3-Chloro-2-chloromethyl-1-propene → S-Allylthiobenzene

Participants

Reaction Steps

To a 1 L flask at 0 C was added 160 mL of methanol. The solution was kept under 30 C as Na metal (5.10 g, 221.24 mmol) was added in small portions. After all the sodium had reacted, 4-hydroxythiophenol (25.0 g, 2.2 eq) was added to the solution of sodium methoxide. The solution was heated to reflux and 3-chloro-2-chloromethyl-1-propene (11.26 g, 1 eq) was added dropwise over 1 hour. The solution was allowed to reflux overnight. The solution was cooled to 25 C, filtered, and reduced in vacuo to remove the methanol. The crude material was taken up in 500 mL of water and extracted with ether (4×150 mL). The ether layer was washed with 1N HCl, water, brine, and dried over sodium sulfate. The organic layer was reduced in vacuo to a crude orange oil. The oil was purified by flash chromatography 90:10 hexanes/ethyl acetate to yield 23.52 g of a colorless oil. Yield 85.8%. 1H NMR (400 MHz, CDCl3, δ): 7.23 (m, 4H, Ar—H), 6.74 (m, 4H, Ar—H), 5.84 (s, 2H, Ar—OH), 4.70 (s, 2H, C═CH2), 3.57 (s, 4H, CH2); 13C NMR (400 MHz, CDCl3, δ): 155.3 (C1), 140.45 (C10), 138.6 (C5), 134.3 (C8), 132.7 (C4), 126.0 (C7), 116.5 (C3), 116.0 (C6), 40.63 (C11); MS (ESI, m/z): [M+Li]+ calcd for C16H16O2S2, 344.3; found, 344.3.

Provenance & Evidence