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Pd-catalyzed transfer hydrogenolysis of benzylic alcohol in acidic 2-propanol
Reaction Kinetics, Mechanisms and Catalysis ( IF 1.8 ) Pub Date : 2021-09-08 , DOI: 10.1007/s11144-021-02063-z
Yuji Ukisu 1
Affiliation  

The hydrogenolysis of 1-phenylethanol over supported palladium catalyst (Pd/SiO2, Pd/C, Pd/Al2O3, Pd/MgO, or Pd/hydroxyapatite) in 2-propanol under reflux conditions (82 °C) was investigated. The effects of nine diffrent acid additives (formic acid, acetic acid, lactic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, malic acid, or p-toluenesulfonic acid) were also examined. Ethylbenzene and acetophenone were both produced in the presence of the acid additives; however, only acetophenone was produced in the absence of acid additive. Selectivity for ethylbenzene tended to increase with increasing acid strength of the additive, although there were some exceptions. The highest ethylbenzene selectivity (73.6%) was achieved over Pd/C catalyst in the presence of formic acid, and moderate selectivity (43–46%) was achieved over all of the Pd catalysts in the presence of oxalic acid. Deuterium-labeling experiments revealed a reaction pathway involving a hydrogen-transfer process, in which 2-propanol, formic acid, and 1-phenylethanol function as hydrogen donors.



中文翻译:

Pd催化苯甲醇在酸性2-丙醇中的转移氢解

研究了在回流条件 (82 °C) 下,1-苯基乙醇在负载钯催化剂(Pd/SiO 2、Pd/C、Pd/Al 2 O 3、Pd/MgO 或 Pd/羟基磷灰石)上在 2-丙醇中的氢解. 九种不同酸添加剂(甲酸、乙酸、乳酸、丙酮酸、草酸、丙二酸、琥珀酸、苹果酸或p-甲苯磺酸)也进行了检查。乙苯和苯乙酮都是在酸添加剂存在下产生的;然而,在没有酸添加剂的情况下仅产生苯乙酮。乙苯的选择性随着添加剂酸强度的增加而增加,但也有一些例外。在甲酸存在下,在 Pd/C 催化剂上实现了最高的乙苯选择性(73.6%),在草酸存在下所有 Pd 催化剂上实现了中等选择性(43-46%)。氘标记实验揭示了一个涉及氢转移过程的反应途径,其中 2-丙醇、甲酸和 1-苯基乙醇作为氢供体。

更新日期:2021-09-08
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