Metal phthalocyanine oxidation catalysts

Abstract: As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Method of oxidizing alkanes by contact with a catalyst comprising diazido derivative of a metal phthalocyanine, including halogenated phthalocyanines. Method of oxidizing alkanes by contact with a catalyst comprising a metal phthalocyanine or halide thereof, including halogenated phthalocyanines, and an alkali metal or ammonium or tetraalkylammonium azide.

Description: BACKGROUND OF THE INVENTION Azide-activated metal phthalocyanine ligands have been disclosed in U.S. Patents 4,895,682 and 5,093,491 equivalent to EP-A-0 274 909 to Ellis, Lyons and Myers, as catalysts for the oxidation of alkanes with air or oxygen. These patents disclose macrocycles which contain an azide group attached to the phthalocyanine ring. DESCRIPTION OF THE INVENTION The present invention involves in one embodiment the preparation and use as alkane oxidation catalysts of metal phthalocyanine compounds having specifically two azide groups. A general formula for such catalysts is: where M is iron, cobalt, manganese or chromium, N 3 is azide, is phthalocyanine and M' is alkali metal, such as sodium, potassium or lithium, or ammonium or tetraalkylammonium such as tetrabutylammonium. The preparation of the metal phthalocyanine diazide according to this embodiment of the invention may be accomplished by reaction of metal phthalocyanine halide with an alkali metal or ammonium or tetraalkylammonium azide. The reaction may be conducted at ambient conditions, preferably with a large weight excess of the azide. In one embodiment of the invention, the preparation of a metal phthalocyanine diazide occurs in situ in an alkane oxidation process. In this embodiment, an alkane is contacted with oxygen-containing gas and a catalyst comprising metal phthalocyanine and alkali metal or ammonium or tetraalkylammonium azide. Preferably, the catalyst used according to the invention is a metal perhalogenated phthalocyanine, as disclosed in EP-A-0 471 561. "Perhalogenated", as used herein, refers to a degree of ligand halogenation which is preferably at least 70%, more preferably at least 90%. The term, "phthalocyanine" as used herein, includes such halogenated ligands. A preferred compound for use according to this embodiment of the invention is sodium diazido-perfluorophthalocyanatoferrate, Na[Fe( F Pc)(N 3 ) 2 ] where F indicates substitution of at least 90% of the hydrogen atoms in the ligand with fluorine, Pc is phthalocyanine ligand and N 3 is azide. In another embodiment of the invention, oxidation of alkanes is carried out in the presence of a metal phthalocyanine or halide thereof, for example iron perfluorophthalocyanine, and an alkali metal or ammonium or tetraalkylammonium azide, under conditions as used previously in the oxidation of alkanes with metal phthalocyanine azides. Although the invention is not to be limited by any theory, it is believed that in this embodiment, the metal phthalocyanine and the aside react to form metal phthalocyanine diazide in situ, which then catalyzes the oxidation reaction. In this embodiment of the invention, the metal phthalocyanine and the alkali metal or ammonium or tetraalkylammonium azide may be added separately or together to the reaction mixture containing the alkane to be oxidized. The reaction conditions used are generally those disclosed in column 3 of U. S. Patent 4,895,682 supra, for oxidation using azide-activated metal phthalocyanines. EXAMPLES The invention will be further described with reference to the following examples: Example 1 Iron phthalocyanine chloride, Fe( F Pc)Cl, was prepared by refluxing the known complex, Fe F Pc, in chlorobenzene. The product, Fe( F Pc)Cl was reacted metathetically with a tenfold weight excess of sodium azide in methanol at room temperature for 48 hours. The reaction product was evaporated to dryness, washed with water and dried. The major product, a dark green