Iodine → 3-(2-Ethylhexyl)thiophene

Participants

Reaction Steps

Dry magnesium turnings (10.2 g, 0.42 mol) and 40 mL of anhydrous THF were placed in a three-necked round-bottomed flask. A crystal of iodine was added to initiate the Grignard reaction. 2-Ethylhexyl bromide (79.0 g, 0.41 mol) in 100 mL of anhydrous THF was then added dropwise to magnesium turnings. After the addition, the reaction was heated to reflux for 1 h, then cooled down to room temperature, and diluted with 100 mL of THF. In another flask were added 3-bromothiophene (50.0 g, 0.31 mol), [1,3-bis(diphenylphosphino)propane]dichloronickel (1.7 g, 0.003 mol), and 100 mL of THF and the flask was cooled in an ice-bath. The Grignard reagent was added to the above solution via a cannula. After stirring at room temperature overnight, the reaction was quenched with 2N HCl, extracted with ethyl ether. The combined organic phase was washed with brine and dried over MgSO4. The crude product was purified by column chromatography on silica gel using hexane as an eluent to give 27.5 g pure product as light yellow liquid (46% yield). 1H NMR (CDCl3) δ (ppm): 0.84-0.89 (m, 6H), 1.19-1.33 (m, 8H), 1.53-1.57 (m, 1H), 2.56 (d, J=6.8 Hz, 2H), 6.87-6.90 (m, 2H), 7.19-7.23 (m, 2H); 13C NMR (CDCl3): 10.86, 14.12, 23.05, 25.70, 28.95, 32.58, 0.34, 40.46, 120.64, 124.79, 128.80, 141.93; FD-MS: m/z 196 (M+).

Provenance & Evidence