Reactions catalyzed by haloporphyrins

Details Reactions catalyzed by haloporphyrins Reactions catalyzed by haloporphyrins

1994-09-07

1996-02-06

Evans, Joseph E.

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

568815, 568821, 568836, 568838, 5689095, 5689098, C07C 2950, C07C 3112

Patent

active

054897165

ABSTRACT:
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.

REFERENCES:
patent: 4864041 (1989-09-01), Hill
patent: 4892941 (1990-01-01), Dolphin et al.
patent: 4895680 (1990-01-01), Ellis et al.
patent: 4895682 (1990-01-01), Ellis et al.
patent: 4900871 (1990-02-01), Ellis et al.
patent: 4970348 (1990-11-01), Ellis et al.
patent: 5118886 (1992-06-01), Ellis et al.
patent: 5120882 (1992-06-01), Ellis et al.
patent: 5120886 (1992-06-01), Lyons et al.
patent: 5345008 (1994-09-01), Lyons et al.
Ellis et al, Cat. Lett., "Halogen Substituent Effects on the Catalytic Activity of Iron Porphyrin Complexes for Selective Air-Oxidation of Alkanes in the Liquid Phase", 3, 389-397, (1989).
Lyons et al, Cat. Lett., Selective Low Temperature Hydroxylation of Isobutane by Molecular Oxygen Catalyzed by an Iron Perhaloporphyrin Complex, 8, 45-51, (1991).
Lyons et al, J. Catalysis, Halogen Substituent Effects on the Catalytic Activity of Iron Porphyrin Complexes for the Decomposition of tert-Butyl Hydroperoxide, 141, 311-315, (1993).
Badger et al, Aust. J. Chem., "Porphyrins VII*. The Synthesis of Porphyrins By the Rothemund Reaction", 17, 1028-35, (1964).
Lindsey et al, J. Org. Chem., Investigation of the Synthesis of Ortho-Substituted Tetraphenylporphyrins, 54, 828-836, (1989).
Adler et al, J. Inorg. Nucl. Chem., On the Preparation of Metalloporphyrins*, 32, 2443-2445, (1970).
Chang et al, J.C.S. Chem. Soc. Comm., NIH Shift in Haemin-Iodosylbenzene-mediated Hydroxylations, 778-779, (1981).
Billig et al, Chem. Ind. (London), Mesomonofluorodeuteroporphyrin IX dimethyl ester, 654-655, (1969).
Naruta et al, Tetr. Lett., meso-Perfluorination of Porphyrins with N-Fluoropyridinium Triflate, 33, 1069-1072, (1992).
Onda et al, Tetr. Lett., Fluoropyrroles and Tetrafluoroporphyrins, 26, 4221-4224, (1985).
Suzuki et al., Heterocycles, Synthesis of 1-Fluoro-1-Demethylmesoporphyrin-IX, 33, 87-90, (1992).
Bonnett et al, J. Chem. Soc. (C), The meso-Reactivity of Porphyrins and Related Compounds. Part II.sup.1 Halogenation, 1600-1604, (1966).
Fischer et al, Liebig's Ann. Chem., Uber einige Derivate von Atioporphyrin I, 494, 225-245, (1932).
Fischer et al, Chem. Ber., Uber Tetrachlor-mesoporphyrin, 46, 2460-2466, (1913).
Gong et al, Can. J. Chem., Nitrooctaethylporphyrins: synthesis, optical and redox properties, 63, 406, (1985).
Marks et al, J. Am. Chem. Soc., Cytodeuteroporphyrin, 82, 3183-3188, (1960).
Andrews et al, J. Am. Chem. Soc., 1,4,5,8-Tetramethyl-2,3,6,7-tetracarbethoxyporphyrin and Some Derivatives.sup.1, 72, 491-494, (1950).
Fischer et al, Hoppe-Eysler's Z. Physiol. Chem., 191, Synthese einiger Prophyrine vom Atioporphyrin III-Typ, sowie eines Tetramethyl-tripropionsaure-porphins.), 36, (1930).
Nudy et al, Tetrahedron, A Study of Bromoporphins, 40, 2359-2363, (1984).
Fischer et al, Chem-Ber., Abbau von Hamatoporphyrin zu Tetramethyl-brom-bromoxathyl-porphrin-dipropionsaure, 60, 1861-1865, (1960).
Goff et al, J. Am. Chem. Soc., Nuclear Magnetic Resonance Investigation of Magnetic and Electronic Properties of "Intermediate Spin" Ferrous Prophyrin Complexes, 99, 3641-3646, (1977).

Affiliated with

Also associated with

Rating

Reactions catalyzed by haloporphyrins does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Reactions catalyzed by haloporphyrins, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Reactions catalyzed by haloporphyrins will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2176217