1-Bromo-2-(2,2-diethoxy-ethylsulfanyl)-benzene

Synthesis

To a suspension of DMF (70 mL) containing K2CO3 (8.186 g, 59.23 mmol) was sequentially added 2-bromothiophenol (7.00 g, 37.02 mmol) and 2-bromoacetaldehyde diethyl acetal (7.821 g, 40.72 mmol). The reaction mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was partitioned between water (100 mL) and EtOAc (100 mL). The organic layer was separated and washed with distilled water (5 x 50 mL). The combined aqueous layers were back-extracted with EtOAc (100 mL). All organic layers were combined, dried with anhydrous MgSO4, filtered and concentrated under reduced pressure. The residue was purified by short-range vacuum distillation and the fractions were collected at 130-140 °C (0.2 mmHg) to afford (2-bromophenyl)(2,2-diethoxyethyl)thioalkane (10.42 g, 92% yield) as a colorless oil. The structure of the product was confirmed by 1H NMR (300 MHz, CDCl3) and 13C NMR (75 MHz, CDCl3).1H NMR (300 MHz, CDCl3) δ 7.51 (dd, J = 7.9,1.3 Hz, 1H), 7.34 (dd, J = 7.9,1.5 Hz, 1H), 7.26-7.20 (m, 1H) , 7.04-6.97 (m, 1H), 4.69 (t, J = 5.5 Hz), 3.69 (dq, J = 9.2,7.0 Hz, 2H), 3.56 (dq, J = 9.2,7.0 Hz, 2H), 3.14 (d, J = 5.5 Hz, 2H), 1.20 (t, J = 7.0 Hz, 6H).13C NMR ( 75 MHz, CDCl3) δ 137.7,133.0,128.8,127.7,126.8,123.8,101.63,62.4,37.0,15.5.

References

[1] Chemistry - A European Journal, 2015, vol. 21, # 35, p. 12303 - 12307
[2] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 14, p. 3933 - 3937
[3] Patent: US6436964, 2002, B1
[4] Patent: US6465453, 2002, B1
[5] Patent: US6353008, 2002, B1. Location in patent: Page column 25-26