Influence of carbocyclic rings on porphyrin cyclizations: Synthesis of geochemically significant cycloalkanoporphyrins

Journal Article · · Energy and Fuels; (USA)

DOI:https://doi.org/10.1021/ef00024a010· OSTI ID:5976397

Lash, T D; Balasubramaniam, R P; Catarello, J J; Johnson, M C; May, Jr, D A; Bladel, K A; Feeley, J M; Hoehner, M C; Marron, T G; Nguyen, T H; Perun, Jr, T J; Quizon, D M; Shiner, C M; Watson, A ^[1]

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1. Illinois State Univ., Normal (USA)

The synthesis of cycloalkanoporphyrins from cycloalkenopyrroles is described. Cycloalkeno(b)pyrroles were prepared in moderate to good yields from the corresponding cyclic ketones. Reaction with lead tetraacetate afforded the corresponding labile acetoxy derivatives. Condensation of the acetoxy compounds with {alpha}-free pyrroles in the presence of an acid catalyst gave pyrrolylcycloalkeno(b)pyrroles in good yields. These dipyrroles were the key intermediates in the total synthesis of porphyrins bearing exocyclic rings. Condensation of dipyrrole dicarboxylic acids with diformyldipyrrylmethanes (the MacDonald condensation) were carried out in the presence of p-toluenesulfonic acid. Good yields of the corresponding porphyrins were obtained when five-, six-, seven-, or sixteen-membered rings were present. The eight-membered ring slightly inhibited this reaction. a,c-Biladienes incorporating carbocyclic rings were also prepared. Poor yields of porphyrin were obtained when copper(II) salts were used to mediate the cyclization of the a,c-biladienes. When six-, seven-, or eight-membered rings were present, moderate to good yields of the corresponding porphyrins could be obtained when cyclizations were carried out with silver iodate-zinc acetate in dimethylformamide. Five-membered carbocyclic rings severely inhibited these cyclizations. This work provides the foundation for reliable syntheses of geochemically significant cycloalkanoporphyrins.

• OSTI ID: 5976397
• Journal Information: Energy and Fuels; (USA), Journal Name: Energy and Fuels; (USA) Vol. 4:6; ISSN 0887-0624; ISSN ENFUE
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020200 -- Petroleum-- Reserves
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& Exploration
04 OIL SHALES AND TAR SANDS
040200* -- Oil Shales & Tar Sands-- Reserves
Geology
& Exploration
ACETATES
AZOLES
BITUMINOUS MATERIALS
CARBONACEOUS MATERIALS
CARBOXYLIC ACID SALTS
CARBOXYLIC ACIDS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHROMATOGRAPHY
CONVERSION
COPPER COMPOUNDS
ENERGY SOURCES
FOSSIL FUELS
FUELS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
KETONES
LEAD COMPOUNDS
LIQUID COLUMN CHROMATOGRAPHY
MAGNETIC RESONANCE
MATERIALS
NUCLEAR MAGNETIC RESONANCE
OIL SHALES
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORIGIN
PETROLEUM
PORPHYRINS
PYRROLES
REACTION INTERMEDIATES
RESONANCE
SEPARATION PROCESSES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
YIELDS