# US 5,345,008 A · Decomposition of organic hydroperoxides with nitrated porphyrin complexes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,345,008 A - Document ID: US5345008A - Status: Granted - Kind: A - Application number: 08/073,840 - Filed: 1993-06-09 - Granted: 1994-09-06 - Earliest claimed: 1993-06-09 - Assignees: Sun Company, Inc. (R&M) - Inventors: James E. Lyons; Paul E. Ellis, Jr. - Web page: https://patentgrep.com/patent/US5345008A ## CPC - C07C 29/132: by reduction of an oxygen containing functional group - C07C 29/50: with molecular oxygen only - C07C 37/08: by decomposition of hydroperoxides, e.g. cumene hydroperoxide - C07C 45/53: of hydroperoxides - C07C 2601/14: The ring being saturated - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Hydroperoxides are decomposed by contact with metalloporphyrin coordination complex catalysts in which hydrogen in the porphyrin molecule has been substituted with at least one nitro group and may be further substituted with other electron-withdrawing elements or groups, for example, halogen or halocarbons, or with hydrocarbon groups. Preferred catalysts are iron tetranitro-.beta.-octaethylporphyrins and iron tetrakispentafluorophenyl-.beta.-nitroporphyrins. ## Claims ### Claim 1 A process for the decomposition of organic hydroperoxide which comprises contacting said hydroperoxide with a catalyst comprising: ##STR9## wherein M is selected from the group consisting of Fe, Mn, Co, Cu, Ru and Cr; at least one X is nitro and the remaining X are selected from the group consisting of hydrogen, nitro fluorine, chlorine, bromine, hydrocarbon and halocarbon or combinations thereof; Y is selected from the group consisting of hydrocarbon, halocarbon, fluorine, chlorine, bromine and hydrogen or combinations thereof; and A is anion or is absent. ### Claim 2 (depends on 1) The process of claim 1 wherein all X comprise nitro and all Y comprise hydrocarbon. ### Claim 3 (depends on 2) The process of claim 2 wherein said hydrocarbon is selected from the group consisting of alkyl and aryl groups. ### Claim 4 (depends on 3) The process of claim 3 wherein said hydrocarbon comprises ethyl. ### Claim 5 (depends on 1) The process of claim 1 wherein M comprise iron. ### Claim 6 (depends on 1) The process of claim 1 wherein A is selected from the group consisting of halide, hydroxide, azide and nitride. ### Claim 7 (depends on 6) The process of claim 6 wherein A comprises chloride. ### Claim 8 (depends on 7) The process of claim 7 wherein said catalyst comprises iron(tetranitro-octaethylporphyrin) chloride. ### Claim 9 (depends on 1) The process of claim 1 wherein said catalyst comprises .mu.-oxo dimer comprising two complexes as shown in claim 1 joined through a M--O--M linkage. ### Claim 10 (depends on 9) The process of claim 9 wherein said catalyst comprises a .mu.-oxo dimer of iron(tetranitrooctaethylporphyrin). ### Claim 11 A process for the decomposition of organic hydroperoxide which comprises contacting said hydroperoxide with a catalyst comprising: ##STR10## wherein M is selected from the group consisting of Fe, Mn, Co, Cu, Ru and Cr; at least one X is halocarbon and remaining X are selected from the group consisting of hydrogen, halocarbon fluorine, chlorine, bromine and hydrocarbon or combinations thereof; at least one Y is nitro and the remaining Y are selected from the group consisting of nitro, hydrogen, fluorine, chlorine and bromine or combinations thereof; and A is anion or is absent. ### Claim 12 (depends on 11) The process of claim 11 wherein all X comprise halocarbon. ### Claim 13 (depends on 12) The process of claim 12 wherein said halocarbon comprises perhalogenated halocarbon. ### Claim 14 (depends on 13) The process of claim 13 wherein halogen in said perhalogenated halocarbon is selected from the group consisting of fluorine, chlorine and bromine. ### Claim 15 (depends on 14) The process of claim 14 wherein said perhalogenated halocarbon is selected from the group consisting of pentafluorophenyl, pentachlorophenyl, trifluoromethyl and trichlorophenyl groups. ### Claim 16 (depends on 15) The process of claim 15 wherein said perhalogenated halocarbon comprises pentafluorophenyl group. ### Claim 17 (depends on 11) The process of claim 11 wherein M comprises iron. ### Claim 18 (depends on 11) The process of claim 11 wherein A is selected from the group consisting of halide, hydroxide, azide and nitride. ### Claim 19 (depends on 18) The process of claim 18 wherein A comprises chloride. ### Claim 20 (depends on 19) The process of claim 19 wherein said catalyst comprises iron (tetrakispentafluorophenyl-nitroporphyrin) chloride. ### Claim 21 (depends on 11) The process of claim 11 wherein said catalyst comprises .mu.-oxo dimer comprising two complexes as shown in claim 11 joined through a M--O--M linkage. ### Claim 22 (depends on 21) The process of claim 21 wherein said catalyst comprises a .mu.-oxo dimer of iron(tetrakispentafluorophenyl-nitroporphyrin). ### Claim 23 A process for the decomposition of organic hydroperoxide which comprises contacting said hydroperoxide with a catalyst comprising: ##STR11## wherein M is selected from the group consisting of Fe, Mn, Co, Cu, Ru and Cr; at least one X is nitro and the remaining X are selected from the group consisting of hydrogen, nitro, fluorine, chlorine and bromine or combinations thereof; at least one Y is nitro and the remaining Y are selected from the group consisting of nitro, hydrogen, fluorine, chlorine and bromine or combinations thereof; and A is anion or is absent. ### Claim 24 (depends on 23) The process of claim 23 wherein all X and all Y comprise nitro. ### Claim 25 (depends on 23) The process of claim 23 wherein M comprises iron. ### Claim 26 (depends on 23) The process of claim 23 wherein A is selected from the group consisting of halide, hydroxide, azide and nitride. ### Claim 27 (depends on 26) The process of claim 26 wherein A comprises chloride. ### Claim 28 (depends on 22, 23) The process of claim 23 wherein said catalyst comprises .mu.-oxo dimer comprising two complexes as shown in claim 22 joined through a M--O--M linkage. ### Claim 29 (depends on 1, 11, 23) The process of Claims 1, 11 or 23 wherein said hydroperoxides comprise R--O--OH , wherein R is selected from the group consisting of alkyl and aryl groups. ### Claim 30 (depends on 29) The process of claim 29 wherein said hydroperoxide is selected from the group consisting of t-butyl hydroperoxide, isobutyl hydroperoxide, isoamyl hydroperoxide, 2-methylbutyl-2-hydroperoxide, cyclohexyl hydroperoxide, cumyl hydroperoxide, phenethyl hydroperoxide and cyclohexyl hydroperoxide. ### Claim 31 (depends on 30) The process of claim 30 wherein said hydroperoxide comprises t-butyl hydroperoxide. ### Claim 32 (depends on 1, 11, 23) The process of claim 1, 11 or 23 wherein said decomposition is performed in a solution comprising 5 to 50 wt.% of said hydroperoxide, at temperature in the range of 0.degree. to 200.degree. C., and pressure in the range of 15 to 1000 psig, for 0.1 to 5 hours. ### Claim 33 (depends on 32) The process of claim 32 wherein said hydroperoxide is maintained in a solution of organic solvent selected from the group consisting of benzene, chlorobenzene, o-dichlorobenzene, acetonitrile, benzonitrile, ketone and alcohol. ### Claim 34 (depends on 33) The process of claim 33 wherein said alcohol comprises an alcohol corresponding to that formed by decomposition of said hydroperoxide.