Kazmierczak Jean C, Cargnelutti Roberta, Barcellos Thiago, Silveira Claudio C, Schumacher Ricardo F
Departamento de Química, CCNE, Universidade Federal de Santa Maria-UFSM, Santa Maria, 97105-900, RS, Brazil.
Instituto de Biotecnologia Universidade de Caxias do Sul-UCS, Caxias do Sul, RS, Brazil.
Beilstein J Org Chem. 2021 Jan 26;17:234-244. doi: 10.3762/bjoc.17.24. eCollection 2021.
We described herein a selective method to prepare α-organylthio esters and α-organylthio ketones by the reaction of β-keto esters with sodium -benzyl sulfurothioate or sodium -alkyl sulfurothioate (Bunte salts) under basic conditions in toluene as the solvent at 100 °C. When 4 equivalents of a base were used, a series of differently substituted α-thio esters were obtained with up to 90% yield. On the other hand, employing 2 equivalents of a base, α-thio ketones were achieved after 18 h under air. Furthermore, after a shorter reaction time, the isolation of keto-enol tautomers was possible, revealing them as significant intermediates for the mechanism elucidation.
我们在此描述了一种选择性方法，即在甲苯作为溶剂、100℃的碱性条件下，通过β-酮酯与苄基硫代硫酸钠或烷基硫代硫酸钠（邦特盐）反应制备α-有机硫代酯和α-有机硫代酮。当使用4当量碱时，可得到一系列不同取代的α-硫代酯，产率高达90%。另一方面，使用2当量碱时，在空气中反应18小时后可得到α-硫代酮。此外，在较短的反应时间后，可以分离出酮-烯醇互变异构体，表明它们是阐明反应机理的重要中间体。
