MnO2 instead of quinones as selective oxidant of tetrapyrrolic macrocycles

Inorganic Chemistry Communications

Volumn 13, Issue 3, 2010, Pages 395-398

  Nascimento, Bruno F O ^a   Rocha Gonsalves, António M d'A ^a   Pineiro, Marta ^a  

^a UNIVERSITY OF COIMBRA   (Portugal)

Author keywords

Bacteriochlorin; Chlorin; Manganese dioxide; Microwave synthesis; Oxidation; Porphyrin

Indexed keywords

EID: 76749153771     PISSN: 13877003     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.inoche.2009.12.032     Document Type: Article

References (26)

1. Milgrom L.R. The Colours of Life, an Introduction to the Chemistry of Porphyrins and Related Compounds (1997), Oxford University Press, Oxford
2. Kadish K.M., Smith K.M., and Guilard R. The Porphyrin Handbook vol. 6 (2000), Academic Press, San Diego
3. Schlesinger W., Corwin A.H., and Sargen L.J. J. Am. Chem. Soc. 72 (1950) 2867-2871
4. Eisner U. J. Chem. Soc. (1957) 3461-3469
5. Bonnett R., Gale I.A.D., and Stephenson G.F. J. Chem. Soc. C (1967) 1168-1172
6. Jaquinod L. In: Kadish K.M., Smith K.M., and Guilard R. (Eds). The Porphyrin Handbook vol. 1 (2000), Academic Press, San Diego 201-232
7. Scheer H. In: Dolphin D. (Ed). The Porphyrins vol. 2 (1978), Academic Press, New York 1-37
8. Rusell H., Ball H., Dorough G.D., and Calvin M.J. J. Am. Chem. Soc. 68 (1946) 2278-2281
9. Inhoffen H.H., Buchler J.W., and Thomas R. Tetrahedron Lett. (1969) 1141-1144
10. Ficken G.E., Linstead R.P., Stephen E., and Whalley M. J. Chem. Soc. (1958) 3879-3886
11. Whitlock Jr. H.W., Hanauer R., Oester M.Y., and Bower B.K. J. Am. Chem. Soc. 91 (1969) 7485-7489
12. Adler A.D., Longo F.R., Finarelli J.D., Goldmacher J., Assour J., and Karsakoff J.L. J. Org. Chem. 32 (1967) 476-478
13. Johnstone R.A.W., Nunes M.L.P.G., Pereira M.M., Rocha Gonsalves A.M.dA., and Serra A.C. Heterocycles 43 (1996) 1423-1437
14. Lindsey J.S., Schreiman I.C., Hsu H.C., Kearney P.C., and Marguerettaz A.M. J. Org. Chem. 52 (1987) 827-836
15. Rocha Gonsalves A.M.dA., and Pereira M.M. J. Heterocyclic Chem. 22 (1985) 931-933
16. 2 60 (12 cm high) and eluted with methylene chloride/n-hexane 5:1 v/v (1b, 1f), methylene chloride/ethyl acetate 9:1 v/v (1c) or methylene chloride/ethyl acetate 1:1 v/v (1d). The red fraction is collected, evaporated under reduced pressure and crystallized in methylene chloride/methanol (1b, 1c, 1f) or ethyl acetate/n-hexane (1d), yielding the corresponding porphyrin as a crystalline dark purple solid. Porphyrins 1a, 1e and 1g are easily crystallized overnight from the cooled crude product mixture by addition of methanol. The dark purple solid is then filtered, washed with methanol and dried in vacuo at room temperature. Procedure adapted from reference [19].
17. Bacteriochlorin synthesis. The selected porphyrin (1a-g, 25 mg), anhydrous potassium carbonate (100 equiv.) and p-toluenesulfonylhydrazide (100 equiv.) are added to 1,4-dioxane (2 mL) and thoroughly mixed in an appropriate thick-walled glass vial. The reaction vessel is then tightly sealed with a Teflon cap and the reaction mixture is magnetically stirred and heated at 120 °C for 25 min under focused microwave irradiation with an initial power setting of 100 W. After cooling to room temperature, the crude product mixture is homogenized with distilled water (50 mL) and neutralized by the drop-wise addition of an aqueous solution of hydrochloric acid (35% v/v). The suspension that immediately precipitates out of the solution is filtered, thoroughly washed with distilled water and rigorously dried in vacuo at room temperature, yielding a mixture of the corresponding bacteriochlorin (major product) and chlorin (minor product) as a brownish solid (2a-g).
18. 2. The liquid filtrate is then evaporated under reduced pressure and rigorously dried in vacuo at room temperature, yielding a mixture of the corresponding chlorin (major product) and porphyrin (minor product) as a dark purple solid (3a-g).
19. Nascimento B.F.O., Pineiro M., Rocha Gonsalves A.M.dA., Ramos Silva M., Matos Beja A., and Paixão J.A. J. Porph. Phthal. 11 (2007) 77-84
20. Fatiadi A.J. Synthesis (1976) 65-104
21. Fatiadi A.J. Synthesis (1976) 133-167
22. Taylor R.J.K., Reid M., Foot J., and Raw S.A. Acc. Chem. Res. 38 (2005) 851-869
23. Varma S.R., Saini R.K., and Dahiya R. Tetrahedron Lett. 38 (1997) 7823-7824
24. Goswami S., and Maity A.C. Chem. Lett. 36 (2007) 1118-1119
25. Bagley M.C., and Lubinu M.C. Synthesis (2006) 1283-1288
26. All experiments were carried out in appropriate 10 mL thick-walled glass vials under closed-vessel conditions using a CEM Discover S-Class single-mode microwave reactor with continuous temperature, pressure and microwave power monitoring.