By Michele Aresta and Rudi van Eldik (Eds.)
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Extra info for CO Chemistry
O R2 O ð2:28Þ OH O This reaction usually proceeds in volatile organic solvents, such as DMF or THF, and requires large amounts of organic solvents and high CO2 pressure (ca. 0 MPa). Recently, Ikarya has reported the use of imidazolin-2-ylidenes with N-alkyl and N-aryl substituents and their CO2 adducts as catalyst of the carboxylative cyclization of internal and terminal propargyl alcohols (281). The reaction of internal propargyl alcohols with CO2 has been carried out also under supercritical conditions.
1 COCl2 þ 2CH3OH DMC þ 2HCl 55 2 (CH2O)2CO þ 2CH3OH DMC þ HO(CH2)2OH 59 3 (NH3)2CO þ 2CH3OH DMC þ 2NH3 72 4 CO þ 1/2O2 þ 2CH3OH DMC þ H2O 83 5 CO2 þ 2CH3OH DMC þ H2O 83 32 Angela Dibenedetto and Antonella Angelini One of the very first reports of a catalytic reaction deals with n-dibutyldialkoxy stannanes (n-Bu2Sn(OR)2) (R ¼ methyl, ethyl n-butyl) as catalytic precursors (90). The best yield is obtained if ethanol is reacted with 10 bar of CO2 in a batch reactor at 443 K for 24 h. 6 is reached.
6). DRIFT studies on the catalyst allowed to collect information on the reactions occurring on surface under the different operative conditions through the characterization of the species formed (83). The reaction mechanism on the surface of Al–Ce mixed oxide was defined through a specific study. 6 DMC yield in five consecutive cycles of reaction. 0 MPa of CO2. Adapted from ref. (80). or a near methoxo moiety on the surface of the catalyst. 3). In order to give an experimental evidence to the mechanism based on the attack by the gas-phase methanol, DRIFT studies were integrated with solid-state or solution multinuclear NMR experiments.
CO Chemistry by Michele Aresta and Rudi van Eldik (Eds.)