A highly catalytic and selective conversion of carboxylic acids to 1-alkenes of one less carbon atom

Journal Article · Fri Jan 01 00:00:00 EST 1993 · Journal of Organic Chemistry; (United States)

DOI:https://doi.org/10.1021/jo00053a008· OSTI ID:6130661

Miller, J A; Nelson, J A; Byrne, M P ^[1]

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1. Henkel Research Corp., Santa Rosa, CA (United States)

An equimolar mixture of a carboxylic acid and acetic anhydride produces a reagent combination that undergoes a highly efficient decarbonylation/dehydration at 250[degrees]C using either Pd- or Rh-based catalyst systems, affording excellent yields of the corresponding 1-alkenes and one less carbon atom. The stoichiometric and catalytic decarbonylation of aliphatic aldehydes and acid chlorides to alkanes and alkenes, respectively, by transition-metal complexes are well-known and synthetically useful transformations. Relatively little, however, has been reported concerning the analogous decarbonylation/dehydration of aliphatic carboxylic acids to olefins, with generally poor results achieved in terms of catalyst efficiency and selectivity toward terminal olefin formation in the product. For example, the decarbonylation/dehydration of stearic acid to heptadecane using a Rh-based catalyst was reported to proceed with a maximum catalyst turnover number (TON; moles of olefin product formed per mole of catalyst used) of ca. 250, with selectivities toward 1-heptadecene formation typically below 50%. Interestingly, results were presented in this work which suggested that the decarbonylation of stearic acid proceeded via intermediate formation of stearic anhydride. Use of a preformed, symmetrical anhydride is not desirable from an economic or synthetic viewpoint, particularly since its decarbonylation should result in the formation of equal amounts of olefin and carboxylic acid coproducts. The authors now report here that the use of a carboxylic acid substrate as an equimolar mixture with acetic anhydride (Ac[sub 2]O) produces a mixed anhydride system which undergoes an extremely facile decarbonylation reaction to provide a general and highly selective route to the corresponding 1-alkenes of one less carbon atom. 19 refs., 1 tab.

• OSTI ID: 6130661
• Journal Information: Journal of Organic Chemistry; (United States), Vol. 58:1; ISSN 0022-3263
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
ALKENES
CHEMICAL PREPARATION
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
PALLADIUM COMPLEXES
CATALYTIC EFFECTS
RHODIUM COMPLEXES
ALDEHYDES
ALKANES
ANHYDRIDES
CARBONYLATION
CHEMICAL REACTION YIELD
CHLORIDES
CONVERSION
DEHYDRATION
EFFICIENCY
HOMOGENEOUS CATALYSIS
STOICHIOMETRY
TRANSFORMATIONS
CATALYSIS
CHLORINE COMPOUNDS
COMPLEXES
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
ORGANIC ACIDS
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties
100200 - Synthetic Fuels- Production- (1990-)