602-98-2Relevant articles and documents
Flash flow pyrolysis: Mimicking flash vacuum pyrolysis in a high-temperature/high-pressure liquid-phase microreactor environment
Cantillo, David,Sheibani, Hassan,Kappe, C. Oliver
supporting information; experimental part, p. 2463 - 2473 (2012/05/20)
Flash vacuum pyrolysis (FVP) is a gas-phase continuous-flow technique where a substrate is sublimed through a hot quartz tube under high vacuum at temperatures of 400-1100 °C. Thermal activation occurs mainly by molecule-wall collisions with contact times in the region of milliseconds. As a preparative method, FVP is used mainly to induce intramolecular high-temperature transformations leading to products that cannot easily be obtained by other methods. It is demonstrated herein that liquid-phase high-temperature/high- pressure (high-T/p) microreactor conditions (160-350 °C, 90-180 bar) employing near- or supercritical fluids as reaction media can mimic the results obtained using preparative gas-phase FVP protocols. The high-T/p liquid-phase "flash flow pyrolysis" (FFP) technique was applied to the thermolysis of Meldrum's acid derivatives, pyrrole-2,3-diones, and pyrrole-2-carboxylic esters, producing the expected target heterocycles in high yields with residence times between 10 s and 10 min. The exact control over flow rate (and thus residence time) using the liquid-phase FFP method allows a tuning of reaction selectivities not easily achievable using FVP. Since the solution-phase FFP method does not require the substrate to be volatile any more -a major limitation in classical FVP-the transformations become readily scalable, allowing higher productivities and space-time yields compared with gas-phase protocols. Differential scanning calorimetry measurements and extensive DFT calculations provided essential information on pyrolysis energy barriers and the involved reaction mechanisms. A correlation between computed activation energies and experimental gas-phase FVP (molecule-wall collisions) and liquid-phase FFP (molecule-molecule collisions) pyrolysis temperatures was derived.
CHEMISTRY OF OXALYL DERIVATIVES OF METHYL KETONES. 28. REACTION OF CARBONYL COMPOUNDS OF ADAMANTANE WITH 5-PHENYL-2,3-DIHYDROFURAN-2,3-DIONE
Andreichikov, Yu. S.,Sivkova, M. P.,Shapet'ko, N. N.
, p. 1008 - 1011 (2007/10/02)
The reaction of substituted methyl 1-adamantyl ketones with an equimolar amount of 5-phenyl-2,3-dihydrofuran-2,3-dione under the conditions of the thermal decarbonylation of the latter leads to the corresponding 2-methyl-2-adamantyl-6-phenyl-1,3-dioxen-4-ones, 6-phenyl-3-benzoyl-2,4-dione, and the starting ketones.The steric and electronic factors that affect the yields of the dioxen-4-ones were examined. α-Hydroxymethyl 1-adamantyl ketones open up the furan ring to give 1-adamantoyl-methyl benzoylpyruvate.Data from the IR, PMR, and UV spectra are presented.