59356-67-1Relevant articles and documents
Synthesis of p-xylene from ethylene
Lyons, Thomas W.,Guironnet, Damien,Findlater, Michael,Brookhart, Maurice
supporting information, p. 15708 - 15711,4 (2012/12/11)
As oil supplies dwindle, there is a growing need to develop new routes to chemical intermediates that utilize alternative feedstocks. We report here a synthesis of para-xylene, one of the highest volume chemicals derived from petroleum, using only ethylene as a feedstock. Ethylene is an attractive alternative feedstock, as it can be derived from renewable biomass resources or harnessed from large domestic shale gas deposits. The synthesis relies on the conversion of hexene (from trimerization of ethylene) to 2,4-hexadiene followed by a Diels-Alder reaction with ethylene to form 3,6-dimethylcyclohexene. This monoene is readily dehydrogenated to para-xylene uncontaminated by the ortho and meta isomers. We report here a selective synthesis of para-xylene, uncontaminated by the ortho or meta isomers, using ethylene as the sole feedstock.
Kinetics of thermal gas-phase isomerizations and fragmentations of cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275°C
Baldwin, John E.,Burrell, Richard C.
, p. 3249 - 3256 (2007/10/03)
Kinetic studies of the thermal isomerization and fragmentation reactions exhibited by cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275°C in the gas phase have provided first-order rate constants for cis,trans interconversions of the cyclobutanes, 1,3-carbon migrations leading to 3,4- and 3,6-dimethylcyclohexenes, isomerizations providing directly and indirectly four acyclic dienes, and fragmentations to ethylene, propene, and mixtures of pentadienes and hexadienes. Both cis and trans isomers of 1-(E)-propenyl-2-methylcyclobutane form trans-3,4-dimethylcyclohexene faster than they are converted to cis-3,4-dimethylcyclohexene; the trans reactant gives rise to cis-3,6-dimethylcyclohexene in preference to its trans isomer, while the cis starting material gives neither at measurable rates; both form the relatively minor product 1,6-(Z)-octadiene. The rate constants derived from 35 kinetic runs starting with four distinct 1-(E)-propenyl-2-methylcyclobutane samples are consistent to within narrow error limits. The stereomutations, isomerizations, and fragmentations of the 1-(E)-propenyl-2-methylcyclobutanes are interpreted in terms of competitive processes involving conformationally flexible short-lived 2-(E)-octene-4,7-diyl and 3-methyl-5-(E)-heptene-1,4-diyl diradicals.
Stereochemical Aspects of the Nickel-Catalyzed Alkylation of Allylic Alcohols
Consiglio, Giambattista,Morandini, Franco,Piccolo, Oreste
, p. 1846 - 1847 (2007/10/02)
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