2-CHLORO-3-HYDROXYBENZALDEHYDE97

To a suspension of 3-hydroxybenzaldehyde (20.12 g, 160 mmol) in HOAC (40 mL) was added carefully tBuOCl (20 mL, 176 mmol) with stirring. The reaction became a clear solution and strongly exothermic. It was allowed to cool and stirred for 16 hours, resulting in a white precipitate. The solid was filtered, washed with H20 and dried to give 2-chloro-3-hydroxybenzaldehyde (13.77 g, 55 percent), GCMS (EI) mlz 156, 158 (M+). To a solution OF 2-CHLORO-3-HYDROXYBENZALDEHYDE (4.55 g, 29 mmol) in DMF (30 mL) was added K2CO3 (4.8 g, 34.9 mmol) followed by MeI (2.7 mL, 43.6 mmol), and the mixture was stirred at room temperature for 16 hours. Following concentration IN VACUO, the residual was taken up in ethyl acetate, washed with H2O, brine, dried over NA2S04, and concentrated. Purification by column chromatography on silica gel with ethyl ACETATE/HEXANES 1/5 afforded 2-chloro-3-methoxybenzaldehyde 3a (4.68 g, 94 percent) as a colorless oil, which solidified upon standing. GCMS (EI) M/Z 170, 172 (M+).To a suspension of 3-hydroxybenzaldehyde (20.12 g, 160 mmol) in HOAC (40 mL) was added carefully tBuOCI (20 mL, 176 mmol) with stirring. The reaction became a clear solution and strongly exothermic. It was allowed to cool and stirred for 16 hours, resulting in a white precipitate. The solid was filtered, washed with H20 and dried to give 2-chloro-3-hydroxybenzaldehyde (13.77 g, 55 percent), GCMS (EI) M/Z 156, 158 (M+).To a suspension of 3-HYDROXYBENZALDEHYDE (20.12 g, 160 mmol) in HOAC (40 mL) was added carefully tBuOCl (20 mL, 176 mmol) with stirring. The reaction became a clear solution and strongly exothermic. It was allowed to cool and stirred for 16 hours, resulting in a white precipitate. The solid was filtered, washed with HZ0 and dried to give 2-chloro-3-hydroxybenzaldehyde (13.77 g, 55 percent), GCMS (EI) m/z 156, 158 (M+).To a suspension of 3-hydroxybenzaldehyde (5 g, 40.98 mmol) in AcOH (10 mL) was added carefully t-BuOC1 (5 mL, 45.08 mmol) with stirring. It was allowed to cool and stirred for 16 hours, resulting in a white precipitate. The solid was filtered, washed with H20 and dried to give the title product (3 g, 46.9percent). ‘H-NMR (400 MHz, CDC13): ö 10.66 (br, 1H), 10.33 (s, 1H), 7.31-7.25 (m, 3H).lntermediate 12; 2-Chloro-3-hydroxybenzaldehyde. Chlorine was bubbled through a solution of m- hydroxybenzaidehyde (CAS 100-83-4) (100 g, 820 mmol) in glacial acetic acid (440 g) at 15

Molecular Weight:156.56
XLogP3:1.7
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:155.9978071
Monoisotopic Mass:155.9978071
Topological Polar Surface Area:37.3
Heavy Atom Count:10
Complexity:127
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes