1-Bromo-2-(bromomethyl)-3-nitrobenzene

2-amino-6-bromobenzyl alcohol (intermediate I-1)2-nitro-6-bromo-toluene (32.20 g, 0.20 mol), N-bromosuccinimide (26.6 g, 0.20 mol), and benzoyl peroxide (0.40 g, 2 mmol) were dissolved in chlorobenzene (100 ml), and heated to reflux for about 20 h. The reaction was stopped, and the reaction mixture was filtered to obtain a filtrate. The filtrate was concentrated under vacuum to obtain a light brown oily product, which was recrystallized with ethanol to obtain a yellow solid 2-nitro-6-bromo benzyl bromide (47.31 g, 81percent).2-nitro-6-bromo benzyl bromide (14.70 g, 0.05 mol) and anhydrous sodium acetate(14.7 g, 0.15 mol) were added into N, N-dimethylformamide (70 ml), heated and reacted for about 1 h at 70° C., and cooled to room temperature. The reaction mixture was added into water (150 ml), extracted with ethyl acetate three times, washed with water three times, washed with saturated sodium chloride solution three times, dried by anhydrous sodium sulfate, and filtered. The filtrate was concentrated under vacuum to obtain a white solid 2-nitro-6-bromo phenyl acetic acid methyl ester (12.65 g, 92percent).2-nitro-6-bromo phenyl acetic acid methyl ester (2.73 g, 0.01 mol) was added into the water (100 ml), and 10percent potassium hydroxide solution (20 ml) was added dropwise. The reaction mixture was heated to reflux for 2 h, cooled to room temperature, and extracted with ethyl acetate for three times. The organic phase was combined, washed with water and with saturated sodium chloride solution sequentially, dried by anhydrous sodium sulfate, and filtered. The filtrate was concentrated under vacuum to obtain a yellow solid 2-bromo-6-nitro-benzyl alcohol (1.91 g, 83percent).2-bromo-6-nitro methanol (1.15 g, 5 mmol), sodium sulfide (0.78 g, 10 mmol), and sulfur (0.32 g, 10 mmol) were dissolved in ethanol (50 ml) and water (25 ml), heated to reflux for 2 h, and then cooled to room temperature. The ethanol was evaporated by concentration under vacuum, and the rest of the reaction mixture was added into water (30 ml), and extracted with ether three times. The organic phase was combined, washed with water and with saturated sodium chloride solution sequentially, dried by anhydrous sodium sulfate, and filtered. The filtrate was concentrated under vacuum to obtain a yellow solid 2-bromo-6-amino-benzyl alcohol (0.78 g, 78percent), [M+H]2-nitro-6-bromo-toluene (32.20 g, 0.20 mol), N-bromosuccinimide (26.6 g, 0.20 mol), and benzoyl peroxide (0.40 g, 2 mmol) were dissolved in chlorobenzene (100 ml), and heated to reflux for about 20 h. A solution of 1-bromo-2-methyl-3-nitro-benzene (16.095g, 74.5 mmol), 1-Bromo- pyrrolidine-2, 5-dione (13.26 g, 74.5 mmol), benzoyl peroxide (180 mg, 0.74 mmol) in CC14 (100 ml) was heated under reflux overnight. After removing the solvent by using rotary evaporator, the residue was partitioned between water and ethyl acetate. The organic layer was washed with water and brine. After drying over MgS04, the organic fraction was concentrated in vacuo and resulting brown residue was purified by flash chromatography to give 1-bromo-2-bromomethyl-3-nitro-benzene as a yellow solid (17.55g, 80percent). 1H NMR (CDCl3, 300MHz) 8 : 4. 89 (s, 2H), 7.35 (dd, 1H, J1=J2 = 8. 1Hz), 7.88 (dd, 2H, J1 = 1. 6Hz, J2=8. lHz).To a solution of 1-bromo-2-methyl-3-nitrobenzene (3.0 g, 13.89 mmol)in CC14 (20 mL)5 was added NBS (2.47 g, 13.89 mmol)and BPO (336 mg, 1.39 mmol). The reaction mixture washeated to 80 oc for 12 h. After cooling the reaction to room temperature, the mixture wasconcentrated in vacuo. EtOAc (20 mL)was added, washed with water (20 mL x 2)and brine (20mL). The organic layer was dried over anhydrous Na2S04, filtered and concentrated in vacuo.The crude residue was purified by silica gel column chromatography (petroleum ether/EtOAc =10 4:1)to give the title compound (3.2 g, 78percent)as a yellow solido a solution of 2-bromo-6-nitrotoluene (21.6 g, 100.0 mmol) at room temperatureAdd NBS (17.8 g, 100.0 mmol) to a solution of BPO (2.4 g, 10.0 mmol) in 30 mL CH3CN.The reaction mixture was stirred at room temperature for 4 h, and after TLC showed that the starting material was completely reacted, The reaction was quenched with water, extracted with EA (30 mL×3), and the organic phase was backwashed with saturated brine.The Na2SO4 was sufficiently dried and evaporated to dryness by column chromatography (PE/EA=10/1)Purification afforded 24.0 g of title compound as a yellow solid.To a solution ofmethanamine in THF (2.0 M, 50 mL, 100 mmol)was added

Molecular Weight:294.93
XLogP3:3
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:294.86665
Monoisotopic Mass:292.86870
Topological Polar Surface Area:45.8
Heavy Atom Count:12
Complexity:171
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes