Hydride abstraction from 9,10-dihydroanthracene and 5,12-dihydronaphthacene in an aprotic molten salt medium
The dissolution of 9,10-dihydroanthracene (DHA) in high purity aprotic molten SbCl/sub 3/-10 mol % AlCl/sub 3/ at temperatures from 100 to 130/sup 0/C results in prompt formation of anthracenium ion (1). In this case, 1 is generated by a formal hydride abstraction from some of the molecules of DHA while the hydrogen abstracted is transferred to unreacted molecules of DHA to form a mixture of THA, 1,2,3,4,5,6,7,8,-octahydroanthracene (OHA), and other hydroanthracenes and/or hydroarenes. The role of the Sb/sup 3 +/ as an oxidant is evident in the recovery of stoichiometric amounts of Sb metal in the product mixtures. A similar reaction occurs for 5,12-dihydronaphthacene (DHN), producing the naphthacenium ion (2). The formation of 1 and 2 was followed by /sup 1/H NMR measurements on the melts both with and without a (CH/sub 3/)/sub 4/N/sup +/ internal standard. Their identities were confirmed by comparison of their respective integrated /sup 1/H NMR spectra with those obtained from authentic samples measured in various molten salt solvents. After quench and separation procedures, the organic reaction products were identified by GC, GC-MS, and high-performance LC. With DHA as the starting material, 20 to 25% of the product was found to be a mixture of hydroarenes about equally divided between those with mass 182 and those with mass 186. Of this 20 to 25%, the main products were THA (mass 182) and OHA (mass 186) with the rest made up of other isomeric hydroanthracenes and/or hydroarenes. The yield of anthracene found after hydrolysis of the reacted melt agreed with the yield of 1 in the melt determined from the NMR integration. With DHN as the starting material, essentially all of the hydrogenated product was found to be two tetrahydronaphthacenes, mass 232, and very little octahydronaphthacene or other mass 236 hydroarenes were detected.
- Research Organization:
- Oak Ridge National Lab., TN
- DOE Contract Number:
- W-7405-ENG-26
- OSTI ID:
- 6644489
- Journal Information:
- J. Org. Chem.; (United States), Vol. 46:2
- Country of Publication:
- United States
- Language:
- English
Similar Records
Electroreduction in aqueous media, saturation of polycyclic aromatics. [Tetrabutylammonium hydroxide]
PHOTON-INDUCED FORMATION OF MOLECULAR HYDROGEN FROM A NEUTRAL POLYCYCLIC AROMATIC HYDROCARBON: 9,10-DIHYDROANTHRACENE
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIMONY CHLORIDES
CHEMICAL REACTIONS
CONDENSED AROMATICS
HYDROGEN TRANSFER
ANTHRACENE
ANTIMONY
CHEMICAL REACTION YIELD
GAS CHROMATOGRAPHY
HIGH TEMPERATURE
MASS SPECTROSCOPY
MEDIUM TEMPERATURE
MOLTEN SALTS
NUCLEAR MAGNETIC RESONANCE
ANTIMONY COMPOUNDS
AROMATICS
CHLORIDES
CHLORINE COMPOUNDS
CHROMATOGRAPHY
ELEMENTS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
MAGNETIC RESONANCE
METALS
ORGANIC COMPOUNDS
RESONANCE
SALTS
SEPARATION PROCESSES
SPECTROSCOPY
YIELDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400201 - Chemical & Physicochemical Properties