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Title: Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1992--June 30, 1992

Abstract

Aryl carbon-oxygen bond cleavage is a chemical transformation of importance in coal liquefaction and the upgrading of coal liquids as well as in the synthesis of natural products. There have been numerous attempts to discover general methods for the cleavage of aryl carbon-oxygen bonds. All the stoichiometric organic methods for phenol deoxygenation have limited applications and involve expensive reagents. Catalytic method, for the hydrodeoxygenation (HDO) of phenols involve supported transition metal oxides, such as Mo/{gamma}-Al{sub 2}O{sub 3}, Ni-MO/{gamma}-Al{sub 2}O{sub 3}, Co-Mo/{gamma}-Al{sub 2}O{sub 3}, and Fe{sub 2}O{sub 3}/SiO{sub 2}. Typical phenol hydrodeoxygenation conditions involve hydrogen pressures in excess of 100 atm and temperatures in excess of 200{degrees}C. Under these conditions arene ring hydrogenation is generally found to compete with phenol deoxygenation; and the coproduct water is found to impair the activity of the catalysts. This proposed research offers the possibility of effecting the selective catalytic deoxygenation of phenolic functional groups using CO. The deoxygenation of phenols by carbon monoxide mediated by Ir(triphos)OAr has provided us with a catalytic Phenol deoxygenation pathway, through the elimination of CO{sub 2} and formation of a benzyne intermediate. Although the [Pt(triphos)(O-Ph-Me)]PF{sub 6} system is not expected to be as efficient a catalyst as some of themore » other transition metals systems we are currently exploring, it will provide more information about the deoxygenation mechanism in these triphos complexes. This is due to the presence of the structurally sensitive {sup 3l}P--{sup 195}Pt coupling constant and comparisons to the extensively studied Pt(dppe)(O-Ph){sub 2} systems.« less

Authors:
Publication Date:
Research Org.:
Purdue Univ., Lafayette, IN (United States). Dept. of Chemistry
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
10191908
Report Number(s):
DOE/PC/89770-T13
ON: DE93002941
DOE Contract Number:  
FG22-89PC89770
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: [1992]
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; COAL LIQUEFACTION; COAL LIQUIDS; REFINING; PHENOLS; HYDROGENATION; TRANSITION ELEMENT COMPOUNDS; CATALYTIC EFFECTS; PROGRESS REPORT; EXPERIMENTAL DATA; CHEMICAL BONDS; CLEAVAGE; OXYGEN; REMOVAL; CARBON MONOXIDE; CATALYSTS; OXIDES; 010405; HYDROGENATION AND LIQUEFACTION

Citation Formats

Kubiak, C P. Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1992--June 30, 1992. United States: N. p., 1992. Web. doi:10.2172/10191908.
Kubiak, C P. Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1992--June 30, 1992. United States. doi:10.2172/10191908.
Kubiak, C P. Sun . "Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1992--June 30, 1992". United States. doi:10.2172/10191908. https://www.osti.gov/servlets/purl/10191908.
@article{osti_10191908,
title = {Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, April 1, 1992--June 30, 1992},
author = {Kubiak, C P},
abstractNote = {Aryl carbon-oxygen bond cleavage is a chemical transformation of importance in coal liquefaction and the upgrading of coal liquids as well as in the synthesis of natural products. There have been numerous attempts to discover general methods for the cleavage of aryl carbon-oxygen bonds. All the stoichiometric organic methods for phenol deoxygenation have limited applications and involve expensive reagents. Catalytic method, for the hydrodeoxygenation (HDO) of phenols involve supported transition metal oxides, such as Mo/{gamma}-Al{sub 2}O{sub 3}, Ni-MO/{gamma}-Al{sub 2}O{sub 3}, Co-Mo/{gamma}-Al{sub 2}O{sub 3}, and Fe{sub 2}O{sub 3}/SiO{sub 2}. Typical phenol hydrodeoxygenation conditions involve hydrogen pressures in excess of 100 atm and temperatures in excess of 200{degrees}C. Under these conditions arene ring hydrogenation is generally found to compete with phenol deoxygenation; and the coproduct water is found to impair the activity of the catalysts. This proposed research offers the possibility of effecting the selective catalytic deoxygenation of phenolic functional groups using CO. The deoxygenation of phenols by carbon monoxide mediated by Ir(triphos)OAr has provided us with a catalytic Phenol deoxygenation pathway, through the elimination of CO{sub 2} and formation of a benzyne intermediate. Although the [Pt(triphos)(O-Ph-Me)]PF{sub 6} system is not expected to be as efficient a catalyst as some of the other transition metals systems we are currently exploring, it will provide more information about the deoxygenation mechanism in these triphos complexes. This is due to the presence of the structurally sensitive {sup 3l}P--{sup 195}Pt coupling constant and comparisons to the extensively studied Pt(dppe)(O-Ph){sub 2} systems.},
doi = {10.2172/10191908},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1992},
month = {11}
}