Reactivity of Anthracene in Liquid SbCl3 ‐ AlCl3 ‐  N  ‐  ( 1 ‐ Butyl ) Pyridinium Chloride Mixtures

Abstract

Mixtures of SbC]~ and N-(1-butyl)pyridinium chloride (BPC1) containing 75-87 m]o (mole percent) SbC13 and SbCI~-A1CI~-BPC1 mixtures containing 60 m/o SbCl~ and 16-23 m/o A1CI~ were found to be liquid at 25~ Dilute solutions of anthracene were stable in ternary mixtures containing 18 m/o A1C13, but in mixtures containing 22-24 m/o A1CI~, anthracene reacted under the influence of the solvent, which behaved as both oxidant and H-transfer catalyst. The oxidized product was protonated anthracene, which Was stable in this melt. The source of protons was provided by hydrogen liberating Scholl condensations combined with the reduction of Sb(III). A part of the hydrogen from Scholl reactions reacted with anthracene to form 9,10-dihydroanthracene. By contrast, a liquid mixture without SbC13, A1C13-BPC1 (2:1 mole ratio) proved to be a much less active H-transfer catalyst than the SbCl~-rich liquids even though it is a stronger Lewis acid, and it did not induce protonation beyond a trace attributable to protic impurities. The role of impurities in these mixtures was investigated with results that are relevant to earlier investigations of liquid A1C13-BPC1 mixtures. An improved procedure for purifying BPC1 is described. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-17 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-17 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-17 to IP

Reduction of Aromatic Compounds in Organic Chloroaluminate Melts: II . Perylene

“…(14). Aluminum chloride (Fluka puriss, grade) was purified in a manner similar to that previously described (15). The syntheses of EMIC (8) and DMPIC (2) have been reported elsewhere.…”

“…UV/visible absorption spectroscopy of stable solutions was performed using a Cary 14 spectrophotometer. The absorption cells have been previously described (2,15).…”

Electronic Absorption Spectra of Protonated Anthracenes and Phenanthrenes, and Their Neutrals in Neon Matrices

“…Several decades ago H-An + was studied in strong acidic solutions (Aalbersberg et al 1959;Dallinga et al 1958;Gold & Tye 1952;Reid 1954) and melted salts (Brigodiot & Lebas 1976;Zingg et al 1984), and its electronic spectrum was reported. The anthracenium ion H-An + exhibits a strong, broad absorption with maximum around 410-430 nm in these environments.…”

Reduction of Aromatic Compounds in Organic Chloroaluminate Melts: I . Phenazine

“…UV/visible absorption spectroscopy of stable solutions was performed using a Cary 14H spectrophotometer. The absorption cells consisted of i cm 2 silica cuvettes with vac: uum-tight closures as previously described (23). Precision silica inserts were used to obtain short path lengths (50-200 ~m).…”

“…Chemicals.--Aluminum chloride (Fluka puriss, grade) was purified in a manner similar to that previously described (23). Acetonitrile (Burdick and Jackson) and 1methylimidazole (Chemical Dynamics Corp.) were also purified as previously described (14).…”