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Title: Reactions catalyzed by haloporphyrins

Patent ·
OSTI ID:870282

The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxygroup containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of alkanes is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of alkanes and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of alkanes and decomposition of alkyl hydroperoxides.

Research Organization:
Sun Refining and Marketing Co., Marcus Hook, PA (United States)
DOE Contract Number:
FC21-90MC26029
Assignee:
Sun Company, Inc. (R&M) (Philadelphia, PA)
Patent Number(s):
US 5489716
OSTI ID:
870282
Country of Publication:
United States
Language:
English

References (20)

Synthesis of 1-Fluoro-1-demethylmesoporphyrin-IX journal January 1992
Cytodeuteroporphyrin 1,2 journal June 1960
Abbau von Hämatoporphyrin zu Tetramethyl-brom-bromoxäthyl-porphin-dipropionsäure journal September 1927
Halogen Substituent Effects on the Catalytic Activity of Iron Porphyrin Complexes for the Decomposition of tert-Butyl Hydroperoxide journal May 1993
The meso-reactivity of porphyrins and related compounds. Part II. Halogenation journal January 1966
Nuclear magnetic resonance investigation of magnetic and electronic properties of "intermediate spin" ferrous porphyrin complexes journal May 1977
Selective low temperature hydroxylation of isobutane by molecular oxygen catalyzed by an iron perhaloporphyrin complex journal January 1991
Organisch-chemischen Institut der Technischen Hochschule München. Über einige Derivate von Ätioporphyrin I journal January 1932
meso-perfluorination of porphyrins with N-fluoropyridinium triflate journal February 1992
Porphyrins. VII. The synthesis of porphyrins by the Rothemund reaction journal January 1964
Synthese einiger Porphyrine vom Ätioporphyrin III-Typ, sowie eines Tetramethyl-tripropionsäure-porphins. journal January 1930
Investigation of the synthesis of ortho-substituted tetraphenylporphyrins journal February 1989
Fluoropyrroles and tetrafluoroporphyrins journal January 1985
On the preparation of metalloporphyrins journal July 1970
NIH shift in haemin–iodosylbenzene-mediated hydroxylations journal January 1981
Nucleophilic substitution of meso -nitrooctaethylporphyrins journal February 1985
Halogen substituent effects on the catalytic activity of iron porphyrin complexes for selective air-oxidation of alkanes in the liquid phase journal September 1989
1,4,5,8-Tetramethyl-2,3,6,7-tetracarbethoxyporphyrin and Some Derivatives 1 journal January 1950
A study of bromoporphins journal January 1984
Über Tetrachlormesoporphyrin journal April 1913