solid, was a material having two azide bands in the infrared (νN-N 1999 cm -1 and 2030 cm -1 ),believed to be the anionic diazido complex, Na(Fe( F Pc)(N 3 ) 2 ]. Iron perfluorophthalocyanine monoazide, Fe( F PcN 3 ), was apparently produced as a minor product. Example 2 The diazido complex prepared in Example 1 was used for light alkane oxidation by stirring 0.0125 millimole of the complex in 25 ml of benzene containing 7 grams of isobutane under 100 psig of oxygen at the temperature designated in Table 1 below for the time indicated. Tert-butyl alcohol and acetone were the major products. The results are shown in Table I. Comparison Example For comparison, Runs 4 to 8 shown in Table II were carried out under the indicated conditions for the oxidation of isobutane with air using as catalyst iron-phthalocyanine complex in Run 4, iron-phthalocyanine nitride in Run 5, iron-perfluorophthalocyanine in Run 6 and iron-perfluorophthalocyanine monoazide in Runs 7 and 8. Comparison of Runs 2 and 3 of Table I with Runs 7 and 8 of Table II show that the diazide complex of Table I gave results similar to the monoazide complex of Table II. In addition, diazide complexes have been found to have superior shelf stability to monoazide complexes. Reactions of Isobutane with Oxygen Catalyzed by Na[Fe F Pc(N 3 ) 2 ] Run Catalyst mmoles T°C. t, hours T.O. Selectivity to t-butyl alcohol 1 0.021 80 6 743 81 2 0.0125 80 6 1029 82 3 0.0125 60 6 162 92 Oxidation of Isobutane Catalyzed by Metal Phthalocyanine Compounds Run Catalyst mmoles T, °C t, Hrs. TON SEL 4 Fe(Pc) 0.030 80 6 0 - 5 [Fe(Pc)] 2 N 0.016 80 6 0 - 6 Fe( F Pc) 0.023 80 6 0 - 7 Fe( F Pc)N 3 0.013 80 6 990 82 8 Fe( F Pc)N 3 0.013 60 6 156 92 Example 3 (Reference) Propane was oxidized with air under the conditions, and with the catalysts shown in Table III. The results are shown in Table III. Runs 12 and 14 used as catalyst, iron perfluorophthalocyanine and sodium azide. Comparison of these runs with Runs 10, 15 and 17, in which the catalyst was metal phthalocyanine azide, indicates that the catalyst of Runs 12 and 14 was active for the reaction, though apparently less active at 150°C than the catalyst of Runs 10, 15 and 17 (567 turnovers in Run 14 against 754 turnovers in Run 15). Oxidation of Propane Catalyzed by Iron Perfluorophthalocyanine Complexes Complex mmoles Solvent. T,°C t.Hrs. TON IPA/Acetone 9 Fe(FPc) 0.023 Benzene 125 3 0 - 10 Fe( F Pc)N 3 0.028 Benzene 125 6 48 0.7 11 Fe( F Pc) 0.023 CH 3 CN 125 3 57 0.7 12 Fe( F Pc)+NaN 3 0.028 CH 3 CN 125 3 98 0.7 13 Fe( F Pc) 0.028 CH 3 CN 150 3 460 0.3 14 Fe( F Pc) + NaN 3 0.028 CH 3 CN 150 3 567 0.4 15 Fe( F Pc)N 3 0.028 CH 3 CN 150 3 754 0.7 16 Fe( F Pc)Cl 0.028 CH 3 CN 150 3 606 0.7 17 Fe( F Pc)N 3 0.028 C 6 H 5 CN 150 3 1210 0.6

Claims: A compound having the formula: where M is iron, cobalt, manganese or chromium, N 3 is azide, ○ is phthalocyanine, and M' is alkali metal or ammonium or tetraalkylammonium. A compound according to Claim 1, wherein the phthalocyanine ligand is at least 70% halogenated. A compound according to Claim 2, wherein the phthalocyanine ligand is at least 90% halogenated. A compound according to Claims 2 or 3, wherein the halogen is fluorine. A compound according to any of Claims 1 to 4, wherein M is iron. A method of oxidizing alkanes which comprises contacting an alkane with air or oxygen and a compound according to any one of the preceding claims. A method of oxidizing alkanes which comprises contacting an alkane with an oxygen-containing gas and a catalyst comprising a metal phthalocyanine or halide thereof and an alkali metal or ammonium or tetraalkylammonium aside such that a compound according to any one of Claims 1 to 5 is formed in situ .

Inventors: ELLIS PAUL E JR, LYONS JAMES E, ELLIS, PAUL E., JR., LYONS, JAMES E.
Applicants: SUN CO INC R & M, SUN COMPANY, INC. (R&M)
Application year: 1993
Main classification: B01J31
IPC codes: C07B41, C07D487, C07C45, B01J27, C07B61, B01J31, C07C29, C07C27