Chlorinated Phthalocyanine Iron(II) Complex Catalyzed Oxidation of Alkanes and Alkenes with Molecular Oxygen in the Presence of Acetaldehyde

Abstract

Chlorinated phthalocyanine iron(II) complex is an excellent catalyst for the oxidation of alkanes and alkenes with molecular oxygen in the presence of acetaldehyde under O₂ (1 atm) at room temperature. The catalyst can be easily separated and reused for the next reaction.

Key words

oxidations - molecular oxygen - alkanes - iron phthalocyanine catalyst

References

• 1 Murahashi S.-I. Angew. Chem., Int. Ed. Engl.  1995,  34:  2443 
• 2a Sheldon RA. Kochi JK. In Metal-Catalyzed Oxidations of Organic Compounds   Academic Press; New York: 1981. 
• 2b Barton DHR. Doller D. Acc. Chem. Res.  1992,  25:  504 
• 2c Shilov AE. Shul’pin G. Chem Rev.  1997,  97:  2879 
• 3a Murahashi S.-I. Komiya N. Oda Y. Kuwabara T. Naota T. J. Org. Chem.  2000,  65:  9186 
• 3b Murahashi S.-I. Oda Y. Naota T. Kuwabara T. Tetrahedron Lett.  1993,  34:  1299 
• 3c Murahashi S.-I. Oda Y. Komiya N. Naota T. Tetrahedron Lett.  1994,  35:  7953 
• 4a Murahashi S.-I. Oda Y. Naota T. J. Am. Chem. Soc.  1992,  114:  7913 
• 4b Murahashi S.-I. Oda Y. Naota T. Komiya N. J. Chem, Soc., Chem. Commun.  1993,  139 
• 4c Komiya N. Naota T. Oda Y. Murahashi S.-I. J. Mol. Catal. A: Chem.  1997,  117:  21 
• 5 Murahashi S.-I. Saito T. Naota T. Kumobayashi H. Akutagawa S. Tetrahedron Lett.  1991,  32:  5991 
• 6 Murahashi S.-I. Naota T. Komiya N. Tetrahedron Lett.  1995,  36:  8059 
• 7 Groves JT. Bonchio M. Carofiglio T. Shalyaev K. J. Am. Chem. Soc.  1996,  118:  8961 
• 8a Berezin BD. In Coordination Compounds of Porphyrins and Phthalocyanies   John Wiley & Sons; Chichester: 1981.  p.11-22  
• 8b In Metalloporphyrin Catalyzed Oxidations   Montanari F., Casella L., Kluwer Academic; Dordrecht: 1994. 
• 9a Bulkus KJ. Eissa M. Levado R. J. Am. Chem. Soc.  1995,  117:  10753 
• 9b Parton RF. Peere GJ. Neys PE. Jacobs PA. Claessens R. Baron GV. J. Mol. Catal A: Chem.  1996,  113:  445 
• 9c Raja R. Ratnasamy P. Catal. Lett.  1997,  48:  1 
• 10a Herron N. Stucky GD. Tolman CA. J. Chem. Soc., Chem. Commun.  1986,  1521 
• 10b Ichikawa M. Kimura T. Fukuoka A. Stud. Surf. Sci. Catal.  1991,  60:  335 
• 11 Parton RF. Vankelecom IFJ. Casselman MJA. Bezoukhanova CP. Uytterhoeven JB. Jacobs PA. Nature (London)  1994,  370:  541 
• 12a Armengol E. Corma A. Forne’s V. Garci’a H. Primo J. Appl. Catal. A.: General  1999,  181:  305 
• 12b Ernst S. Selle M. Micropor. Mesopor. Mater.  1999,  27:  355 
• 13 Parton RF. Neys PE. Jacobs PA. Sosa RC. Rouxhet PG. J. Catal.  1996,  164:  341 
• 14 d’Alessandro N. Liberatore L. Tonucci L. Morvillo A. Bressan M. New J. Chem.  2001,  25:  1319 
• The complexes are commercially available except 1-Ru(III), 2-Fe(II), and 5-Fe(II) complexes.
• 15a 1-Ru(III), see: Keen IM. Malerbi BW. J. Inorg. Nucl. Chem.  1965,  27:  1311 
• 15b 2-Fe(II), see: Jones JG. Twigg MV. Inorg. Chem.  1969,  8:  2018 
• 15c 5-Fe(II), see: Metz J. Schneider O. Hanack M. Inorg. Chem.  1984,  23:  1065 
• 18a Kasuga K. Tsuboi K. Handa M. Sugimori T. Sugebe K. Inorg. Chem. Commun.  1999,  2:  507 
• 18b Nino ME. Giraldo SA. Pez-Mozo EA. J. Mol. Catal. A: Chem.  2001,  175:  139 
• 19 Khanna RK. Pauling TM. Vajpayee D. Tetrahedron Lett.  1991,  32:  3759 
• 20 Sakurai H. Hosomi A. J. Am. Chem. Soc.  1967,  89:  458 
• 21 Sorokin A. Robert A. Meunier B. J. Am. Chem. Soc.  1993,  115:  7293 
• 22 Ohkatsu Y. Hara T. Osa T. Bull. Chem. Soc. Jpn.  1977,  50:  692 

16

If the amount of acetaldehyde was increased, the conversion of cyclohexane went up; however, the selectivity was decreased due to the formation of undesirable over-oxidation products such as adipic acid, glutaric acid, and succinic acid. [3a]

17

Evaporation of dichloromethane under vacuum (to ca. 2 mL), addition of diethyl ether (30 mL), and filtration gave 3-Fe(II) complex.