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Gas‐Phase Hydrogenolysis of Benzene and Derivatives at Elevated Pressure; Methane Formation
Author(s) -
van Scheppingen Wibo B.,
Cieplik Mariusz K.,
Louw Robert
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200106)2001:11<2101::aid-ejoc2101>3.0.co;2-e
Subject(s) - chemistry , benzene , methane , isomerization , hydrogenolysis , hydrogen , photochemistry , catalysis , bar (unit) , cyclopentadienyl complex , medicinal chemistry , gas phase , kinetic energy , hydrogen atom , organic chemistry , group (periodic table) , physics , quantum mechanics , meteorology
Benzene, in 20−30 bar of hydrogen, reacts smoothly in a quartz tubular flow reactor between 1163−1262 K, to give high yields of methane. With dwell times of 3−23 s, degrees of conversion ranged from 10 to 95%. Substituents such as Cl and CH 3 are displaced more easily: ca. 350 times more rapidly at 1250 K. Mechanisms are discussed on a quantitative thermochemical‐kinetic basis. Of the alternatives considered, only a pathway through H atom addition, (reversible) isomerisation of C 6 H 7 · species, H‐transfer from H 2 to give − for example − methylcyclopentadiene ( F ), followed by splitting into ·CH 3 and cyclopentadienyl radical ( G ), would fully explain the observed rates of conversion of benzene.