Allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones

被引:41
作者
Di Cosimo, JI [1 ]
Acosta, A [1 ]
Apesteguía, CR [1 ]
机构
[1] UNL, CONICET, Inst Invest Catalisis & Petroquim, Catalysis Sci & Engn Res Grp, RA-3000 Santa Fe, Argentina
关键词
hydrogen transfer; basic catalysis; alpha; beta-unsaturated ketone; reduction; chemoselectivity;
D O I
10.1016/j.molcata.2005.03.002
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The gas-phase hydrogen transfer reduction (HTR) of mesityl oxide (MO) with 2-propanol to selectively obtain allylic alcohols was studied on MgO. MO was converted directly to 4-methyl-3-penten-2ol(UOL1) or isomerised to iso-mesityl oxide (i-MO), which consecutively formed 4-methyl-4-penten-2ol (UOL2). Significant amounts of methyl isobutyl carbinol (MIBC) were also formed by the simultaneous reduction of C=C and C=O groups of MO. The effect of reaction conditions on catalyst activity and selectivity was determined in order to improve total UOL yield that was about 28 % under standard reaction conditions (T=523 K, 2-propanol/MO=5, W/F-MO(0)=15 g h/mol). Total UOL yield increased continuously with contact time up to 42 % but when the 2-propanol/MO ratio was varied, UOL yield reached a maximum at a reactant ratio of about 4. UOL2 yield markedly increased with temperature at expenses of MIBC. The increase of temperature also improved the catalyst stability because suppressed formation of coke intermediates. Regarding the effect of the hydrogen donor, higher total UOL yields were obtained by using secondary alcohols, such as 2-propanol and 2-butanol, than primary (1-propanol) or secondary aryl (1-penylethanol) alcohols. (c) 2005 Elsevier B.V All rights reserved.
引用
收藏
页码:111 / 120
页数:10
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