Electrophilic Nitration of meso-Tetraarylporphyrin Complexes at the β-Pyrrolic Position

Abstract

The selective nitration of meso-tetraphenylporphyrin complexes is described. The reaction of the above porphyrinates with 25% HNO₃ or 5% HNO₃ at room temperature or 0-5 °C, respectively, results in the formation of the corresponding mono β-nitroporphyrins (56-81%), accompanied by small amounts of a mixture of β,β-dinitro by-products. The results described above are the first known examples of β-mononitration of meso-tetraarylporphyrin complexes under electrophilic conditions. Reactions with nickel(II), copper(II), and cobalt(II) porphyrinates are discussed.

Key words

porphyrin complexes - electrophilic aromatic nitration - dimerization

References

• 1a Hsi RA. Rosenthal DI. Glatstein E. Drugs  1999,  57:  725 
• 1b Sternberg ED. Dolphin D. Brückner C. Tetrahedron  1998,  54:  4151 
• 1c DeLaney TF. Glatstein E. Compr. Ther.  1988,  14:  43 
• 2 Clausen C. Gryko DT. Dabke RB. Dontha N. Bocian DF. Kuhr WG. Lindsey JS. J. Org. Chem.  2000,  65:  7363 ; and references cited therein
• 3a Imahori H. Hagiwara K. Aoki M. Akiyama T. Taniguchi S. Okada T. Shirakawa M. Sakata Y. J. Am. Chem. Soc.  1996,  118:  11771 
• 3b Cheng P. Wilson SR. Schuster DI. Chem. Commun.  1999,  89 
• 3c Zheng G. Dougherty TJ. Pandey RK. Chem. Commun.  1999,  2469 
• 3d Lee J.-C. Kim T.-Y. Kang SH. Shim YK. Bull. Korean Chem. Soc.  2001,  22:  257 
• 3e Ostrowski S. Mikus A. Mol. Divers.  2003,  6:  315 
• 4a Catalano MM. Crossley MJ. Harding MM. King LG. J. Chem. Soc., Chem. Commun.  1984,  1535 
• 4b Crossley JM. King LG. J. Org. Chem.  1993,  58:  4370 
• 4c Shea KM. Jaquinod L. Smith KM. J. Org. Chem.  1998,  63:  7013 
• 6a Alonso CAA. Neves MGPMS. Silva AMS. Cavaleiro JAS. Hombrecher HK. Tetrahedron Lett.  1997,  38:  2757 
• 6b Evans B. Smith KM. Cavaleiro JAS. J. Chem. Soc., Perkin Trans. 1  1978,  768 
• 7a Kruper WJ. Chamberlin TA. Kochanny M. J. Org. Chem.  1989,  54:  2753 
• 7b Meng GG. James BR. Skov KA. Can. J. Chem.  1994,  72:  1894 
• 7c Matthews SE. Pouton CW. Threadgill MD. J. Chem. Soc., Chem. Commun.  1995,  1809 
• 7d Faustino MAF. Neves MGPMS. Cavaleiro JAS. Neumann M. Brauer H.-D. Jori G. Photochem. Photobiol.  2000,  72:  217 
• 7e Ostrowski S. Shim YK. Bull. Korean Chem. Soc.  2002,  22:  9 
• 7f Ostrowski S. £opuszyñska B. Synth. Commun.  2003,  23:  4101 
• 7g Ostrowski S. Mikus A. £opuszyñska B. Tetrahedron  2004,  60:  11951 
• 8 Luguya R. Jaquinod L. Fronczek FR. Vicente MGH. Smith KM. Tetrahedron  2004,  60:  2757 
• 9 Dahal S. Krishnan V. Proc. Indian Acad. Sci., Chem. Sci.  1998,  110:  37 
• 10a Dahal S. Nethaji M. Krishnan V. Acta Crystallogr., Sect. C  1994,  50:  314 
• 10b Dahal S. Krishnan V. J. Photochem. Photobiol.  1995,  81:  105 
• 11 Dahal S. Krishnan V. Chem. Phys. Lett.  1997,  274:  390 
• 13 Inaba Y. Kobuke Y. Tetrahedron  2004,  60:  3097 ; and references cited therein
• 14 Fuhrhop J.-H. Smith KM. In Porphyrins and Metalloporphyrins   Smith KM. Elsevier; Amsterdam: 1975.  p.795-811  
• 16a Shine HJ. Padilla AG. Wu S.-M. J. Org. Chem.  1979,  54:  4069 
• 16b Malinovskii VL. Vodzinskii SV. Zhilina ZI. Andronati SA. Mazepa AV. Zh. Org. Khim.  1996,  32:  119 
• 17 Giraudeau A. Callot HJ. Jordan J. Ezhar I. Gross M. J. Am. Chem. Soc.  1979,  101:  3857 
• The demetallation of the complexes was carried out with the CF₃CO₂H-H₂SO₄ system; see:
• 18a Smith KM. Bisset GMF. Bushell MJ. J. Org. Chem.  1980,  45:  2218 
• 18b Ostrowski S. Mikus A. Shim YK. Lee J.-C. Seo E.-Y. Lee K.-I. Olejnik M. Heterocycles  2002,  57:  1615 

5

Aldrich Catalog 2003/2004; Cat. No 29,558-2: ca 450 g/365.30 ı.

12

The isomers, due to small amounts of the mixture, were not separated.

15

Prepared directly before reaction by diluting fuming yellow nitric acid (d = 1.53).