Methyl iodide → 3-Bromo-2-formyltoluene, 6-Bromo-o-tolualdehyde

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Reaction Steps

1H NMR (500 MHz, CDCl3) δ [ppm] 7.55 (d, 3J=8.0 Hz 2H, ar), 7.00 (t, 3J=8.0 Hz 1H, ar), 6.19 (s, 1H, CH), 4.33-4.29 (m, 2H, CH2), 4.02-3.97 (m, 2H, CH2), 2.44-2.34 (m, 1H, CH2), 1.44-1.40 (m, 1H, CH2); 13C{1H} NMR (125.77 MHz, CDCl3) δ [ppm] 133.9, 132.5, 129.8, 122.9, 101.6, 66.7, 24.1. The acetal (10.1 g, 31.25 mmol) was dissolved in THF, abs. (200 ml). At −78° C. n-BuLi (15.1 ml, 2.5 M in hexane, 37.8 mmol) was added within 25 min, followed by 90 min additional stirring at that temperature. Then the reaction mixture was treated with methyliodide (5.99 g, 42.2 mmol) and stirred for 25 min at −78° C. Next the reaction mixture was allowed to warm to ambient temperature within 1.5 h. The resulting solution was quenched with HCl (290 ml of a 5 N solution) and stirred for 1.5 h at ambient temperature. The complete deprotection of the aldehyde was checked via GC analysis. Then the reaction mixture was subsequently extracted with diethylether (4×100 ml), the combined organic layers were washed with a 10% solution of sodium thiosulfate (100 ml), water (100 ml), dried over MgSO4, filtered and the volatiles removed in vacuo. The resulting slightly yellow solid was purified via Kugelrohr distillation to afford 50 (5.97 g, 96%) as white crystals. Rf 0.56 (cyclohexane:ethylacetate 10:1).

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