3-Bromo-4-methoxybenzaldehyde

WHITE TO BEIGE SOLID

General procedure: 1-Methoxy-3, 5-dimethylbenzene(100mg, 0.73 mmol), N-Bromosuccinimide (NBS, 260 mg, 1.46 mmol) and one ball (5 mmdiameter, stainless steel) were transferred to a milling jar (10 mL, stainlesssteel). The ball-milling operation was performed and the progress of reaction was monitored by TLC/General procedure: 1-Methoxy-3, 5-dimethylbenzene (100mg, 0.73 mmol), N-Bromosuccinimide (NBS, 260 mg, 1.46 mmol) and one ball (5 mmdiameter, stainless steel) were transferred to a milling jar (10 mL, stainlesssteel). The ball-milling operation was performed and the progress of reactionwas monitored by TLC/General procedure: To a reaction tube charged with NBS (1.5 equiv, 0.3 mmol), catalyst (10 molpercent, 0.02 mmol) and CHGeneral procedure: A mixture of arene (0.5 mmol), IGeneral 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 NaGeneral procedure: To a solution of alkoxybenzylalcohol 1 (0.2 mmol) in CF3CH2OH (1 mL) were added LiBr·H2O (0.2 mmol) and PhI(OAc)2 (0.2 mmol) atroom temperature. After completion of the reaction as indicated by TLC monitoring, saturated aq. Na2SO3 wasadded and the mixture was extracted with CH2Cl2. The combined organic layers were washed with brine, driedover anhydrous Na2SO4 and then concentrated in vacuo. The residue was purified by silica gel columnchromatography to afford pure monobrominated compounds 2.To a stirred solution of 4-methoxybenzaldehyde (30.0 g, 220.4 mmol) taken in DOE (300 mL), at 0 00 bromine (38.7 g, 242.2 mmol) was added drop wise. It was heated at 60 00 over night. The reaction mixture was quenched with ice water, and then extracted with ethyl acetate. The organic layer was washed with sodium thiosulphate, water and brine solution, was dried over anhydrous Na2SO4 and concentrated. The product was purified by column chromatography to yield the title product (20.0 g, 42.1percent) as an off white solid.To a stirred solution of 4-methoxybenzaldehyde (30.0 g, 220.4 mmol) was taken inDOE (300 mL), at 0 00 was added bromine (38.7 g, 242.2 mmol) drop wise. It washeated at 60 00 for over night. The reaction mixture was quenched with ice water, and then extracted with ethyl acetate. The organic layer was washed with sodium thiosulphate, water and brine solution, over anhydrous Na2SO4 and concentrated. The product was purified by column chromatography to yield the title product (20.0 g, 42.1percent) as an off white solid.Dimethyl sulfate (6.6 g, 0.053 mol) was added dropwise at a ratethat maintained <0 C reaction temperature to a stirred solution of3-bromo-4-hydroxybenzaldehyde (10 g, 0.05 mol) and anhydrouspotassium carbonate (10.28 g, 0.075 mol) in DMF (40 mL). Uponcompletion of addition, the mixturewas stirred at 25 C for another2 h. The reaction mixture was slowly poured into cold water(100 mL) and stirred for 20 min. The solid was separated byfiltration as a gray powder (9.7 g) in 90.6percent yield, mp 40.1e41.0 C.1H NMR (300 MHz, CDCl3): d 9.84 (s, 1H, CHO), 8.08 (d, 1H, J 2.0 Hz, AreH), 7.80 (dd, 1H, J 2.0 & 8.5 Hz, AreH), 6.98 (d, 1H, J 8.5 Hz, AreH), 3.86 (s, 3H, OCH3).To a solution of dimethyl sulfoxide (6.50 mL, 91.5 mmol) in CH(2) In 4000mL reaction vessel, nitrogen protection, 740.7 g of 3-bromo-4-hydroxybenzaldehyde was put into the reaction vessel.2000 g of N, N-dimethylformamide and558.0g potassium carbonate, Control temperature drop 0 ~ 5 °C drop775g iodomethane, After the control of raw materials is complete, Concentrate the reaction solution into ice water, Precipitation of solids, Recrystallization gave white crystalline product 3-bromo-4-methoxybenzaldehyde 752.7g, yield 95.0percent;General procedure: DBDMH (1 mmol) was added to a mixture of 1b (1 mmol) and dichloromethane (20ml). The reaction was kept at room temperature. After the mixture was stirred for0.5h, the mixture was washed with water (330 ml), dried with anhydrous MgSO4, filtered, and vacuum evaporated. The residue was purified by column chromatography (silica gel: petroleum ether/ethyl acetate, 30:1) to afford the product as light yellowsolid (93percent yield).

Molecular Weight:215.04
XLogP3:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:213.96294
Monoisotopic Mass:213.96294
Topological Polar Surface Area:26.3
Heavy Atom Count:11
Complexity:138
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes