane (HMDS) and p-toluene sulfonic acid (PTSA) in DMF at 120 °C. This reaction provides a new preparative method under mild conditions for direct synthesis of metalloporphyrazines having a variety of metals and substituted maleonitriles.

Key words

macrocycles - porphyrazines - maleonitrile - template - hexamethyldisilazane

    References and Notes

  • 1a Suslick KS. Rakow NA. Kosal ME. Chou J. J. Porphyrins Phthalocyanines  2000,  4:  407 
    Google Scholar
  • 1b Li YJ. Fan Y. Zhang LG. Jiang DP. Lu AD. Wang S. Leblanc RM. J. Porphyrins Phthalocyanines  1998,  2:  527 
    Google Scholar
  • 1c Leznoff CC. Lever ABP. Phthalocyanines, Properties and Applications   Vol. 3:  VCH Publishers Inc; New York: 1993. 
    Google Scholar
  • 1d Schultz H. Lehmann H. Rein M. Hanack M. Struct. Bond. (Berlin)  1991,  74:  41 
    Google Scholar
  • 2a Drain CM. Hupp JT. Suslick KS. Wasielewski MR. Chen X. J. Porphyrins Phthalocyanines  2002,  6:  243 
    CrossrefGoogle Scholar
  • 2b Sauer T. Caseri W. Wegner G. Vogel A. Hoffmann B. J. Phys. D: Appl. Phys.  1990,  23:  79 
    CrossrefGoogle Scholar
  • 3a Rao SV. Rao DN. J. Porphyrins Phthalocyanines  2002,  6:  233 
    CrossrefGoogle Scholar
  • 3b Rao SV. Srinivas NNKM. Rao DN. Giribabu L. Maiya BG. Philip R. Kumar GR. Optics Commun.  2001,  192:  123 
    CrossrefGoogle Scholar
  • 3c Rao SV. Srinivas NNKM. Rao DN. Giribabu L. Maiya BG. Philip R. Kumar GR. Optics Commun.  2000,  182:  255 
    CrossrefGoogle Scholar
  • 4 Bonnet R. Chem. Soc. Rev.  1995,  24:  19 
    CrossrefGoogle Scholar
  • 5a Nazeeruddin MK. Humphry-Baker R. Officer DL. Campbell WM. Burrell AK. Gratzel M. Langmuir  2004,  20:  6515 
    CrossrefGoogle Scholar
  • 5b Campbell WM. Burrell AK. Officer DL. Jolley KW. Coord. Chem. Rev.  2004,  248:  1363 
    CrossrefGoogle Scholar
  • 5c Nazeeruddin MK. Humphry-Baker R. Gratzel M. Murrer BA. Chem. Commun.  1998,  719 
    CrossrefGoogle Scholar
  • 6 Linstead RP. Whalley M. J. Chem. Soc.  1952,  4839 
    Google Scholar
  • 7 Makarova EA. Korolyova GV. Luk’yanets EA. Zh. Obshch. Khim.  1999,  69:  1356 
    Google Scholar
  • 8 Donzello MP. Dini D. D’Arcangelo G. Ercolani C. Zhan R. Ou Z. Stuzhin PA. Kadish KM. J. Am. Chem. Soc.  2003,  125:  14190 
    CrossrefGoogle Scholar
  • 9a Vesper BJ. Salaita K. Zhong H. Mirkin CA. Barrett AGM. Hoffman BM. J. Am. Chem. Soc.  2004,  126:  16653 
    CrossrefGoogle Scholar
  • 9b Mitzel F. FitzGerald S. Beeby A. Faust R. Eur. J. Org. Chem.  2004,  1136 
    CrossrefGoogle Scholar
  • 9c Jaung JY. Bull. Korean Chem. Soc.  2004,  25:  1453 
    CrossrefGoogle Scholar
  • 9d Montalban AG. Baum SM. Barrett AGM. Hoffmann BM. J. Chem. Soc., Dalton Trans.  2003,  2093 
    CrossrefGoogle Scholar
  • 9e Goldberg DP. Michael SLJ. White AJP. Williams DJ. Barrett AGM. Hoffmann BM. Inorg. Chem.  1998,  37:  2100 
    CrossrefGoogle Scholar
  • 9f Nalwa HS. Engel MK. Hanack M. Pawlowski G. Appl. Phys. Lett.  1997,  71:  2070 
    CrossrefGoogle Scholar
  • 9g Gantchev TG. Ali H. vanLier JE. Eur. J. Biochem.  1993,  217:  371 
    CrossrefGoogle Scholar
  • 10a Uchida H. Tanaka H. Yoshiyama H. Reddy PY. Nakamura S. Toru T. Synlett  2002,  1649 
    CrossrefGoogle Scholar
  • 10b Uchida H. Reddy PY. Nakamura S. Toru T. J. Org. Chem.  2003,  68:  8736 
    CrossrefGoogle Scholar
  • 10c Uchida H. Yoshiyama H. Reddy PY. Nakamura S. Toru T. Bull. Chem. Soc. Jpn.  2004,  77:  1401 
    CrossrefGoogle Scholar
  • 11 With the HMDS method, 2,3-diphenylmaleonitrile (3) directly tetramerizes to the corresponding porphyrazine. The direct conversion was not possible in Mg-propoxide method, where the maleonitrile was first converted to the pyrrolinediimine before tetramerization. See: Gan Q. Xiong F. Li S. Wang S. Shen S. Xu H. Yang G. Inorg. Chem. Commun.  2005,  8:  285 
    CrossrefGoogle Scholar
  • 12 These five-membered aromatic maleonitriles are not converted directly to the corresponding porphyrazines. Indirect formation has been reported: Bauer EM. Ercolani C. Galli P. Popkova IA. Stuzhin PA. J. Porphyrins Phthalocyanines  1999,  3:  371 
    CrossrefGoogle Scholar
13

Representative Procedure.
Bis(dimethylamino)maleonitrile (328 mg, 2 mmol), HMDS (1.68 mL, 8 mmol), Zn(OAc)2 (220 mg, 1 mmol), PTSA (38 mg, 0.2 mmol) and DMF (1 mL) were taken in a sealed tube. The reaction mixture was heated at 120 °C for 24 h under Ar atmosphere. The reaction mixture was then evaporated to dryness under reduced pressure. The resultant solid material was subjected to neutral alumina column and eluted with hexane-EtOAc (9:1). The front running blue color band was collected and evaporated to dryness under reduced pressure to get Zn-porphyrazine 2b (160 mg) in 43%. Anal. Calcd: C, 53.22; H, 6.70; N, 31.03. Found: C, 53.70; H, 6.65; N, 31.30. UV/Vis (CH2Cl2): λmax (log e) = 630 (4.27), 545 (sh), 330 (4.72) nm. 1H NMR (CDCl3): δ = 3.70 (s) ppm. 13C NMR (CDCl3): δ = 43.8, 137.7, 150.7 ppm. MS (MALDI-TOF): m/z = 722. All the compounds obtained are known and in agreement with the reported spectral and analytical data.