1-Bromo-4-methoxynaphthalene

Oil

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: 1 mL [Bmim]NO3, 0.5 mmolsubstrate and 0.25 mmol Br2 were added to a dried 45 mL tube equipped witha magnetic stirring (note: the air in the tube was not removed). Then thereaction tube was sealed to perform the reaction at 80 C for 24 h. Once thereaction time was reached, the mixture was cooled to room temperature and3 mL water was added. Then the desired product was extracted with CH2Cl2(3 10 mL). GC analysis of the mixture provided the GC yield of the product.The product in another parallel experiment was purified by columnchromatography, and identified by 1H NMR and 13C NMR.The 50 g(316 of 1-methoxynaphthalene and 600 ml of acetonitrile were added to a reaction vessel. 62 g(348 mmol) of N-bromosuccinimide was added under ice-cooled conditions, and the mixture was stirred for 6 hours and then left for one night. 2000 ml of water was added, the organic layer was extracted with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica gel to give product(50.9 g, 215 mmol, 68percent).General procedure: A mixture of substrate (1 mmol), CuBrGeneral procedure: 1mL [Bmim]NOGeneral 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/1H NMR.[1]After completion, the reaction mixture was transferred into 30 mL ethyl acetate and cooled at 0 C. The product was isolated as filtrate upon paper filtration and waste succinimide as precipitate. The resulting filtrate were concentrated in vacuo to isolate 250 mg (yield: 85%) of 2b as colourless powder. To test the efficiency in large scale, the reaction was also performed for the mono-bromination of 1-methoxy-3, 5-dimethylbenzene in 1.3 g scale for 1 h and the product was isolated in 87% yield.[1] The milling apparatus was stopped and small portion of the sample was collected from the reaction jar to study either TLC/ proton NMR. Following, the reaction was started again andthis operation time was excluded for reporting the reaction timing.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/1H NMR.[1]After completion, the reaction mixture was transferred into 30 mL ethyl acetateand cooled at 0 C. The product was isolated as filtrate upon paper filtrationand waste succinimide as precipitate. The resulting filtrate were concentrated in vacuoto isolate 250 mg (yield: 85%) of 2bas colourless powder. To test the efficiency in largescale, the reaction was also performed for the mono-bromination of1-methoxy-3, 5-dimethylbenzene in 1.3 g scale for 1 h and the product wasisolated in 87% yield.[1] Themilling apparatus was stopped and small portion of the sample was collectedfrom the reaction jar to study either TLC/ proton NMR. Following, the reaction was started again andthis operation time was excluded for reporting the reaction timing.General procedure: 1 mL [Bmim]NO3, 0.5 mmolsubstrate and 0.25 mmol Br2 were added to a dried 45 mL tube equipped witha magnetic stirring (note: the air in the tube was not removed). Then thereaction tube was sealed to perform the reaction at 80 C for 24 h. Once thereaction time was reached, the mixture was cooled to room temperature and3 mL water was added. Then the desired product was extracted with CH2Cl2(3 10 mL). GC analysis of the mixture provided the GC yield of the product.The product in another parallel experiment was purified by columnchromatography, and identified by 1H NMR and 13C NMR.The 50 g(316 of 1-methoxynaphthalene and 600 ml of acetonitrile were added to a reaction vessel. 62 g(348 mmol) of N-bromosuccinimide was added under ice-cooled conditions, and the mixture was stirred for 6 hours and then left for one night. 2000 ml of water was added, the organic layer was extracted with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica gel to give product(50.9 g, 215 mmol, 68%).Bromination using NBS has been found to be applicable for use with a wide range of aromatic starting materials or substrates, as is EPO General procedure: A mixture of substrate (1 mmol), CuBr2 (22.4 mg, 10 mol%), LiBr (130.3 mg, 1.5 equiv.), and 0.05 mL of water was placed in a 50 mL stainless steel autoclave equipped with an inner glass tube in room temperature. CO2 (4 MPa) and O2 (1 MPa) were subsequently introduced into the autoclave and the system was heated under the predetermined reaction temperature for 15 min to reach the equilibration. Then the final pressure was adjusted to the desired pressure by introducing the appropriate amount of CO2. The mixture was stirred continuously for the desired reaction time. After cooling, products were diluted with acetone and analyzed by gas chromatograph (Shimadzu GC-2014) equipped with a capillary column (RTX-17 30 m × 25 mum and RTX-wax 30 m × 25 mum) using a flame ionization detector by comparing the retention times of authentic samples. The residue was purified by column chromatography on silica gel (200-300 mesh, eluting with petroleum ether/ethyl acetate from petroleum ether to 50:1) to afford the desired product. The isolated products were further identified with NMR spectra (Bruker 400 MHz) and GC-MS or GCD, which are consistent with those reported in the literature.General procedure: To the solution of anisole (0.50 g, 4.6 mmol), TBAB (0.75 g, 2.3 mmol), KBr (0.83 g, 6.9 mmol), ethyl acetate (3.0 mL) and water (0.050 g, 2.8 mmol) were added and stirred at room temperature. A solution of BTC (1.78 g, 6.0 mmol) in ethyl acetate (6.0 mL) was dropwised to the reaction mixture. After the reaction finished, the reaction mixture was washed with water (10 mL × 2) and evaporated. The product was obtained with 99% purity by HPLC. 1 H NMR (400 MHz, DMSO-d6, ppm): delta 7.46-7.42 (m, 2H), 6.78-6.76 (m, 2H), 3.74 (s, 3H).

Synthetic intermediate.

Molecular Weight:237.09
XLogP3:4.3
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:1
Exact Mass:235.98368
Monoisotopic Mass:235.98368
Topological Polar Surface Area:9.2
Heavy Atom Count:13
Complexity:172
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes