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A Modified Water‐Gas Shift Reaction. The Decomposition of Alkyl Formate in the Presence of Water Using a Ruthenium Carbonyl
Author(s) -
Jou DerChing,
Cheng ChienHong
Publication year - 1991
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199100040
Subject(s) - chemistry , nitrobenzene , catalysis , formate , alkyl , ruthenium , ethyl formate , medicinal chemistry , aniline , water gas shift reaction , decomposition , ethylene , inorganic chemistry , organic chemistry
Alkyl formates in the presence of water were rapidly decomposed to H 2 , CO 2 and the corresponding alcohols using Ru 3 (CO) 12 and KOAc as catalyst. Based on the hydrogen gas produced, a turnover rate as fast as 8446/h for ethyl formate at 140°C was observed. The catalyst system was also active for the decomposition of other alkyl formates. The rate of decomposition increased both with increasing amount of KOAc and with decreasing number of carbon atom in the alkyl group of the formate. In addition to Ru 3 (CO) 12 , several other transition metal complexes RuCl 3 , RuCl 2 (PPh 3 ) 3 , Os 3 (CO) 12 , H 2 Os 3 (CO) 10 , RhCl 3 , and RhCl(PPh 3 ) 3 , were active in the catalytic decomposition of alkyl formates, although their activities varied greatly. The Ru 3 (CO) 12 ‐KOAc system also catalyzed the reduction of nitrobenzene by HCOOEt‐H 2 O to aniline in EtOH and to a mixture of N ‐phenylformamide and N ‐methyl‐ N ‐phenylformamide in HCOOEt. Under coditions the same as for the hydrogenation of nitrobenzene, ethylene styrene and cyclohexenone were reduced to the corresponding alkanes, whereas 1‐hexene and 1‐octene were isomerized to the corresponding 2‐alkene products.