Thermal Decomposition Mechanisms of the Methoxyphenols: Formation of Phenol, Cyclopentadienone, Vinylacetylene, and Acetylene

Citations Over TimeTop 10% of 2011 papers

Abstract

The pyrolyses of the guaiacols or methoxyphenols (o-, m-, and p-HOC6H4OCH3) have been studied using a heated SiC microtubular (μ-tubular) reactor. The decomposition products are detected by both photoionization time-of-flight mass spectroscopy (PIMS) and matrix isolation infrared spectroscopy (IR). Gas exiting the heated SiC μ-tubular reactor is subject to a free expansion after a residence time of approximately 50–100 μs. The PIMS reveals that, for all three guaiacols, the initial decomposition step is loss of methyl radical: HOC6H4OCH3 → HOC6H4O + CH3. Decarbonylation of the HOC6H4O radical produces the hydroxycyclopentadienyl radical, C5H4OH. As the temperature of the μ-tubular reactor is raised to 1275 K, the C5H4OH radical loses a H atom to produce cyclopentadienone, C5H4═O. Loss of CO from cyclopentadienone leads to the final products, acetylene and vinylacetylene: C5H4═O → [CO + 2 HC≡CH] or [CO + HC≡C–CH═CH2]. The formation of C5H4═O, HCCH, and CH2CHCCH is confirmed with IR spectroscopy. In separate studies of the (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectra, we observe the presence of C6H5OH in the molecular beam: C6H5OH + λ275.1 nm → [C6H5OH Ã] + λ275.1nm → C6H5OH+. From the REMPI and PIMS signals and previous work on methoxybenzene, we suggest that phenol results from a radical/radical reaction: CH3 + C5H4OH → [CH3–C5H4OH]* → C6H5OH + 2H.

Related Papers

• → The hydrogenation of acetyleneII. The reaction of acetylene with hydrogen catalyzed by alumina-supported palladium(1966)103 cited
• → Infrared Spectra of Acetylene and Acetylene Derivatives Adsorbed on Alumina and Silica(1961)58 cited
• → Selective Catalysis. The Catalytic Reaction between Acetylene and Hydrogen(1950)11 cited
• Control of higher alkynes in purification process of acetylene in natural gas to acetylene plant(2014)
• → OPTIMIZATION OF TECHNOLOGICAL PARAMETERS OF HYDRAGENERATION PROCESS OF ACETYLENE USING A PILOT CATALYTIC PLANT(2020)