1-(3-BROMO-2-HYDROXYPHENYL)ETHANONE

To a solution of commercially available 2-bromophenol (10; 10.0 g, 57.8 mmol) in anhydrous CH2Cl2 (50 mL) in a round-bottom flask were added AcCl (5.0 g, 63.6 mmol) and Et3N (4.67 mL, 63.6 mmol) and the mixture was stirred at r.t. for 1 h. The solvent was evaporated under reduced pressure to give the pure 2′-bromophenylacetate (9; 12.18 g, 56.6 mmol, 98percent). The ester 9 was dissolved in 1, 2-dichlorobenzene (100 mL), then AlCl3 (11.3 g, 84.9 mmol) was added. The mixture was heated and stirred at 140 °C for 3 h. Ice and 10percent HCl were added till the solution was slightly acidic (pH). The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (3 × 50 mL). The combined organic phases were dried (MgSO4) and filtered. The CH2Cl2 was evaporated under vacuum. The crude residue was treated with hexane (300 mL) and cooled at –20 °C when most of the para-substituted by-product 11 crystallized and filtered off. The solution was filtered through silica gel and washed with hexanetill the 1, 2-dichlorobenzene was eluted, then the eluent was changed to CH2Cl2–Et3N (20:1). After chromatography and evaporation of the eluent, the pure product 8 was isolated as a colorless oil; yield: 7.55 g (35.1 mmol, 62percent). IR (ATR): 3008, 2925, 2570, 1643, 1473, 1428, 1364, 1250, 1146, 1071, 968, 836, 775, 738, 627, 595, 523, 437 cm–1. 1H NMR (CDCl3): δ = 12.97 (s, 1 H, OH), 7.73 (m, 2 H, 4-H, 6-H), 6.82 (t, J = 7.9 Hz, 1 H, 5-H), 2.66 (s, 3 H, CH3). 13C NMR (CDCl3): δ = 204.3 (C=O), 158.9 (C-2), 139.6 (C-4), 129.9 (C-6), 120.5 (C-1), 119.6 (C-5), 112.0 (C-3), 26.7 (CH3). MS: m/z = 214 [M+], 216 [M+ + 2, 100percent], 201, 199, 143, 145, 92, 77, 63. Anal. Calcd for C8H7BrO2: C, 44.68; H, 3.28. Found: C, 44.50; H, 3.19.N-Bromosuccinimide (5.25 g, 29.5 mmol) was added at 0° C. to a mixture of 1-(2-hydroxyphenyl)ethanone (4.00 g, 29.5 mmol) and diisopropylamine (0.42 mL, 2.95 mmol) in carbon disulfide (50 mL), and the mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated sodium bicarbonate aqueous solution and water, then dried over magnesium sulfate, filtered, and concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane 0:10-->2:8) to give 1.60 g of the titled compound (yield 25percent).General procedure: Oxone (1.352 g, 2.2 mmol) was added to the well stirred solution of substrate (2 mmol) and NHGeneral procedure: Reaction conditions: Thiourea (5.1 molpercent, 2 mg, 0.026 mmol) was added to an acetonitrile solution (10 mL) containing NBS (1.15 equiv, 104.4 mg, 0.587 mmol). Anisole (56.3 mg, 0.51 mmol) was added immediately to the resulting stirred solution and allowed to stir at room temperature for 10 min. The reaction was quenched by the addition of 10percent aqueous solution of NaN-Bromosuccinimide (5.25 g, 29.5 mmol) was added at 0° C. to a mixture of 1-(2-hydroxyphenyl)ethanone (4.00 g, 29.5 mmol) and diisopropylamine (0.42 mL, 2.95 mmol) in carbon disulfide (50 mL), and the mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated sodium bicarbonate aqueous solution and water, then dried over magnesium sulfate, filtered, and concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane 0:10-->2:8) to give 1.60 g of the titled compound (yield 25percent).

Molecular Weight:215.04
XLogP3:2.5
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:213.96294
Monoisotopic Mass:213.96294
Topological Polar Surface Area:37.3
Heavy Atom Count:11
Complexity:158
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes