硫代酰胺或硫代羧酸和α-鹵代酮反應(yīng)后，通過(guò)環(huán)硫化合中間體脫硫生成烯胺酮或β-羰基酮的反應(yīng)。生成的環(huán)硫中間體是通過(guò)和親硫的三芳基膦或三烷基膦反應(yīng)脫硫的。
反應(yīng)機(jī)理
反應(yīng)操作
Thioester (6). To a solution of thiobutyric acid 5 (3.16 g, 30 mmol) and Et3N (4.20 mL) in Et2O was added 1-bromobutan-2-one (3.06 mL, 30 mmol). After 2 h reflux, the mixture was filtered through Celite, the solvent evaporated and the residue distilled (Kugelrohr, 110℃/0.3 Torr) to afford 4.925 g of 6 (95%).
3,5-Octandione (7). To a solution of 6 (442 mg, 2.54 mmol) and anhyd LiBr (259 mg, 2.83 mmol) in MeCN was added bis(3-dimethylaminopropyl) phenylphosphine (2.2 mL). The reaction mixture was heated under N2 for 17 h at 70 ℃. The cooled mixture (0 ℃) was quenched with ice water (10 mL) and
conc HCl (1.3 mL). Extraction with Et2O:DCM (5:1), evaporation of the solvent and distillation (Kugelrohr, 90–105 ℃/10 Torr) afforded 336 mg of 7 (93%).
【Eschenmoser A, Helv Chim Acta., 1971, 54, 710】
相關(guān)文獻(xiàn)
1 Eschenmoser A Angew Chem Int 1969 8 343
2 Eschenmoser A Pure Appl Chem 1969 20 1
3R Eschenmoser A Quart Rev 1970 24 366
4 Eschenmoser A Helv Chim Acta 1971 54 710
5 Shiosaki K Compreh Org Synth 1991 2 865
6 Horikawa H Tet Lett 1994 35 2187
7 Gaurat O Can J Chem 2004 82 1289
編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 143.
