List of used abbreviations - RosDok - Universität Rostock

General procedure for the synthesis of 2-(arylthio)benzoates 12a-r: To a
dichloromethane solution (5 mL / mmol of 3) of 3 (1.0 mmol) and of 11 (1.5 mmol)
was added TiCl4 (1.5 mmol) at –78 °C. The solution was allowed to warm to 20 °C
within 20 h. To the solution was added a saturated aqueous solution of NaHCO3 (15
mL). The organic and the aqueous layer were separated and the latter was extracted
with diethyl ether (3 x 20 mL). The combined organic layers were dried (Na2SO4),
filtered, and the filtrate was concentrated in vacuo. The residue was purified by
chromatography (silica gel, EtOAc / n-heptane = 1:4).
S
O
Me
OMe
4-Methyl-2-phenylsulfanyl-benzoic acid methyl ester (12a):
Starting with 3a (420 mg, 1.5 mmol), 11a (0.23 mL, 2.25 mmol),
TiCl4 (0.25 mL, 2.25 mmol) and CH2Cl2 (9 mL), 12a was isolated
as a highly viscous oil (205 mg, 53%). 1 H NMR (250 MHz, CDCl3):
δ = 2.27 (s, 3H, CH3), 3.80 (s, 3H, OCH3), 7.05-7.24 (m, 8H, Ar);
13 C NMR (63 MHz, CDCl3): δ = 18.6 (CH3), 51.1 (OCH3), 126.1, 128.1, 128.3, 128.9,
129.3, 130.1 (ArCH), 132.1, 134.7, 134.9, 135.6, 167.9 (C); IR (KBr, cm −1 ): v� = 3056
(w), 2994 (w), 2948 (w), 2927 (w), 2857 (w), 1727 (s), 1606 (m), 1581 (m), 1476 (m),
1449 (s), 1437 (s), 1380 (w), 1266 (s), 1240 (s), 1188 (m), 1152 (m), 1105 (s), 1066
(s), 1023 (m), 954 (m), 738 (s), 688 (s); MS (EI, 70 eV): m/z (%) = 258 (M + , 69), 227
(46), 226 (22), 225 (100), 197 (15), 184 (33), 165 (8), 152 (6), 63 (3); HRMS (EI):
calcd for C15H14O2S [M + ]: 258.07090, found: 258.070766.
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