Hydrogen transfer reactions of arenes in molten antimony trichloride

Journal Article · Wed Aug 29 04:00:00 EDT 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00512a031· OSTI ID:5879265

Dworkin, A S; Poutsma, M L; Brynestad, J; Brown, L L; Gilpatrick, L O; Smith, G P

The reactions of polycyclic aromatic hydrocarbons in molten antimony trichloride at temperatures from 80 to 175/sup 0/C have been studied by in situ /sup 1/H NMR and quench and separation techniques. Decomposition takes place by a complex series of hydrogen redistribution reactions whose net effect is a disproportionation of a type not previously known to occur. The reaction of anthracene (I) was studied in detail. Some of the anthracene molecules lose aryl-bound hydrogen and are condensed into larger molecules with aryl-aryl bonds such as the asymmetric bianthracenes (IV, V, and VI) and anthraaceanthrylenes (VII and VIII). The hydrogen released by these reactions is quantitatively captured by other anthracene molecules to form hydroaromatic molecules such as the 9,10-dihydro- and 1,2,3,4-tetrahydroanthracenes (II and III). The catalytic role of the solvent's Lewis acidity was demonstrated by the fact that the addition of a few mol % of a strong chloride donor reduced the reaction rates by a large factor. The reaction behavior of a group of related arenes (naphthalene, phenanthrene, chrysene, pyrene, perylene, and naphthacene) of widely varying basicity and oxidizability was also surveyed. 2 figures.

• Research Organization: Oak Ridge National Lab., TN
• DOE Contract Number: W-7405-ENG-26
• OSTI ID: 5879265
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:18; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ANTHRACENE
ANTIMONY CHLORIDES
ANTIMONY COMPOUNDS
AROMATICS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
CHRYSENE
CONDENSED AROMATICS
DECOMPOSITION
HALIDES
HALOGEN COMPOUNDS
HEAT TREATMENTS
HIGH TEMPERATURE
HYDROCARBONS
KINETICS
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
NAPHTHALENE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
PHENANTHRENE
POLYCYCLIC AROMATIC HYDROCARBONS
PYRENE
QUENCHING
REACTION KINETICS
RESONANCE
SEPARATION PROCESSES
SOLVOLYSIS
TEMPERATURE DEPENDENCE
YIELDS