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Mono-crowned substituded iron porphyrin: synthesis, analytical properties and catalytic activity

Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes, 3900, Ribeirão Preto 14040-901, São Paulo, Brasil

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Antonio G. Ferreira

Departamento de Química, Universidade Federal de São Carlos, Rodovia Washington Luis, Km 235, São Carlos 13595-905, São Paulo, Brasil

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Maria Carolina A. F. Gotardo

Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes, 3900, Ribeirão Preto 14040-901, São Paulo, Brasil

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, and

Marilda das Dores Assis

Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes, 3900, Ribeirão Preto 14040-901, São Paulo, Brasil

Corresponding author, fax: +55 16-6338151.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424605000745Cited by:2 (Source: Crossref)

Abstract

A substituted porphyrin bearing a crown ether unit, H₂(M18C6P), was synthesized from the reaction between (5-mono(o-aminophenyl)10,15,20-triphenylporphyrin) and the acyl derivative of the ether (4-carboxy-18-crown-6). The corresponding iron porphyrin, Fe(M18C6P)Cl, was obtained through iron insertion into H₂(M18C6P). The new free-base porphyrin was analyzed by C, N, and H elemental analysis, UV-vis and IR spectroscopies, electrospray mass spectrometry (MS) and ¹H NMR. It selectively extracts 18% of the K⁺ ions present in aqueous medium to the organic phase (chloroform). UV-vis spectroscopy studies showed that H₂(M18C6P) is also capable of forming aggregates with K⁺, probably the 1:1 complex, in methanol. This happens because the ionic radius of the potassium ion is appropriate for its accommodation inside the cavity of the crown ether, and also because of the associative effect between the porphyrin and the crown ether unit. The iron porphyrin Fe(M18C6P)Cl was used as catalyst for the epoxidation of cyclooctene by iodosylbenzene or sodium hypochlorite, in methanol or biphasic water/dichloroethane system, respectively. The results obtained with sodium hypochlorite show that Fe(M18C6P)Cl is a potential catalyst for selective oxidations, because the crown ether unit can select or orient substrates. This iron porphyrin can also be employed as a catalyst in a biphasic water/organic solvent system, with no need of a phase transfer agent.

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References

M. Biesaga, M. Pyrzynska and M. Trojanowicz, Talanta 51, 209 (2000), DOI: 10.1016/S0039-9140(99)00291-X. Crossref, Web of Science, Google Scholar
J. H. Chouet al., The Porphyrin Handbook 6, eds. K. M. Kadish, K. M. Smith and R. Guilard (Academic Press, Boston, MA, 2000) p. 43. Google Scholar
Many authors in ICPP-3 Abstract Book New Orleans (USA), published as J. Porphyrins Phthalocyanines 2004; 8(4-6) . Google Scholar
I. Gurol and V. Ahsen, J. Porphyrins Phthalocyanines 4, 620 (2000). Link, Web of Science, Google Scholar
M. Yoshio and H. Noguchi, Anal. Lett. 15, 1197 (1982). Crossref, Web of Science, Google Scholar
H. Shinmori and A. Osuka, Tetrahedron Lett. 41, 8527 (2000), DOI: 10.1016/S0040-4039(00)01544-6. Crossref, Web of Science, Google Scholar
K. M. Kadishet al., J. Porphyrins Phthalocyanines 4, 639 (2000). Link, Web of Science, Google Scholar
H. Xuet al., Mater. Sci. Technol. 10, 71 (1999). Web of Science, Google Scholar
L. Michaudet, P. Richard and B. Boitrel, Tetrahedron Lett. 41, 8289 (2000), DOI: 10.1016/S0040-4039(00)01462-3. Crossref, Web of Science, Google Scholar
H. Shinmori, H. Furuta and A. Osuka, Tetrahedron Lett. 43, 4881 (2002), DOI: 10.1016/S0040-4039(02)00832-8. Crossref, Web of Science, Google Scholar
C. Ruzie, L. Michaudet and B. Boitrel, Tetrahedron Lett. 43, 7423 (2002), DOI: 10.1016/S0040-4039(02)01659-3. Crossref, Web of Science, Google Scholar
X.-B. Shaoet al., Tetrahedron 59, 4881 (2003), DOI: 10.1016/S0040-4020(03)00702-6. Crossref, Web of Science, Google Scholar
E. J. Shin and H. S. Jung, J. Photoscience 11, 83 (2004). Google Scholar
C. Sirlinet al., Chem. Phys. Lett. 139, 362 (1987), DOI: 10.1016/0009-2614(87)80573-0. Crossref, Web of Science, Google Scholar
O. Bekaroglu, M. Kandaz and I. Yilmaz, Polyhedron 19, 115 (2000). Crossref, Web of Science, Google Scholar
S. Banfiet al., J. Mol. Catal. A: Chemical 113, 369 (1996), DOI: 10.1016/S1381-1169(96)00154-9. Crossref, Web of Science, Google Scholar
M. J. Gunteret al., J. Chem. Soc. Perkin Trans. 1 1945 (1998), DOI: 10.1039/a801302k. Google Scholar
J. G. Sharefkin and H. Saltzman, Org. Synthesis 5, 658 (1963). Google Scholar
A. D. Adler, F. R. Longo and J. D. Finarelli, J. Org. Chem. 32, 476 (1967), DOI: 10.1021/jo01288a053. Crossref, Web of Science, Google Scholar
J. P. Collmanet al., J. Am. Chem. Soc. 12, 102 (1980). Google Scholar
J. S. Lindseyet al., J. Org. Chem. 52, 827 (1987), DOI: 10.1021/jo00381a022. Crossref, Web of Science, Google Scholar
D. D. Perrin and W. L. F. Armarego, Purification of Laboratory Chemicals, 4th edn. (1997) p. 440. Google Scholar
A. H. Haines, I. Hodgkisson and C. Smith, J. Chem. Soc. Perkin Trans. 1 311 (1983), DOI: 10.1039/p19830000311. Google Scholar
J. Jones , Amino Acids and Peptide Synthesis , ed. S. G. Davies ( Oxford Science Publications , Oxford , 1992 ) . Crossref, Google Scholar
P. Kus, J. Planar Chromat. 9, 435 (1996). Web of Science, Google Scholar
M. D. Assis and J. R. S. Lindsay, J. Chem. Soc., Perkin Trans. 2 2221 (1998). Google Scholar
K. Yujiet al., Tetraedron Lett. 40, 6019 (1999). Web of Science, Google Scholar
J. W. Steed, Coord. Chem. Rev. 215, 171 (2000), DOI: 10.1016/S0010-8545(01)00317-4. Crossref, Web of Science, Google Scholar
B. Z. Gullariet al., Talanta 53, 1083 (2001). Web of Science, Google Scholar
C. Hamamci, H. Hosgoren and S. Erdogan, Talanta 47, 229 (1998), DOI: 10.1016/S0039-9140(98)00082-4. Crossref, Web of Science, Google Scholar
Y. Kikuchi and Y. Sakamoto, Anal. Chim. Acta 403, 325 (2002), DOI: 10.1016/S0003-2670(99)00648-0. Crossref, Web of Science, Google Scholar
M. A. Schiavonet al., J. Mol. Catal. A: Chemical 174, 213 (2001), DOI: 10.1016/S1381-1169(01)00176-5. Crossref, Web of Science, Google Scholar
B. Meunier, Chem. Rev. 92, 1411 (1992), DOI: 10.1021/cr00014a008. Crossref, Web of Science, Google Scholar